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In a tournament which is seeing the lower teams really step up against the big guns, Argentina's clash with Switzerland proved to be no different. Switzerland lost 1-0 to the South American team, but managed to take the opposition, which possesses one of the most quality attacks in the world at the moment, into the dying embers of the extra minutes.
One of the more dull matches of the tournament saw a very exciting finish as Di Maria's goal was scored in the 118th minute, just moments away from the whistles taking the two teams into a penalty shootout.
In the stoppage time of the extra time, Switzerland midfielder Blermin Dzemaili thundered a header against the post from a cross; Switzerland came that close to taking the Lionel Messi led side to the penalty shootout. Ottmar Hitzfeld will unfortunately end his legendary managerial career on this note.
Argentina Raise Doubts As Potential World Champions
A 1-0 win against Switzerland only raises already present questions of why Argentina is not winning more convincingly. The team won against Bosnia 2-1, where one of the goals for the Latin American side was an own goal. The win against a low seeded Iran was probably the most unconvincing one there has been, as Argentina only got points because of some Messi-brilliance in the stoppage time. They won the match 1-0, but didn't look like potential world champions, at all. The win against Nigeria was also not as compelling as it should have been as the South Americans got a winner through Marcos Rojo and went back with a 3-2 scoreline and the three points. However, it did make for a fantastic, evenly-contested match.
It was again Messi who rescued his team this time. It was he who set up di Maria's goal; it was his drive and refusal to give up that eventually saved Argentina the blushes of a penalty shootout, and a possible unwarranted exit.
Argentina set about in a somewhat 4-2-3-1 formation and initially struggled to find space which was because of Switzerland's brilliant organization defensively. In the second half, the South Americans started looking more comfortable as they started finding space in the tight Swiss defence. Lavezzi and Di María started leaving their flanks and foraging through the middle. The chances started coming steadily.
Argentina attempted 29 shots and got one goal in the 118th minute, which speaks two things – wasteful chances, brilliant defensive organization on part of the Swiss. Gonzalo Higuain was his side's worst player on the field. He was hardly visible in the first half. In the second half, he started trying harder. Two headers were planted by him around the hour mark – the former requiring a great save by Diego Benaglio to tip over the bar, and the latter being driven straight at him, an attempt the Napoli striker wouldn't be proud of.
Lavezzi regularly came up-front and tried to be the unlikely scorer. He attempted a couple of shots but looked highly ineffective and provided no sort of threat to Switzerland. Eventually he was substituted by Rodrigo Palacio who provided far more mobility in the game. He was also, however, guilty of a wasteful attempt as he failed to convert from a delicious scooped cross sent in by his captain.
Di Maria was also very ineffective for most parts of the game. The Real Madrid player was regarded as the second most important player for the Argentines but has not done anything menacing in the tournament so far. Capable of swapping positions, the player's runs through the middle were undamaging. He completed 2 of the 12 he attempted – an embarrassing tally for any player but an unexpected one from him.
A player of his caliber could not miss the chance Messi created for him for the goal, and at least he didn't disappoint there. However, a lot has to be said about his perseverance – he kept running and trying to make things happen (even if they didn't) and he refused to be complacent. Just for his persistence, the goal seemed like an apt reward.
Javier Mascherano and Fernando Gago provided little drive or dynamism in the heart of the pitch and didn't help their side create more pressure on the Europeans.
The defence of Argentina was not troubled much later on, with the battle mostly happening in the midfield, but initially, Argentina's ability to recover the ball was not good. Switzerland could launch counter attacks in the first half, and the Argentinean defensive duo – Mascherano and Gago – were not able to deal with these easily. The defenders were also not fast in coping with these counters and this lack of speed and coverage at the back can prove to be a huge problem when they take on Belgium in the quarter final, a side with a deadlier attack.
The Big Question
How is it that the attack of Argentina is not doing more damage than this? When Portugal crashed out of the tournament embarrassingly, it was pointed out that Portugal is over-reliant on Cristiano Ronaldo. Argentina, au contraire, has a clinical striker who scored nine times as Argentina topped the South American section, with only Messi and Suarez netting more, in Higuain; a world-class versatile winger in Angel di Maria and a player who can be employed in various attacking positions, in Lavezzi. Add to that the talents of players who can chip in from the bench in the forms of Palacio, Perez and Rodriguez. For a team that possesses an attack of this quality, they are curiously reliant on just one man – Messi.
The question is now whether they really can go all the way to the Maracana while dependent on one man – because from the way things are panning out, there probably isn't another way for Argentina.
Switzerland give in all they have
The Swiss would certainly return home proud of their efforts. Even though Shaqiri was the centre of almost all of Switzerland's attacks, Ottmar Hitzfeld's Switzerland are definitely reliant more on well-drilled teamwork, than on individual lustre. But it was still the Bayern Munich player who shone for the Swiss, in most stages. Nicknamed the 'Alpine Messi', it was Shaqiri who delivered his side's best moments. He was the best player on the pitch in the first half and created numerous chances for his side. Unfortunately, if the Swiss had only been able to finish what they started, they would probably not be heading home just now. Two times Shaqiri set up Drmic, both times Drmic failed to capitalize. The first one was a beautiful diagonal ball from the deep that sent Drmic running towards goal with only goalkeeper Sergio Romero to beat. Shockingly, he decided to chip the standing goalkeeper. Romero gladly collected the ball, which he received at waist-height and Switzerland's best chance was wasted. But the Bayern Munich player's influence wore-off towards the end of the match as Switzerland mostly dealt with Argentinean attack during the period.
Otmar Hitzfeld had hinted at a plan to keep Messi quiet in the game. He said, "How to stop Messi? We'll show you tomorrow how we do it". His plan worked well in the first half as Valon Behrami, Gokhan Inler and Granit Xhaka – the midfielders – were entrusted with the responsibility of keeping Messi quiet. They were asked to cut the supply and they executed it perfectly for most parts of the game. They didn't let Messi have a lot of space; when the Argentinian captain got the ball, he was surrounded by a pack of Red shirts. But after about sixty minutes, the plan was not able to come off. Containing the genius became more difficult and Messi started getting more space and began to exploit any loose gaps he found.
12 of the 29 shots attempted by Sabella's side were blocked and the Swiss defence deserves much credit for it. Johan Djourou was terrific at the heart of the Swiss defence. He stood tall and did not panic when Messi, Di Maria and Lavezzi made advancing runs. He did not give away any cheap possession and his composure in front of the goal was commanding. Fabian Schär's work was heavily cut out because of Djourou. The Swiss left back Ricardo Rodriguez also enjoyed a good day in the office – he was firm defensively, and made offensive surges. However, the 21 year old has to improve the offensive side of his game, but his performance deserves a lot of praise and the Swiss surely have a solid player for the future.
Switzerland almost managed to take the game to penalties which is immense credit to them but they might feel that they did a little bit of self-damage, as they were unsuccessful in eventually doing so. It was Swiss full back Stephan Lichtsteiner who initially lost possession in midfield, allowing Messi the opportunity to set up the Real Madrid winger for the winner (Lichtsteiner has admitted his fault in the goal). Minutes later, as the match was seconds away from the final whistle, Dzemaili hit the post with his header and squandered the rebound wide.
Switzerland have a lot of positives to take from the tournament, but they have a lot to work on as well – their counter attacks were slow, almost all of the chances were being created by one man and there was absolutely no finish – the majority of the shots were off target and the ones on the money were too easy for Romero. They were the lesser of the two sides in the end, but eventually would be proud of their effort.
Farewell Hitzfeld
One of the most successful managers, Hitzfeld bid farewell to the game. He has guided both Borussia Dortmund and Bayern Munich to victory in the Champions League and said emotionally that he felt "pride" at what Switzerland had achieved in the World Cup. 'Der General' leaves the game a hero, even though Switzerland couldn't progress further.
Man of the Match: Diego Benaglio
Benaglio plays for German side Wolfsberg and showed exactly why he is rated so highly in Germany. He saved numerous shots from di Maria, Palacio, Higuain and Messi. After suffering one embarrassing defeat to France, where Benaglio and the Swiss defenders would have to share the blame, the 30 year old, with the help of his defence, made sure Argentina didn't embarrass his side. He kept up his good work for most parts of the match and eventually there was nothing he could do to keep di Maria's crackling goal out.


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Remember On Thanksgiving
Friends and Family let us gather here,
To share this day's Thanksgiving cheer,
Set aside all petty fights,
And let us be grateful on this night.
For many have no cheer to share,
No friends and family to love and care,
They sit alone in sad and gloom,
In prison walls and whitewashed room.
You have your family and freedom now,
But there are those who know not how,
To smile and be with good glee,
When prison guards are all they see.
You may not know how much you own,
With family and what you call home,
With turkey brown and smelling fine,
When others have much less then grime.
Warm clothes and gloves you have to keep,
While some have not blankets to sleep,|
You wish and want without a thought,
Of what to give and what is wrought.
Now stop and think of those alone,
Who have little food and are not home,
Whose sadness grows when holidays are here,
Please pray to bring some comfort there.
You know not what you have from day to day,
Until at last its torn away,
And then you'll wish for some to pray,
For you on this Thanksgiving day!

subset: commoncrawl


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Alumni Program
Upon successful completion of treatment, clients are encouraged to participate in alumni activities. The open-ended alumni group meets once a month at the Lifeskills South Florida clinical offices. The group offers ongoing support for individuals post discharge. Many strong bonds and connections are made through participation in alumni activities. In addition to having a monthly meeting, there are social events held throughout the year. Many alumni continue to participate in alumni activities for months and years post discharge.


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Miramar Hotel Bangkok
Miramar Hotel Bangkok Rates and Deals
Miramar Hotel Bangkok Reviews
11 reviews
Hotel for stay in bkk May 30, 2012
Hotel is far from kaosan so you need walk about 20 min. If you wanna go by taxi you need pay about 50 baht but price changeable. Hotel clean and laundry service very good. Hotel has wifi connection but its with charge and very expensive. I dont suggestion wifi service. Hotel is new so you need hotel card for recipe hotel taxi driver. Hotel has massage service if you want you can use but i didnt try. Hotel area is not many people at night time so if you want to turn back hotel by walk it can be dangereous. I dont suggest this hotel for travellers.
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2 reviews
Jan 22, 2007
if you're looking for a clean, quiet, comfortable, inexpensive and safe place to spend a few days in the Nakhon Kasem area of Bangkok, I would recommend this place. The hotel is also within a short taxi or tuk tuk ride to the Hualampong train station. Not very far from here are Bangkok's Chinatown and The Thieves Market - an underground labyrinth where merchants sell products of every description. In Bangkok's "bad old days" this was one of the places where smugglers would unload their merchandise. The Thieves Market is not for the claustrophobic. ;-) The hotel is just up the street from a little park (the former location of a prison) where local Thais like to meditate, relax and take their exercise. The antique Chinese clocks on every floor of this hotel are a nice touch.
Miramar Hotel Bangkok Overview
The Miramar Hotel Bangkok is located in Bangkok's Phra Nakhon, a short walk from The Old Siam Plaza. Bangkok city centre is within a short 10 minute drive from the hotel.
The Miramar Hotel Bangkok employees are available 24-hours a day and can assist with booking tours and tickets. The hotel operates a well-equipped business centre and offers conference facilities. Amenities offered include meeting rooms, babysitting / child services and a concierge. For an easy and effortless check-in and departure experience, take advantage of the Miramar Hotel Bangkok's express check-in/check-out feature which minimises the usual hassles leaving you with more time to enjoy your trip.
All rooms feature a private bathroom including a bathrobe and amenities. Each room at the hotel has a TV, a safe and cable / satellite channels. Guests have the option of choosing a non-smoking room. Equipped to ensure a comfortable stay, rooms offer a DVD player, a mini bar and tea and coffee making facilities.
Travellers wishing to socialise can take advantage of the Miramar Hotel Bangkok's bar, located on-site for your convenience. Guests can order room service 24 hours a day.
Miramar Hotel Amenities


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Just finished vetting three new tapes (2 NPN's and 1 REO's). Will be posting the information on each tape here and on my Facebook page tomorrow for your consideration. I can tell you these are great deals and will go fast.
Stay tuned.........................
Mark Bogan
Boamar Investments
Show email
Posted 11/19/15


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On April 11, 2016, Prof. Geoffrey Cowan hosted the annual Master in Public Diplomacy reception for current students and special guests. The guests shared their experiences in public diplomacy and engaged in small-group discussions with the students about the global role of Los Angeles, possible careers, and overcoming hardship and discrimination.
Special Guests:
Anita DeFrantz was the first American woman and first African American to serve on the International Olympic Committee in 1986. She won a Bronze medal in rowing at the 1976 Games in Montreal. Ms. DeFrantz also served on the Board of the U.S. Olympic Committee (USOC) from 1976 to 1984, on the staff of the Los Angeles Olympic Organizing Committee in 1981, and will continue to serve as a member of the USOC Board of Directors until her term ends in 2032. She served as president of the LA84 Foundation from 1987 to 2015.
David Huebner is a partner at Arnold & Porter, where he is an arbitrator in international disputes. Previously, he was President Obama's Ambassador to New Zealand and to Samoa from 2009 to 2014. He was known for his whole-of-society outreach, social media work, and efforts in youth engagement. He was also the first openly gay ambassador in the Obama administration and the third such in U.S. history. He is a Fellow of the Chartered Institute of Arbitrators and has a distinguished international legal career.
Vilma Martinez is president of the Los Angeles Harbor Commission. From 2009 to 2013, she served as U.S. Ambassador to Argentina under the Obama Administration. She has had a distinguished legal career in civil rights, having served as President and General Counsel of the Mexican American Legal Defense and Education Fund from 1973 to 1982 and as litigator and partner at Munger Tolles & Olson in Los Angeles from 1982 to 2009. Currently, in addition to her work at the Los Angeles Harbor Commission, she serves on the Boards of the Pacific Council on International Policy and The LBJ Foundation in Austin, TX.
Photo // Skye Featherstone


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Philippe Bibi has been named senior managing director and chief technology officer of Putnam Investments. Previously, Bibi served as managing director and head of investments and technology at Enron Corp. in Houston.
Richard Horlick has been appointed president of Fidelity Management Trust Company. Horlick was promoted from Fidelity International Limited in London where he was president of the international institutional business.
Scott Sipple, John Gagliano, and Catherine Wood have joined the management team of Regent Investor Services, a division of Alliance Capital. Sipple, currently a senior VP responsible for global mutual fund product management at Alliance, will become Regent's managing director. Gagliano, a regional sales manager for the broker dealer division of Alliance's mutual fund business, will become Regent's national sales manager. And Wood, who is senior vice president and portfolio manager at Alliance, will retain those responsibilities in addition to that of chief investment officer at regent.
Richard Talley has been named VP of global alternative investments of PFPC in Wilmington, Del. Talley was most recently VP, sales and marketing, for LIVETRADE.com in Garden City, N.Y. Gerald Winchester has also joined PFPC as VP of new business development. Previously, Winchester was manager of strategic business development for Q.E.D Information Systems in Marlton, N.J.
Denis Bovin has joined the board of directors at BISYS of Little Falls, N.J. Bovin is vice chairman of investment banking and senior managing director of Bear Stearns & Co.


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Smart Office Standards: BREEAM
Some organizations have designed standards by which to measure a building's health and efficiency ratings. These ratings focus on the health of the building itself as well as the building's local and global impacts.
Britain's BREEAM program — "BREEAM" stands for Building Research Establishment Environmental Assessment Method"–was established to assess indoor environmental quality and covers a wide range of buildings, from superstores and supermarkets to new and existing offices.
BREEAM is a voluntary program that allows building owners and occupants to find out about their impacts on a variety of environmental factors, including ozone depletion, global warming, and the destruction of rainforests and other resources. It also illuminates a number of other building issues, from noise and air pollution to lighting and hazardous materials. For more information on BREEAM, click here.
Adapted from The Smart Office, by A.K.Townsend.Copyright (c) 1997 by A.K.Townsend .Reprinted by permission of Chelsea Green Publishing Company.
Adapted from The Smart Office, by A.K.Townsend.


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There's never a lot of TV coverage of spring training games but I have the gut feeling that there are less planned this year. Maybe it's just because I WANT to see live VIDEO more this year tha I have in the past so I'm feeling the lack more strongly. But since we are almost all stuck to whatever radio coverage we have for every spring training game, I tend to never be very far from my radio. This has also contributed to a significant level of discussion about the various radio affiliates throughout Twins Territory that I thought I would publish the information that the Twins have out. It can be surprising for even people that live in various areas outside of the twin cities when they hear that it's possible they could be getting these games on the radio.
So here's the connection for those of you without Cable/Satellite access during the season or without MLB.tv during spring training.
Treasure Island Baseball Network Map
I do think it would be kind of nice if we couldn't start making better in-roads into Iowa. I wonder how we would go about that….


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|Sun Java Enterprise System 2004Q2 Deployment Example Series: Evaluation Scenario
Chapter 1
Evaluation Scenario Overview
This chapter describes the goals of the evaluation deployment, explains the architecture used in the evaluation deployment, and summarizes the procedures that are contained in this document for installing, configuring, and using the evaluation deployment.
This chapter contains the following sections:
About Java Enterprise System
Sun Java Enterprise System (Java ES) is infrastructure software that supports a wide range of enterprise computing needs, such as creating a secure intranet portal that provides the employees of an enterprise with secure access to email, calendar, and in-house business applications.
Java ES provides many end-user services without custom programming, and it also supports custom, distributed, enterprise applications.
Java ES is composed of software components, such as Sun Java System Directory Server and Identity Server. To meet the computing needs of different enterprises, Java ES components can be combined in many different ways.
Each enterprise assesses its own needs and plans its own deployment of Java ES components. The optimal deployment for an enterprise depends on the Java ES services that are needed, the number of users that must be served, the kind of hardware that is available, and similar considerations.
For more information on Java ES technical concepts and terminology see Java Enterprise System Technical Overview (http://docs.sun.com/doc/817-5764). For more information on planning a Java ES deployment, see Java Enterprise System Deployment Planning White Paper (http://docs.sun.com/doc/817-5759).
Goals of the Evaluation
This document describes how to install a basic set of Java ES components and configure them to provide networked messaging, calendar, and portal services without any custom application programming. This document also describes how to set up LDAP user accounts so you can access these services through their web-based interfaces.
The set of components you install for evaluation also supports single sign-on and proxy authentication, so that you can evaluate these Java ES features. This document describes how to configure these features.
By following the procedures in this document, you learn how Java ES components provide core, shared, networked services for an organization's employees and customers. You learn how to access these core services through built-in, web-based interfaces. You also learn enough about the capabilities of Java ES to imagine how a Java ES deployment could deliver services to your organization's employees and customers.
About the Evaluation Deployment
The evaluation deployment uses a set of Java ES components that provide portal, messaging, and calendar services. This section describes how the deployment architecture for the evaluation deployment was developed. It follows the deployment planning methodology described in Java Enterprise System Deployment Planning White Paper.
Evaluation Use Cases
The first stage of the deployment planning methodology is developing a set of use cases that describe the desired behavior of the Java ES deployment. The evaluation deployment is designed to demonstrate some basic Java ES features. It supports the following use cases:
- Installer use case: install the Java Enterprise System components on one system.
- Component configuration use case: use Java Enterprise System administrative interfaces to configure component instances.
- Administrator use case: configure the evaluation organization's directory tree and provision a single end user.
- End user use case: use the mail, calendar, and portal services.
- Administrator use case: configure Identity Server single sign-on (SSO).
- End user use case: use single sign-on to access the mail, calender, and portal services.
- Administrator use case: configure proxy authentication.
- End user use case: use the portal desktop to interact with the mail and calendar services to demonstrate successful configuration of proxy authentication.
This document shows you how to set up a working Java Enterprise System that implements these use cases.
Evaluation Deployment Scenario
The second step in the deployment planning methodology is developing a deployment scenario. A deployment scenario identifies the Java Enterprise System components that are needed to implement the use cases. This section describes the deployment scenario developed for the evaluation use cases listed in Evaluation Use Cases.
A deployment scenario consists of two pieces, a logical architecture and a set of system requirements.
Logical Architecture
The logical architecture identifies the Java Enterprise System components that provide the services described in the evaluation use cases. The logical architecture for the evaluation use cases is illustrated in Figure 1-1.
Figure 1-1 Evaluation Deployment Logical Architecture
Figure 1-1 shows the logical architecture that implements the evaluation use cases. The components are shown in several tiers. The tiers show how the components could be distributed in a networked, production deployment.
For the purposes of the evaluation deployment, the significant features of Figure 1-1 are the following:
- The components that provide the services for the evaluation deployment are Portal Server, Communications Express, Messaging Server, Identity Server, Calendar Server, and Directory Server. Web Server is included in the deployment to provide web container support for Portal Server and Identity Server. (Messaging Server and Calendar Server have their own web containers.)
- Evaluation end users access mail, calendar, and portal services through built-in web interfaces. This is represented by the web browser clients that appear at the far left.
- The multi-tiered architecture makes it possible to configure other user interfaces, such as stand-alone mail clients, for use with Java ES services. For more information on Java ES architecture, see Java Enterprise System Technical Overview (http://docs.sun.com/doc/817-5764).
- Directory Server provides directory services that support all of the other components.
System Requirements
A logical architecture identifies the Java ES components that provide the services described in the use cases. A logical architecture does not tell you how the components are installed on your network. In a typical production deployment, multiple instances of the components are distributed among several hardware systems, in order to achieve desired levels of response time, service availability, service reliability, and so on.
To determine this level of detail for your deployment, you analyze your business needs and develop a set of system requirements. The system requirements specify important characteristics of the deployment, such as the number of users that must be supported, the response time that your users must experience, and the amount of down time that is permitted.
You apply the system requirements to the logical architecture, and you determine what kind of distribution of the Java ES components is needed to support your system requirements and what kind of hardware is necessary to run the distributed deployment. For more information on these aspects of a planning a Java ES deployment, see Java Enterprise System Deployment Planning White Paper (http://docs.sun.com/doc/817-5759)
The evaluation deployment described in this document only needs to support a handful of users, and there is no need for continuous availability or the other features of a production deployment. Therefore, the system requirements for the evaluation deployment are minimal. These requirements are listed below:
Evaluation Deployment Architecture
You apply the system requirements to the logical architecture, and you determine what kind of hardware is needed to support your user base at the desired levels of availability and performance. This is expressed in a deployment architecture.
The evaluation deployment's minimal system requirements are easily satisfied by installing the components that appear in the logical architecture on one system. The rest of this document describes how to install, configure, and use the evaluation deployment on one system.
Evaluation Procedure Summary
This section summarizes the procedures that appear in this document for installing, configuring, and using the Java ES evaluation deployment. The procedures are summarized in Table 1-1.
Table 1-1 Summary of Evaluation Procedures
For Instructions
Implement the evaluation deployment architecture.
Use the Java Enterprise System installer to install the components that are included in the deployment architecture.
The installer configures most of the components.
Configure the components not configured by the installer and start all of the components.
Use the individual component configuration tools.
This includes configuring the evaluation deployment's LDAP directory tree.
Chapter 3, "Configuring and Verifying the Evaluation Deployment."
Further configure the evaluation deployment's LDAP directory tree, for messaging, calendar and portal services.
Use the User Management Utility and the Identity Server console.
Create a Java Enterprise System end user and provision the user for messaging, calendar, and portal services.
Use the User Management Utility and the Identity Server console.
Log in to and use the portal desktop, the messaging service, and the calendar services.
Use the web-based interfaces to these services.
Chapter 5, "Using the Portal, Messaging, and Calendar Services."
Configure Identity Server single sign-on (SSO).
Use the configuration tools.
Use the SSO feature to access the portal, messaging, and calendar services.
Single sign-on allows you to sign on once and access all of your services.
Configure proxy authentication.
Proxy authentication allows the portal desktop direct access to the messaging and calendar services.
Use the proxy authentication feature.
Open the mail and calendar tools from the portal desktop.
These procedures begin in Chapter 2, "Installing the Evaluation Deployment."


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Ok so I vote BLUE! ( although secretly Pink is my fave!)
Originally Posted by ColoradoBride11
Thank you! They are aqua and coral
So do my bridesmaids!
Thank you!
2 for hot pink!
3 for hot pink! This is gonna be tough! I found all 3 pairs on Zappos.com -- in my opinion the best shoe website, you can search by style and color and size... and the prices aren't bad either! They are RSVP - Lovely - http://www.zappos.co...st=prodPage2a:0


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U.S. Senate Republican Leader Mitch McConnell made the following remarks on the Senate floor today regarding the status of the fiscal cliff negotiations:
"My office submitted an offer to the majority leader last night at 7:10 pm and offered to work through the night to find common ground. The majority leader's staff informed us they would be getting back to us this morning at 10 a.m.-- despite our obvious time crunch. It's now 2 p.m. and we've yet to receive a response to our good-faith offer.
"I'm concerned with the lack of urgency here. There's far too much at stake for political gamesmanship.
"We need to protect American families and businesses from this looming tax hike. Everyone agrees that action is necessary.
"In order to get things moving, I have just spoken with Sen. Reid. I also placed a call to the Vice President to see if he could help jump start the negotiations on their side. The Vice President and I have worked together on solutions before and I believe we can again.
"I want my colleagues to know that we'll keep everyone updated.
"The consequences of this are too high for the American people to be engaged in a political messaging campaign. I'm interested in a result here. And I'm willing to work with whomever can help.
"There is no single issue that remains an impossible sticking point - the sticking point appears to be a willingness, an interest, or courage to close the deal.
"I'm willing to get this done but I need a dance partner."
Source: http://www.mcconnell.senate.gov/public/index.cfm?p=PressReleases&ContentRecord_id=cdceca38-cf72-4725-ae2c-e95b21948207&ContentType_id=c19bc7a5-2bb9-4a73-b2ab-3c1b5191a72b&Group_id=0fd6ddca-6a05-4b26-8710-a0b7b59a8f1f


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Clifford Chance's Paris office has landed the former head of staff to France's ministry of justice as of counsel.
On joining the magic circle firm Patrick Hubert will work closely with its anti-trust, public law and environmental practices. Hubert has enjoyed a long and illustrious career within the French government including terms as deputy and then head of staff to the ministry of justice.
He has also held the post of rapporteur general (general counsel) at the French anti-trust regulatory authority.


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Oh, how fast optimism dissipates, how quickly hope sinks after a bad defeat – and the Washington Huskies' 34-14 stinker at Stanford was, plain and simple, a rude reality check.
Blame can be painted in every corner:
• Like quarterback Jake Locker, who wasn't nearly as efficient as he was in the first game. The early interception was his fault – he threw into double coverage. The second one was a miscue off a broken play, and debatable.
• Or how about the special-team corps, in general. Inexplicably, Erik Folk booted the kickoff in the opposite direction to start the game, and the Huskies paid on Chris Owusu's 91-return for a touchdown. Or bad decisions by Johri Fogerson or Jordan Polk on the UW's returns on kickoffs.
• And there's the issue of 321 Stanford rushing yards. UW defensive coordinator Nick Holt indicated that his defensive tackles need to get tougher on the interior. Shoddy tackling seemed to be a defense-wide plague. And again, linebacker E.J. Savannah was on the sideline, this time with a foot injury.
All of these are genuine concerns as a 2-2 UW squad heads to Notre Dame this weekend.
Today, I want to address offensive personnel. Today, I ask as the Huskies prepare for another road trip, what exactly is receiver Jordan Polk giving this offense?
Polk, the 5-foot-8, 162-pound sophomore from Portland, had a super preseason camp – enough that the UW staff awarded him a starting position opposite James Johnson (and the duo is often paired up together in coach Steve Sarkisian's personnel groupings).
Polk is a tough, shifty runner in open space, with the ability to break off a long-gainer at any time. It's for that reason he is also a kick returner.
And, Polk can be utilized at any time on end-arounds, or "fly" sweeps, just to give a defense that element to think about during a game.
Thing is, for all that he can do – for all that he's a threat to prepare for, which I understand is a big plus in football – is he truly a weapon or an overskilled decoy?
I broke down all the receiving snaps through four games. Here is how that shakes out (of course, unofficially):
Wide Receiver Plays from Scrimmage
James Johnson, 185.
Jermaine Kearse, 116.
Devin Aguilar, 115.
Jordan Polk, 111.
D'Andre Goodwin, 104.
Wide Receiver Average Plays Per Game
JJ, 46.3 per game.
Aguilar, 38.3 per game.
Kearse, 29.0 per game.
Polk, 27.7 per game.
Goodwin, 26.0 per game.
Wide Receiver Production
JJ – 19 receptions, 220 yards, two TDs.
Kearse – 11 receptions, 128 yards, TD.
Goodwin – eight receptions, 155 yards.
Aguilar – seven receptions, 107 yards.
Polk – two receptions, 20 yards.
Polk has touched the ball three times – twice on catches, and one on a reverse against Louisiana State. He's been targeted, by my count, eight other times on pass plays by Locker.
In the past two games against USC and Stanford, Polk hasn't caught a pass.
Question is, if you were a defensive coordinator, would Polk – who occupies a great deal of snaps in the receiver rotation – be somebody you would seriously game-plan for?
One of the emerging entities in Sarkisian's two-running back sets is Chris Polk's pass-catching on the edge. In essence, this tailback-Polk can do what that receiver-Polk can in open space, only with more power behind it.
This isn't a rage against Jordan Polk, rather it's reason to question how often, or in what manner the coaching staff is utilizing him, especially when it might be taking away playing time from more productive players in the passing game.


text:
Patent application title: OPTOELECTRONIC DEVICES EMPLOYING PLASMON INDUCED CURRENTS
Dawn Bonnell (West Chester, PA, US)
Parag Banerjee (Creve Coeur, MO, US)
David Conklin (Wappingers Falls, NY, US)
Sanjini Nanayakkara (Denver, CO, US)
IPC8 Class: AH01L5146FI
USPC Class:
257 21
Class name: Quantum well superlattice light responsive structure
Publication date: 2012-11-08
Patent application number: 20120280209
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An electro-optical device includes a substrate on which first and second
electrodes are formed. A plurality of nanoparticles are arrayed on the
surface of the substrate between the first and second electrodes. The
arrayed nanoparticles exhibit plasmonic activity in at least one
wavelength band. A plurality of linking molecules are coupled between
respective adjacent ones of the nanoparticles and between each of the
electrodes and nanoparticles that are adjacent to the electrodes. The
linking molecules are selected to exhibit photo-activity that is
complementary to the arrayed nanoparticles.
1. An electro-optical device comprising: a substrate; first and second
electrodes formed on the substrate; a plurality of nanoparticles on the
surface of the substrate between the first and second electrodes wherein
the plurality of nanoparticles exhibit plasmonic activity in at least one
wavelength band; and a plurality of linking molecules electrically
coupled between respective adjacent ones of the plurality of
nanoparticles, between the first electrode and ones of the plurality of
nanoparticles adjacent to the first electrode and between the second
electrode and ones of the plurality of nanoparticles adjacent to the
second electrode, the plurality of linking molecules exhibiting
photo-activity that is complementary to the plasmonic activity exhibited
by the plurality of nanoparticles.
2. An electro-optical device according to claim 1, wherein the nanoparticles are metallic nanoparticles comprising at least one metal selected from the group consisting of copper, aluminum, silver, gold, lead and platinum.
3. An electro-optical device according to claim 1, wherein the linking molecules are conjugated molecules comprised of at least one chromophore and at least two end groups bonded to atoms on surfaces of the nanoparticles.
4. An electro-optical device according to claim 1, wherein the plurality of linking molecules exhibit photo-activity in a wavelength band that overlaps the at least one wavelength band in which the plurality of nanoparticles exhibit plasmonic activity.
5. An electro-optical device according to claim 4, wherein the wavelength band in which the plurality of nanoparticles exhibit plasmonic activity is narrower than the wavelength band in which the linking molecules exhibit photo-activity.
6. An electro-optical device according to claim 4, wherein the photo-activity exhibited by the linking molecules is absorption of photons and the plasmonic activity of the plurality of nanoparticles tends to enhance photon absorption in the linking molecules.
7. An electro-optical device according to claim 1, wherein the plurality of linking molecules exhibit less photo-activity in the wavelength band that overlaps the at least one wavelength band in which the plurality of nanoparticles exhibit plasmonic activity than in an other wavelength band that does not overlap the at least one wavelength band in which the plurality of nanoparticles exhibit plasmonic activity.
8. An electro-optical device according to claim 7, wherein the wavelength band corresponds to one of red or green light and the other wavelength band corresponds to blue light.
9. An electro-optical device according to claim 1, wherein the plurality of nanoparticles are arrayed on the substrate with random separations.
10. An electro-optical device according to claim 9, wherein: the average separation between adjacent nanoparticles is a distance d; the wavelength band in which plasmonic activity is exhibited by the arrayed nanoparticles is related to the distance d; and the photo-activity exhibited by the linking molecules is in a wavelength band substantially co-extensive with the wavelength band in which the plasmonic activity is exhibited by the arrayed nanoparticles.
11. An electro-optical device according to claim 9, wherein the arrayed nanoparticles are separated by different distances such that the arrayed nanoparticles exhibit plasmonic activity in at least two wavelength bands.
12. An electro-optical device according to claim 11, wherein the plurality of nanoparticles include nanoparticles of different sizes.
13. An electro-optical device according to claim 12, wherein the plurality of nanoparticles include nanoparticles of different shapes.
14. An electro-optical device according to claim 1, wherein the plurality of nanoparticles include nanoparticles of different sizes.
15. An electro-optical device according to claim 1, wherein the linking molecules include multiple different linking molecules which exhibit photo -activity in multiple wavelength bands.
16. An electro-optical device according to claim 1, wherein at least a portion of the linking molecules are conjugated molecules comprised of at least one conjugated macrocycle.
17. An electro-optical device according to claim 1, wherein at least a portion of the linking molecules have a structure EG1-Cn1-[-MC-Cn2-]n-EG2 wherein EG1 and EG2 are the same or different and are functional groups capable of bonding to a metal, Cn1 and Cn2 are the same or different and are conjugated connecting groups, MC is a chromophore selected from the group consisting of conjugated macrocycles, and n is an integer of at least 1, wherein if n is greater than 1 different chromophores may be present within the structure.
[0002] The invention concerns photoelectric devices and, in particular, photoelectric devices that include photo-active molecules and exhibit plasmonic activity.
[0003] Metal nanostructures have been studied extensively in the field of nano-science. Nanostructures have interesting physical properties that make them ideal for fundamental research and applications. In particular, nanostructures made from noble metals (e.g., gold and silver) with their associated strong plasmon resonance have generated great interest. The fact that the plasmon response is a sensitive function of nanostructure geometry, coupled with synthetic advances that allow for controlled and systematic variations in nanostructure geometries, is leading to a dramatic increase in interest in this topic. This interest has caused the development of a new field called "plasmonics," associated with the design and fabrication of nano-optical components that focus and manipulate light at spatial dimensions far below the classical diffraction limit. Applications of plasmonics include surface enhanced Raman spectroscopy (SERS) and chemical sensing. To date, the applications of plasmonics have been largely in the optical domain.
[0004] In one aspect of the invention, an electro-optical device is provided which comprises a substrate on which first and second electrodes are formed. A plurality of nanoparticles are arrayed on the surface of the substrate between the first and second electrodes. The arrayed nanoparticles exhibit plasmonic activity in at least one wavelength band. A plurality of linking molecules are coupled between respective adjacent ones of the nanoparticles and between each of the electrodes and nanoparticles that are adjacent to the electrodes. The linking molecules are selected to exhibit photo-activity that is complementary to the arrayed nanoparticles.
[0005] FIG. 1a is a perspective drawing that illustrates an electronic path through an array of linked nanoparticles; FIGS. 1b, 1c and 2 are schematic drawings that illustrates the linking of two nanoparticles as shown in FIG. 1
[0006] FIG. 3 is a perspective and side-plan view of an example photovoltaic device that may include linked arrays of nanoparticles as shown in FIG. 1a.
[0007] FIG. 4 is a side-plan view of an example photo-active switch that may include a linked array of nanoparticles as shown in FIG. 1a.
[0008] Metal nanoparticles respond to electromagnetic waves by creating surface plasmons or particle plasmons, collectively known as plasmons. These are localized collective oscillations of conductive electrons on the surface of the nanoparticles. When inter-particle distances are small, plasmons generated in neighboring nanoparticles can couple to one another creating locally intense electromagnetic fields. The coupled particles can then act as optical antennae capturing and refocusing light between them. Furthermore, the electrical properties of molecules linking such nanoparticles may be affected by these interactions. For example the molecules and metal nanoparticles may exhibit charge transfer in which an electron is transferred from the highest molecular orbital of the linking molecule to the Fermi level of the metal and from the Fermi level of the metal to the lowest unoccupied orbital of the molecule.
[0009] In addition, the inventors have determined that plasmons may be used to control the electrical properties of photo-active, electrically conductive organic molecules that are used to electrically couple the nanoparticles in an array of metal nanoparticles. In particular, the magnitude of the observed photoconductivity of interconnected plasmon-coupled nanoparticles can be tuned independently of the optical characteristics of the molecule.
[0010] According to the example embodiments of the invention described below, optically induced plasmons may be used to alter the electrical properties of molecular junctions, greatly enhancing electrical conduction across the junctions. One example device, described below, consists of a disordered array of gold nanoparticles fabricated on an insulating glass substrate. The nanoparticles are linked by conjugated multi-porphyrin chromophoric molecules.
[0011] Plasmonic activity in nanoparticle arrays depends on the size, shape distribution of and separation between the nanoparticles in the array. Whereas the sizes of the nanoparticles can be controlled by modification of the conditions under which they are synthesized, inter-particle distances may be determined by the nature of the organic molecules that link each nanoparticle to its neighbors.
[0012] High-density closely packed arrays of nanoparticles exhibit metallic conductivities with resistances higher than that of the bulk material due to electron scattering at nanoparticle boundaries. At larger inter-particle separations, electrons can tunnel between nanoparticles. In such systems, temperature-dependent transport data may exhibit an Arrhenius dependence (σ αexp T -1) or suggest other conduction mechanisms, for example, (σ αexp T -1/2). In the case of a random array, however, conduction occurs via a percolative path spanning from one electrode to another. The percolative path comprises the "path of least resistance." FIG. 1a shows an example of such a path between electrodes 102 and 104 formed by metal nanoparticles 106 that are coated with organic linking molecules.
[0013] The inventors have discovered a method for producing arrays of nanoparticles in which the separation between neighboring nanoparticles corresponds to, or is influenced by, the length of a conjugated molecule having appropriate linkage functionality at its termini. These molecules, linking the nanoparticles, ensure a percolative conduction path in the device.
[0014] An illustrative gold nanoparticle to gold nanoparticle interconnect is shown schematically in Fig. lb. As shown in FIG. 1b, nanoparticles 106 are joined by molecular interconnects 108. Nanoparticles 106 proximate to electrodes 102 and 104 may also be joined to the electrodes by molecular interconnects 108 (i.e., molecular interconnects 108 may bridge from a nanoparticle to an adjacent surface of an electrode).
[0015] In the example embodiments of the invention described below, the molecular interconnects (also referred to herein as linking compounds or linking molecules) are selected to have physical properties that are matched to the gold nanoparticles and possess optoelectronic characteristics optimal for coupling to plasmons generated in the array of gold nanoparticles and that exhibit charge transfer effects with the gold nanoparticles. For example, because isolated and coupled plasmon resonances in arrays of gold nanoparticles occur at wavelengths greater than or equal to 520 nm, it is desirable for the linking molecules to have a large absorptive oscillator strength in this regime of the electromagnetic spectrum. A meso-to-meso ethyne-bridged (porphinato)zinc(II) oligomer (PZnn compound, where n is 2 or greater) is one example of a molecule that exhibits this spectroscopic property. FIG. 1c shows the structure of an exemplary linking molecule 108 which serves as a 4.6 nm long gold nanoparticle to gold nanoparticle bridge in these devices.
[0016] When optical radiation excites plasmons and the nanoparticles are coupled, a large electromagnetic field may be established between the particles. As shown in FIG. 2, the particles 106 act as optical antennae and focus light into the region 210 between the particles. The size, shape, separation and distribution of the nanoparticles may be tailored to control both the wavelength of light at which the particles interact with the light and the regions into which they focus the light. Alternatively, the array of nanoparticles may exhibit a random distribution such that plasmonic activity exists in multiple wavelength bands. In addition, the optical excitation may contribute to the charge transfer between the particles and the molecular interconnects. The focused light has the consequence of increasing the photon flux at the molecular junction. When the size, shape and separation of the particles are controlled to produce "resonant" optical antennae, the conductivity of the array of nanoparticles may be enhanced by as much as 104.
[0017] In general terms, the size and shape of the nanoparticles as well as their spacing in the array may be controlled to sharpen or shift the plasmon and coupling energies as well as the antennae enhancement factor while the linking molecule may be designed to control the absorption wavelength, oscillator strength and the nature of excition and polaron states.
[0018] An illustrative photovoltaic device including an embodiment of the subject invention is shown in FIG. 3. In this example photovoltaic device, arrays of nanoparticles linked by photoactive linking molecules are arranged between electrodes having different Fermi levels. These electrodes form heterojunctions which attract the holes and electrons of the excitons generated in the linking electrodes in different directions. The enhanced conductivity of the array of nanoparticles due to the formation of plasmons as well as charge transfer effects makes it less likely that the holes and electrons of the excitons will recombine before reaching the electrodes.
[0019] The structure shown in FIG. 3 includes three layers, the bottom layer 310 is sensitive to red light, the middle layer 312 to green light and the top layer 314 to blue light. In the example embodiment, the bottom layer is formed from nanoparticles 302 on a glass substrate 300. In this example, the nanoparticles 302 may be coated with a linking molecule that exhibits absorptive oscillator strength in the red region of the spectrum. The coated nanoparticles may be randomly positioned on the substrate such that the average spacing between the nanoparticles without the linking molecules is approximately 5 nm. As described above, it is desirable for the coated nanoparticles to be in electrical contact. In this example embodiment, the nanoparticles may have diameters of in the range of 5-100 nm. In a particular array that is tuned to a specific wavelength band, the diameters of the particles are approximately equal. In this example the nanoparticles are generally spherical and have a diameter of approximately 30 nm. In the example, this layer of linked nanoparticles is the red sensitive layer 310.
[0020] A dielectric layer 316 of, for example, silicate glass is formed on top of the coated nanoparticles 302 of the bottom layer 310 and another layer of coated gold nanoparticles 304 is formed on top of the dielectric layer 316. The example nanoparticles 304 in this layer are coated with a linking molecule that exhibits absorptive oscillator strength in the green region of the spectrum. These nanoparticles, have approximately the same configuration as the nanoparticles in the red sensitive layer 310 except that they are randomly arranged on the dielectric layer 316 to have an average spacing of approximately 10 nm. This array of linked nanoparticles is the green sensitive layer 312. A second dielectric layer, which may also be silicate glass, is deposited on top of the linked nanoparticles of the green sensitive layer 312. On top of this layer is deposited a layer 320 of photo-active molecules that exhibit a relatively large absorptive oscillator strength in the blue region of the spectrum. This layer is the blue sensitive layer 314. A spun-on glass layer 322 is formed on top of the layer 320 to seal the device. In this example, the nanoparticles may be formed from gold and the is linking molecule may be dithiol PZn3 (containing three zinc porphyrin moieties linked by ethynyl groups and functionalized at each end of the molecule with a thiol group).
[0021] Each of the layers 310, 312 and 314 is formed to be in electrical contact with two electrodes, anode 324 and cathode 326. As described above, these electrodes have different Fermi levels and, so, form a heterojunction with the intervening nanoparticle arrays. In this example, electrode 324 may be formed from an N-type semiconductor, for example, N-type silicon while electrode 326 may be formed from a metal, for example, gold. The example photovoltaic device includes alternating electrodes 324 and 326 where each pair of electrodes is separated by layers 310, 312 and 314 as described above. All of the anode electrodes 324 are electrically connected on one side of the device while all of the cathode electrodes 326 are electrically connected on the other side of the device.
[0022] In operation, white light impinging on the device generates excitons in all three layers. In the red layer 310, red components of the white light also generate plasmons that increase the conductivity of the linking molecules in the red layer, allowing the holes to migrate to the anode electrode 324 and the electrons to migrate to the cathode electrode 326. Similarly, green components of the white light generate plasmons in the green layer 312 increasing the conductivity of that layer so that holes and electrons of the excitons generated in layer 312 migrate to the electrodes 326 and 324, respectively. The top layer does not include nanoparticles because, as described above, blue light (i.e. light having wavelengths less than 520 nm) does not interact with gold nanoparticles to generate plasmons. The layers are arranged with the blue layer 314 on the top, the green layer 312 in the middle and the red layer 310 on the bottom because relatively little blue light will propagate through the layer 314 and relatively little green light will propagate through layer 312.
[0023] In this example embodiment, dithiol-PZn3 has a relatively large absorption oscillator strength in the blue wavelength band and reduced absorption oscillator strength in the green and red wavelength bands. The augmented conductivity generated by the arrays of nanoparticles in the red and green layers allows the photocharges generated in these layers to contribute at about the same level as the blue photocharges generated in the top layer 314. It is contemplated that the device may be improved by using respectively different linking molecules having high absorption oscillator strength in the green and red wavelength bands, 312 and 310 in place of the dithiol-PZn3. These molecules are selected to form bonds with the gold nanoparticles as well as with the electrodes 324 and 326. In addition, it is contemplated that other materials than gold may be used for the nanoparticle array and that the size and spacing of the nanoparticles may be changed as long as the result is red and green arrays that exhibit plasmonic activity in their respective wavelength bands.
[0024] Alternatively, a photovoltaic device which is sensitive to light in multiple wavelength bands may be made using randomly distributed linked nanoparticles which may have different sizes and shapes. Such an array may exhibit plasmonic activity in multiple wavelength bands. This example array may include a single linking molecule or multiple different linking molecules, each exhibiting increased sensitivity to light in a different wavelength band. Desirably, the photoactivity of the linking molecules is complementary to the plasmonic activity of the array of nanoparticles.
[0025] FIG. 4 is a side plan view of an example optical switch or light detector. This optical switch includes a single layer of linked metal nanoparticles 410, for example gold nanoparticles, formed on a glass substrate 402. The array of nanoparticles 410 is coupled to first and second electrodes 404 and 406 which may be, for example, gold electrodes. A protective spun-on glass layer 408 is formed over the array of nanoparticles 410.
[0026] In this example device, the linking molecule that joins the gold nanoparticles is selected to be conductive when illuminated by light in the desired wavelength band. In addition, the size and spacing of the gold nanoparticles are selected to generate plasmons and the linking molecules are selected to enhance charge transfer effects when illuminated in the desired wavelength band. Both the linking molecule and the configuration of the gold nanoparticles are selected to have much lower conductivity in wavelength bands outside of the desired band. In operation, the device shown in FIG. 4 may be coupled to positive and negative supplies and a current sensor may be placed in series with the device. When illuminated by light in the desired wavelength band, the conductivity of the device will increase, causing a greater current flow than when the device is illuminated by light in other wavelength bands.
[0027] The present invention utilizes nanoparticles. In one particularly advantageous aspect of the invention, at least a portion of the nanoparticles are particles comprised of metal which are electrically conductive. The nanoparticles should be capable of being induced to generate plasmons when subjected to optical interactions. That is, the nanoparticles should respond to electromagnetic waves by creating plasmons, which are localized, collective oscillations of conduction electrons. Preferably, the metal is selected from one or more of gold, silver, copper, a transition metal, or an element of groups 1B to IV of the periodic table. These include aluminum, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, is zinc, gallium, germanium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, lanthanum, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, tellurium and lead. Gold may be an especially advantageous metal for use in the nanoparticles of the present invention. The metallic nanoparticles can be pure elemental metals or alloys or composites of different metals. A single type of metallic nanoparticle may be employed, but mixtures of different metallic particles varying in size, shape, elemental composition, and/or surface characteristics or the like are also usable.
[0028] The size of the nanoparticles may be varied as desired and may be selected so as to impart particular properties or characteristics to the arrays that are fabricated using such nanoparticles in accordance with the present invention. Generally speaking, however, the nanoparticles may range in size from about 1 nm to about 200 nm, with the range of from about 10 to about 100 nm being preferred in certain embodiments. As discussed previously, different layers or regions of a device in accordance with the invention may contain nanoparticles of different compositions and sizes. The nanoparticles may take the form of spheres, cubes, cones, discs, rods, tubes, wires, fibers or any other regular or irregular geometric shape.
[0029] In certain embodiments of the invention, ligand-stabilized metallic nanoparticles are employed as starting materials. Stabilizing metallic nanoparticles with ligands such as citrate can assist in keeping the nanoparticles from clustering together or agglomerating and in maintaining the nanoparticles as discrete, separated particles, while the nanoparticle arrays in accordance with the invention are being assembled. Deposition of nanoparticle arrays from such colloids results in a random distribution of positions (i.e., the nanoparticles are randomly distributed on a substrate surface). In an alternative embodiment of the invention, a stabilizing ligand is employed which is capable of linking the nanoparticles at a specified distance while in the colloid. This approach would result in nanoparticle arrays having more ordered and more closely packed position distributions, thereby increasing the number of nanoparticle pairs with the desired separation.
[0030] If so desired, the nanoparticles may be affixed to a substrate surface. For example, metallic nanoparticles may be chemically bonded to a substrate surface using one or more coupling agents, such as silane coupling agents. Suitable coupling agents include silanes which contain a functional group capable of being reacted with a metal in the metallic nanoparticle, such as an amino group, thiol group, or the like as well as a functional group capable of being reacted with a functional group on the surface of the substrate (for instance, where the substrate surface bears hydroxyl groups, the coupling agent may contain an alkoxy group or the like). In one embodiment of the invention, the coupling agent has little or no electrical conductivity (e.g., the coupling agent does not provide a conjugated structure connecting the substrate and the nanoparticles).
[0031] Compounds which are particularly preferred for use in linking nanoparticles in accordance with the present invention (sometimes referred to herein as "linking compounds" or "linking molecules") include compounds which are conjugated, with the compound in one embodiment being comprised of at least one (but preferably more than one) chromophore per molecule selected from the group consisting of conjugated macrocycles and at least two end groups in each molecule that are capable of bonding to a metal. "Conjugated" in the context of the present invention means a chemical structure characterized by a chain wherein each contiguous atom in the chain possesses a p-orbital. For example, such a chain may contain a series of alternating carbon-carbon double (or triple) bonds and carbon-carbon single bonds. One or more aromatic rings may also comprise part of the conjugated structure.
[0032] The linking compounds may be "multichromophoric," i.e., molecular entities containing more than one chromophore per molecule, in particular more than one conjugated macrocycle chromophore per molecule. If the compound contains more than one chromophore per molecule, the chromophores may be the same as or different from each other. "Chromophores" are chemical moieties capable of selective electromagnetic radiation absorption, particularly at visible light, ultraviolet, and near infrared wavelengths. For example, a chromophore can be a region or moiety in a molecule where the energy difference between two different molecular orbitals fall within the range of the visible spectrum. Visible light that hits the chromophore can thus be absorbed by exciting an electron from its ground state into an excited state. Typically, a chromophore takes the form of a conjugated pi system or a metal complex. The chromophores are preferably present in the main chain ("backbone") of the linking compounds utilized in the present invention, but can also or alternatively be pendant to the main chain (e.g., in the form of substituents attached to the backbone of the linking compound). The chromophores may also be useful for creating the electron bands that are relevant for molecule to metal and metal to molecule charge transfers.
[0033] Conjugated macrocycles function as polarizable bridging moieties serving to augment electronic coupling between attached donor and acceptor groups. As such, any cyclic or polycyclic moieties comprising a plurality of unsaturations manifest as double or triple bonds can be used as a conjugated macrocycle in the present invention. In some embodiments, the conjugated macrocycles can be heterocyclic, comprising one or more heteroatoms. Some heterocyclic conjugated macrocycles include, but are not limited to, porphyrins, chlorins, phorbins, benzoporphyrins, bacteriochlorins, porphyrinogens, sapphyrins, texaphryins, and phthalocyanines, as well as N-confused versions of these species.
[0034] Conjugated macrocycles can also comprise one or more metal atoms such as, for example, transition metals, lanthanides, actinides, alkaline earth, and alkali metals. Further, any atom of the conjugated macrocycle can bear substituents, except possibly for atoms that are bonded to groups which interconnect conjugated macrocycles within the linking molecule. These substituents, as well as any metal atom complexed to the conjugated macrocycle, can be chosen for their particular steric or electronic properties, for instance, to control intramolecular interactions and/or molecular order in the bulk phase as well as to influence ground state and excited state energy levels. Conjugated macrocycle substituents can include H, electron-donating groups, and/or electron-withdrawing groups in any number and combination. More particularly, conjugated macrocycle substituents can include one or more of H, alkyl groups having 1 to about 20 carbon atoms, alkenyl groups having 2 to about 20 carbon atoms, alkynyl groups having 2 to about 20 carbon atoms, aryl groups having 3 to about 50 carbon atoms, arylalkynyl groups having 8 to about 24 carbon atoms, heterocycloalkyl groups having 2 to about 24 carbon atoms, heteroaryl groups having 2 to about 50 carbon atoms, heterocycloalkylalkynyl groups having 4 to about 24 carbon atoms, heteroarylalkynyl groups having 4 to about 50 carbon atoms, and groups including, but not limited to, halo, amino, nitro, nitroso, cyano, azido, aldehyde, carboxyl, carbonyl, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkoxy, hydroxyl, mercapto, thiolato, sulfo, phosphino, phospho, and phosphono, to name a few.
[0035] Conjugated macrocycles are well known in the art. For example, any of the conjugated macrocycle moieties described in U.S. Pat. No. 5,986,090 and U.S. Pat. Pub. Nos. 2004-0152826 and 2004-0067198 (each incorporated herein by reference in its entirety for all purposes) may be adapted for use in the present invention. Moieties other than conjugated macrocycles may also or alternatively be present as chromophores in the linking compounds used to construct nanoparticle arrays in accordance with the present invention. Such chromophoric moieties can include, for example, polypyridyl complexes of various metals such as ruthenium, osmium and iron as well as polycyclic aromatic systems such as fused or linked benzene ring systems, particularly polycyclic aromatic systems containing more than two benzene rings linearly attached to each other such as anthracene moieties and higher homologs thereof such as pentacene (including substituted polycyclic aromatic systems where the aromatic rings are substituted with one or more substituents other than hydrogen, such as halogen, alkyl, alkoxy, carboxylic acid, esters and/or cyano groups). The chromophores may be hydrocarbon in character (i.e., contain only carbon and hydrogen), but may also contain one or more heteroatoms such as oxygen, sulfur or nitrogen in addition to carbon and hydrogen. Functional groups such as ketones and the like may be present in the chromophore. The chromophore may also be a polycyclic aromatic moiety wherein one or more of the cyclic structures within such moiety contains one or more heteroatoms.
[0036] The compounds that may be used to link together metallic nanoparticles in accordance with the invention are characterized by having at least two end groups per molecule capable of bonding to a metal. In one embodiment, such compounds contain only two such end groups per molecule. The bonding may ionic or coordinative in nature, but in one advantageous embodiment the bonding is covalent. These end groups may either bond or react directly with a metal or after being treated or otherwise converted so as to remove a masking or protective group which initially is part of the end group. The end groups of the linking molecule may displace ligands present on the surface of the nanoparticles such as, for example, citrate ligands. In certain embodiments of the invention, the end groups are selected such that a metal to heteroatom bond is formed, particularly a metal to oxygen (e.g., M--O), metal to sulfur (e.g., M--S), or metal to nitrogen (e.g., M--N) bond, especially a covalent bond. In addition to N, O and S, other heteroatoms such as selenium, phosphorus, arsenic or tellurium can be similarly utilized. Suitable end groups include, for example, thiol (--SH) groups, amino groups (e.g., --NH2, --NHR, or --NR2, where R is an organic substituent such as an alkyl or aryl group), thiocarboxyl groups (e.g., a thioacetoxyl group --SCOCH3), carboxyl (carboxylic acid) groups (--CO2H), cyano groups (--CN), sulfonic acid groups, phosphonic acid groups or the like.
[0037] In one embodiment of the invention, the compound employed to link together the metallic nanoparticles to form arrays contains, in addition to one or more conjugated macrocyclic chromophores, one or more unsaturated carbon-carbon bonds such as carbon-carbon double bonds or carbon-carbon triple bonds. That is, the chain of the conjugated compound may contain one or more alkene and/or alkyne groups that are arranged so as to render the chain conjugated in character. Such alkene and alkyne groups may, for example, be interspersed between an end group and a conjugated macrocyclic chromophore and/or between two conjugated macrocyclic chromophores. Multiple alkene and/or alkyne groups may be arranged adjacent to each other. For example, two conjugated macrocyclic chromophores may be linked via conjugated connecting groups containing one or more carbon-carbon double and/or triple bonds. Thus, two adjacent macrocyclic chromophores may be connected to each other by an ethynyl group or a butadiynyl group. Aromatic groups (e.g., phenyl and/or fused benzene rings) may also be employed to construct the chain of the conjugated compound.
[0038] Each connecting group can be attached to any position on the conjugated macrocycle. For example, when the conjugated macrocycle is a porphyrin, the connecting group can be attached to meso or pyrrolic (beta) positions. In some embodiments, two connecting groups are attached at opposite meso positions in a porphyrin (i.e., at the 5 and 15 positions or the 10 and 20 positions on the porphyrin ring).
[0039] The compound that is used to treat or coat metallic nanoparticles in accordance with the invention may, for example, have the structure EG1-Cn1-[-MC-Cn2-]n-EG2 wherein EG1 and EG2 are the same or different and are functional groups capable of bonding to a metal, Cn1 and Cn2 are the same or different and are conjugated connecting groups, MC is a chromophore selected from the group consisting of conjugated macrocycles, and n is an integer of at least 1, wherein if n is greater than 1 different chromophores may be present within the structure. In certain embodiments of the invention, EG1 and EG2 are AcS-Ph-, Cn1 and Cn2 are ethynyl groups, MC is a metalloporphyrin, and n is an integer of from 2 to 5. Meso-to-meso ethyne-bridged (porphinato)zinc(II) oligomers containing thiol end groups have been found to be particularly useful in the present invention. The value of n may be varied as desired to adjust the overall length of the linking molecule.
[0040] The aforementioned compounds thus can yield arrays of metallic nanoparticles comprising a structure M1-X-Cn1-[-MC-Cn2-]n-Y-M2 wherein M1 and M2 are the same or different and are metal atoms on surfaces of metallic nanoparticles in the array, X and Y are the same or different and each contain a heteroatom selected from S and N bonded to M1 and M2 respectively, Cn1 and Cn2 are the same or different and are conjugated connecting groups, MC is a chromophore selected from the group consisting of conjugated macrocycles, and n is an integer of at least 1, wherein if n is greater than 1 different chromophores may be present within the structure. For example, X and Y may each be --S-Ph-, wherein sulfur is bonded to gold and the Ph (phenyl) group links to a connecting group Cn1 or Cn2.
[0041] Linking compounds useful in the present invention can be prepared by a variety of methods, including for example, metal-mediated cross-coupling techniques.
[0042] Metal-mediated cross-coupling is known to those skilled in the art as an efficient synthetic method for elaborating porphyrins and other related macrocycles as described in U.S. Pat. Nos. 5,371,199; 5,756,723; 5,986,090; and 5,493,017 as well as U.S. Pat. Pub. Nos. 2004-0152826 and 2004-0067198 and International Patent Application Publication WO 94/04614; and other publications including, DiMagno, et al., J. Am. Chem. Soc. 1993, 115, 2513; DiMagno, et al., J. Org. Chem. 1993, 58, 5983; and Lin, et al., Science, 1994, 264, 1105, each of which is incorporated herein by reference in its entirety for all purposes. Condensation techniques are also useful in the preparation of the present linking compounds and are described, for example, in DiMagno, et al., J. Org. Chem. 1994, 59, 6943.
[0043] In one aspect of the invention, useful linking compounds can be assembled by covalently coupling appropriately derivatized starting materials using metal-mediated cross-coupling techniques. One process for preparing linking compounds useful in the present invention involves contacting a conjugated macrocycle precursor, such as a porphyrin-containing or oligoporphyrin-containing precursor, with an end group precursor. The conjugated macrocycle precursor may comprise a conjugated macrocycle bearing at least one first reactive substituent such as an alkynyl group. In one embodiment, the conjugated macrocycle bears at least two such reactive substituents. If it is desired that the linking compound contain two or more conjugated macrocycles per molecule, oligomeric conjugated macrocycle precursors may be assembled using metal-mediated cross-coupling techniques.
[0044] The end group precursor comprises a moiety, typically an organic moiety, containing the desired end group (e.g., --SH) or precursor thereof (e.g., a masked or protected end group such as --SAc) and bearing a second reactive substituent such as a halogen (e.g., I, Br). The first and second reactive substituents are selected such that they are capable of participating in the desired metal-mediated cross-coupling reaction so as to form a covalent bond between the conjugated macrocycle precursor and the end group precursor. Contacting can be carried out in the presence of one or more metal-containing catalysts, such as a palladium-containing catalyst, under metal-mediated cross-coupling reaction conditions for a time and at a temperature sufficient to form the desired covalent linkage between the conjugated macrocycle precursor and end group precursor.
[0045] Appropriate catalysts and mechanisms for metal-mediated cross-coupling reactions are described in detail in U.S. Pat. No. 5,756,723, which is incorporated herein by reference in its entirety for all purposes. The principles and techniques relating to metal-mediated cross coupling are well known to those skilled in the art to consist of three general steps: (1) oxidative addition, (2) transmetalation, and (3) reductive elimination. See, e.g., Collman, et al., Principles and Applications of Organotransition Metal Chemistry, University Science Books, 1987, Mill Valley, Calif.; Kumada, Pure & Appl. Chem., 1980, 52, 669; Hayashi, et al., Tetrahedron Letters, 1979, 21, 1871, each of which is incorporated herein by reference in its entirety for all purposes.
[0046] The following publications also describe end-functionalized linking molecules containing chromophoric groups suitable for use in the present invention: WO 96/07487; US 2005/0056828; and US 2002/0127756, each of which is incorporated herein by reference in its entirety for all purposes. The molecular structure of the linking molecule may be varied as may be desired to modify the characteristics of the nanoparticle array. For example, the length of the linking molecule may be selected so as to influence or conform to the spacing of the nanoparticles in the array. Arrays may be produced in which the average separation between neighboring nanoparticles corresponds to the length of a linking molecule which is conjugated and which features appropriate linkage functionality at each terminus to ensure a percolative conduction path in a device containing an array of such interconnected nanoparticles. The chromophore(s) present in the linking molecule may be chosen to optimize coupling to metal plasmons.
[0047] Combinations or mixtures of different linking molecules which vary, for example, in chain length and/or chemical structure may be utilized in the present invention. Linking molecules of the same length which contain different chromophores or linking molecules of differing length containing the same type of chromophoric moieties (e.g., porphyrins) may be used within the same device. Different linking molecules may be employed in different layers or regions of the device. Although the invention is illustrated and described herein with reference to specific embodiments, the invention is not intended to be limited to the details shown. Rather, various modifications may be made in the details within the scope and range of equivalents of the claims and without departing from the invention.
Fabrication of Nanoparticle Arrays
[0048] To fabricate nanoparticle arrays, glass substrates (Fisher) were cleaned in piranha solution (1:3 30% H2O2: conc. H2SO4) for 10 minutes, rinsed with ultra-pure water, and immediately immersed into a 5% solution of 3-aminopropyl-methyl-diethoxysilane (Sigma-Aldrich) in hexanes (HPLC grade, Sigma-Aldrich). The glass substrates were kept in this solution at 80° C. for 24-48 hours. Citrate-stabilized AuNPs (gold nanoparticles) of diameters 16, 32, and 46 nm were synthesized according to a previously published methodology (Turkevich et al. Discussions of the Faraday Society, 55 (1951)). The amine-functionalized glass substrates were then immersed in aqueous solutions of AuNPs for ca. 96 hours under ambient conditions. The surface coverage and the particle size distribution of the AuNPs were established using dynamic light scattering (DLS) and scanning electron microscopy (SEM) in the as-prepared colloid, and on the substrate, respectively. Both techniques independently confirmed the size and size distribution of the AuNPs.
Adsorption of Dithiol-PZn3 onto AuNP Arrays
[0049] Adsorption of dithiol-PZn3 onto the AuNP (gold nanoparticle) arrays was performed under a nitrogen atmosphere in a glove box (PlasLabs). The solvent tetrahydrofuran (THF, HPLC grade, Fisher) was distilled from sodium under nitrogen and collected into a vacuum-sealed flask (Chemglass) and subjected to repeated freeze-pump-thaw-degas cycles. To an acetyl-protected dithiol-PZn3 solution (ca. 1 μM in THF), 4 μl/ml of NH4OH was added to unmask the thiolate functionality. The glass substrates with surface-bound AuNPs were then immersed into adsorption vials (Wheaton) containing this solution and set aside for 4 hours. The substrates were rinsed with THF and dried under a stream of N2. Molecular attachment to the AuNPs was verified via electronic absorption spectroscopy, which showed the characteristic chromophore transition centered at 420 nm, and the AuNP plasmon band. Furthermore, the Raman spectra of these samples showed the strong surface-enhanced, characteristic peaks associated with the linker porphyrin system (Li et al. Thin Solid Films, 457, 372 (2004); Seth et al. J. Am. Chem. Soc., 116, 10578 (1994)). Gold electrodes (ca. 35 nm thick) separated by thin channels were thermally evaporated (Thermionics) on the AuNP covered glass substrate using a shadow mask technique. Channel lengths between the electrodes varying from 26 to 68 μm were obtained with this technique. The photoresponse of the devices prepared as described herein was found to be independent of this channel length. The samples were then transferred immediately to the probe station for electrical measurements.
[0050] The transport measurements were obtained using a Lakeshore Desert Cyrogenics TT6 probe station under vacuum and cooled using liquid nitrogen. Current-voltage (IV) characteristics were acquired with an electrometer (Keithley 6515A) using CuBe probe tips. After obtaining the transport data in the absence of illumination, the wavelength dependent current-voltage characteristics were obtained by exposing the samples to 405 nm (5 mW), 532 nm (2 mW), and 655 nm (5 mW) laser diodes (Edmund Optics). Transport properties were determined at temperatures ranging from 78 to 298° K.
Patent applications by THE TRUSTEES OF THE UNIVERSITY OF PENNSYLVANIA
Patent applications in class Light responsive structure
Patent applications in all subclasses Light responsive structure
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text:
Loftus, B. J., Kim, U. J., Sneddon, V. P., Kalush, F., Brandon, R., Fuhrmann, J., Mason, T., Crosby, M. L., Barnstead, M., Cronin, L., Deslattes Mays, A., Cao, Y., Xu, R. X., Kang, H. L., Mitchell, S., Eichler, E. E., Harris, P. C., Venter, J. C., Adams, M. D.
Genome Duplications and Other Features In 12 Mb of DNA Sequence from Human chromosome 16p and 16q
Genomics. 1999 Sep 15; 60(3): 295-308.
Several publicly funded large-scale sequencing efforts have been initiated with the goal of completing the first reference human genome sequence by the year 2005. Here we present the results of analysis of 11.8 Mb of genomic sequence from chromosome 16. The apparent gene density varies throughout the region, but the number of genes predicted (84) suggests that this is a gene-poor region. This result may also suggest that the total number of human genes is likely to be at the lower end of published estimates. One of the most interesting aspects of this region of the genome is the presence of highly homologous, recently duplicated tracts of sequence distributed throughout the p-arm. Such duplications have implications for mapping and gene analysis as well as the predisposition to recurrent chromosomal structural rearrangements associated with genetic disease.


text:
Madness, again, this time in the nation's capital
Published 5:56 pm, Monday, September 16, 2013
Once again, a mass shooting inflicted horror, panic, chaos and a staggering loss of life in the unlikeliest of settings.
This time, it wasn't an elementary school, a packed theater or an unguarded workplace. This time, the random gun violence struck the high-security Washington Navy Yard, where employees and visitors are checked at entrances and armed guards are on site to respond to trouble.
Once again, we are reminded there is no refuge from the madness of twisted minds in a land where firearms capable of mass slaughter are readily available.
A 34-year-old suspect, a full-time Navy reservist from 2007 to 2011, was shot dead on the scene. But that hardly stilled the anxiety. Bridges and streets were closed, airline flights were halted and nearby schools and buildings - including U.S. Senate offices - were locked down as police searched for a possible second suspect. A city that is as prepared as any on the planet for emergencies was confronted with its largest loss of life since a plane plunged into the Potomac River in 1982.
President Obama mourned the loss of Americans whose occupation was to make a safer world for the rest of us. "They're patriots," Obama said. "They know the dangers of serving abroad, but today they faced the unimaginable violence that they wouldn't have expected here at home."
- 1963 newsreel footage of the last prisoners leaving Alcatraz Federal Penitentiary Onyx Media/Getty Images
- CHP rescue a hiker in Sonoma County CHP Golden Gate Division Air Operations
- SF Firefighters rescue woman from 4th floor SF Fire Dept.
- Visionary Journey, Laurie Green San Francisco Chronicle
- Visionary Journey, Laurie Green San Francisco Chronicle
- Visionary Leader, Sarahi Espinoza Salamanca San Francisco Chronicle
- Visionary Journey, Sarahi Espinoza Salamanca San Francisco Chronicle
- Map shows an Oakland that's no longer there East Bay Yesterday/Front Group Design
- Elementary school in Oakland opens time capsule from 1927 San Francisco Chronicle
- Brides of March walk through San Francisco San Francisco Chronicle
It is the American nightmare that keeps returning: Littleton, Sandy Hook, Aurora, Fort Hood, Virginia Tech. The circumstances vary, but the human devastation and determined cries of "never again" are hauntingly familiar.
Once again, we rage, and mourn, and summon our resolve against the forces of futility.


text:
Having problems with your Dell Latitude D620 Laptop (Latitude-C620) PC Notebook ?
Dell I formated my Dell latitude D620 laptop.So I need to get a factory recovery Disk. Where can I get one? I lost all my drivers. So now I can not get on the internet. Now I need Drivers that can get me back on the internet. I'm on a friends computer.
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You will have to order it from www.dell.com, but if you have a retail copy of Windows, you can install that, and then download/install all of the necessary device drivers at this link
\015\012Good luck, and thank you for using FixYa
\015\012Good luck, and thank you for using FixYa
Repair Help & Product Troubleshooting for Dell Latitude D620 Laptop (Latitude-C620) PC Notebook
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