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The following comes from the CNA:
God's promise of a new and eternal life deserves priority over earthly desires for things that can never satisfy the heart, Pope Benedict XVI taught in his Aug. 5 Sunday Angelus address at Castel Gandolfo.
"Jesus wants to help people move beyond the immediate satisfaction of their material needs, although they are important too. He wants to open a horizon of existence which is not simply that of the daily concerns of eating, dressing and career," the Pope told pilgrims at his summer residence.
The true "center of existence," giving "full meaning and firm hope" to life, "is faith in Jesus … our encounter with Christ," the Pope reflected.
Thousands of enthusiastic visitors listened from the courtyard of the Apostolic Palace as the Pope discussed Sunday's reading from the "Bread of Life" discourse in the Gospel of John.
In it, Christ tells the multitude not to labor for the "food that perishes" but "for the food which endures to eternal life, which the Son of Man will give to you." Jesus proclaims himself as "the bread of life," declaring: "Whoever comes to me will never hunger, and whoever believes in me will never thirst."
Pope Benedict stressed that this encounter with Christ goes far beyond "an idea" or "a project," to reach Jesus "as a living person" who wants everyone "to be fully involved with him and his Gospel."
In the midst of everyday concerns, Christ calls humanity to "look ahead and to open the human horizon to the horizon of God, the horizon of faith."
During their journey of faith, believers are sustained by something infinitely greater than the miraculous manna given to the Israelites in the Old Testament. Jesus, the Pope said, does not merely "give something," but instead "gives himself" to the faithful in Holy Communion.
"Let us put our faith in him, and let us put our trust in his promises, so that we may have life in abundance," the Pope urged the crowd, before leading them in reciting the traditional midday Marian prayer.


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Looking for sustainable and ethical meat? You've come to the right place. Our premium quality free range beef is produced with animal welfare and the environment in mind. Choose from succulent steaks, delicious roasting joints and classic burgers. Get free delivery when you spend £50 or more.
Read More
Here at Graig Farm Organics, we understand why people are concerned about where their food comes from. After all, we want to be able to trust the suppliers of our food. When you shop with us, you can rest assured that your produce is fully traceable from farm gate to dinner plate.
Our award-winning British beef isn't just popular because of its delicious taste. It's reared to very strict standards of animal welfare, and we think this makes all the difference. We believe that animals should be free to explore the outdoors instead of being confined to cages for most of their lives. Having access to pasture and sunlight means they're able to exercise, socialise and enjoy a higher quality of life.
As well as their free range lifestyle, our animals are reared on a nutritious diet. This means no routine drugs, growth enhancers or GMOs. With generations of Welsh farming knowledge at the centre of our system, you can rest assured that you're getting premium meat that's packed with goodness.
You'll find a range of beef cuts in our selection, from warming silverside joints and mouth-watering rump steaks to tasty mince and juicy burgers. We even have organic meat boxes for you to stock up on your favourite cuts of beef.
Organic meat offers many benefits. Produced without pesticides or synthetic preservatives, you get great tasting food without the unwanted extras.
Here are just a few more advantages of going organic:
Why not make the change today? You really will be able to taste the difference. Check out our beef recipes over on the blog and see for yourself.
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Artist description:
Oh My God....that was tough!I found this picture on google..and I thought it would be pretty interesting to draw it...and challenging. A little practice on anatomy,movement,rain(never drawn before) and uhmm..clothes.:D Work in progress : [Link]
Java Draw Created Jul 03, 2009 338 x 470px Unless noted Copyright 2009 Roxana.
We encourage you to submit a comment and let the artist know what you think of this drawing. Please log in or join to post a comment.
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wow really amazing :D i like how you draw his hair :) and a great backround 5/5h C:
haha niiice
woooooow so brillant you are an excellent artist 5h fav
brilliant work!! 5h nd fav!
wow....wonderful! The action is perfect! 5H :)
Amazing, when SaveTheSeals said you were her idol, I thought I must see what Roxana can do, now you may just be the same. . . My Idol! :D
wow, just wow... 5! i cant believe somebody voted less than 5!!
lovely job
I love reading fan girl comment on this one xD nice job


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Public Library Vouchers
Procedures for Using Vouchers (Public Libraries):
Sample voucher to use as an example.
When ordering items yourself, have the invoice made out to your library and have the items shipped to your library. Do not "Bill to Peace Library System" and ship to "Your Library".
Do not use the "Sample Voucher" form in the Procedure Manual. Call Peace Library System and we will send vouchers with the proper numbering system for your library.
Procedure for filling out the form:
a. Check books received against books charged for on the invoice. This ensures that the invoice is correct.
b. Fill out voucher form:
• VOUCHER NO.: Vouchers are numbered by PLS sequentially and sent to the library.
• DATE: Write the date the voucher was filled out.
• CHEQUE TO: Indicate who payment should go to.
• DETAILS: Indicate any special instructions for PLS.
Example: Please catalogue all books OR books highlighted on the invoice are sent in for cataloguing; Invoice #23568.
Authorized signatory: Have the form signed by an authorized person.
c. Package up books, voucher, and invoice in a separate box
d. Send books, voucher and invoice to PLS for cataloguing and payment of invoice.
However, there are things to keep in mind:
a. PLS gets better discounts than a single library can get from a publisher or bookstore.
b. The larger the volume that PLS orders, the larger the discount that we get. So, ordering through PLS eventually benefits all libraries in the System with bigger discounts. The bottom line is that you get more book value for your dollar by ordering through PLS.
c. Thirdly, when you order directly from a publisher, you are paying shipping charges. When you order through PLS, the shipping charges are absorbed through the headquarters. Some large vendors, such as ULS, do not charge shipping to PLS headquarters because of the volume we order from them.


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Due to variances in monitors, the colors and patterns displayed may vary slightly from the actual product. Physical samples should be ordered prior to specifying.
Esquire introduces Allerton, a crisp vertical texture. When Allerton is washed with metallic ink, the vertical combed striations glimmer beautifully: tailored, structured and elegant. For a softer look, Allerton is shown in 7 matte ink finishes. Found in the palette of 21 colors are anthracite, antique gold, copper and pewter along with midnight blue, white pearl, tans and warm golden hues. Allerton provides the backbone and structure for any interior scheme. For a unique effect, try running the material horizontally!
Allerton is a 20 oz., Type ll vinyl made with Second-Look recycled technology.


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Welcome to Hindu Center of Virginia
Welcome to Hindu Center of Virginia (HCV) located at 6051 Springfield Road, Glen Allen, Virginia. Hindu Center offers religious services at the new Richmond Temple located on same campus. Hindu Center conducts several cultural activities through out the year in the community hall/auditorium capable of seating approximately 250 people. Most of the cultural programs are open to public and visit the events calendar to see the activities for this month. HCV holds to major events around April and September of each year.
In April the Center holds the Spring Festival and around the September the Festival of India. This year Festival of India is celebrating the 31st anniversary on September 29th and 30th. For more information on the Festival of India, visit the festivalofindia.org.
The community hall is available for personal use to the members for a nominal donation and you may call (804) 346-9954 for reservation. See rental information for more details.
The Hindu Center also offers cultural, language, yoga, and religious classes to the Richmond Community starting from age 5 and above. Please click on classes tab to see more details.


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Friday February 21, 2020; 08:26 pm EST
Can the Geminids outshine December's full moon?
The moon lights up the night this week, starting as a waxing gibbous, reaching full moon Tuesday and waxing slowly through the middle of the week. Look for the near-full moon beside the Pleiades star cluster Saturday.
You know the Big Dipper and the Little Dipper. The Pleiades, also known as the Seven Sisters and categorized as celestial object M45, could be called the Mini Dipper. The belt stars of the constellation Orion point up toward Taurus the bull and its orange-glowing eye, Aldebaran, with jagged V-shape of the Pleiades marking the bull's face. The star cluster is a test of your eyesight, as most people can see at best six of the seven sisters. But with binoculars or a small telescope, you'll see hundreds of stars.
Sunday the moon is beside the bull's glowing eye, Aldebaran. They are low in the east at nightfall and almost directly overhead at midnight. As daybreak approaches, they are sinking beneath the north-northwest horizon.
December's full moon Tuesday is commonly called the Long Night Moon, as well as the Cold Moon and the Moon Before Yule. The moon's nighttime path along the ecliptic during these longest nights of the year is long and high-arching. Six months from now, the sun will be traveling the same path during daylight hours. Conversely, where you see the sun speeding low through the sky, that's where you'll find the moon at night six months from now.
North of the Arctic Circle, the moon provides the only natural light, as the sun never rises. And south of the equator, where the daytime sun is at its highest and the moon traveling low against the horizon, the sun never sets at the Antarctic Circle and the moon never rises.
The full moon is joined by Jupiter, a few degrees to the lower left. The not-quite-so-bright star Betelgeuse, marking the shoulder of Orion the hunter, is about the same distance to the moon's right.
Unfortunately, the near-full moon competes with this year's Geminids Meteor Shower, which peaks between Friday night and Saturday morning. Year in and year out, this is one of the best showers, delivering up to 80 meteors an hour under ideal conditions. This year, only the brightest meteors will appear against the moon's glare … until the moon sets. Then, in the hour leading up to sunrise, the Geminids could be dazzling, with some predictions calling for up to 120 "shooting stars" during this narrow window.
Unlike all other meteor showers, which are the result of comets orbiting the sun, the Geminids are the offspring of an asteroid. The shower was first recorded just 150 years ago, and it wasn't until 1982 when the source was discovered, asteroid 3200 Phaethon. As the earth crosses the path of this interloper, tiny bits of ice, dust and other debris ignites upon hitting the atmosphere, resulting in meteors and even the occasional fireball.
The Geminids rain from December 7 through the 17, so keep your eyes to the sky all week. The meteors appear to emanate from between Castor and Pollux amid the constellation Gemini. While this is the apparent source, you can see meteors from anywhere in the sky; it's all just a matter where the meteors enter our atmosphere.


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Tequila helps make money flow
The drive to raise $6 million for the restoration of the Historic Elitch Gardens Theatre moved one step closer to completion after a tequila-and-tapas tasting held at Lola. A party room at the popular restaurant in Denver's Highland neighborhood was filled with a mix of those interested in sampling Proximus tequila and food prepared by owner/chef Jamey Fader while helping to preserve a city treasure.
Guests also were treated to a lively recollection of Elitch Gardens in its heyday, courtesy of retired Denver County Court Judge Frank Jamison and his wife, Joyce. The couple, 1947 graduates of North High School, had enjoyed Elitch's since they were children. The original Elitch Gardens at 38th & Tennyson was a popular attraction for over a century; from 1897 to 1963, its theater was home to the oldest summer stock theater company in the nation with such stars as Douglas Fairbanks, Lana Turner, Jose Ferrer, Robert Redford, Debbie Reynolds, William Shatner and Grace Kelly gracing its stage.
Kelly, in fact, was about to perform there when she received a telegram saying she had been cast in "High Noon."
"I was working in the office at the time," Joyce Jamison recalled, "and Grace Kelly was about the size of my arm … so darling and delicate that a whiff of wind would have blown her away."
"The history of Elitch's is amazing," remarked Jose Mercado, an actor and assistant professor of theater, video and film at the University of Colorado Denver. "The renovation will have a huge impact on our city." Mercado is a member of the Historic Elitch Theatre Foundation, formed to facilitate the restoration. The tequila party at Lola was the second in a series of fundraisers he is coordinating to raise money for the cause.
Paul Frank, the foundation's chairman, was among the guests at Lola. He acknowledged that raising money is tough in a down economy, but was confident that the funds will come in over the next two years of the campaign.
The drink of the evening was Tequila Proximus, a company founded by University of Colorado Boulder graduates Carlos Gonzalez and his wife, Claudia Moran, and partner Aaron Forman.
Along with the tequila and tapas, guests like Lois Paul and Kasia Jankowski also enjoyed tequila-infused ice cream donated by Little Man. Paul, in fact, was celebrating her appointment to the Excelsior Youth Center board; she's one of four new members.
Anyone wishing to contribute to the capital campaign may do so by sending checks to the Historic Elitch Theatre Foundation, 1225 Fifteenth St., Denver CO 80211.
Joanne Davidson: 303-809-1314 or email@example.com; also, GetItWrite on Twitter


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The raked sand in this dry garden suggests water rippling around stone islands. Bloedel Reserve, Japanese Garden on Bainbridge Island, Washington.
Japanese gardens have weathered the test of time.
Principles originating centuries ago still guide and inspire garden designers in search of harmony and beauty. Japanese gardens are often described as beautiful, simple, serene and harmonious. For the aspiring designer, intimidating also comes to mind. Some design principles are consistent across all design disciplines, while others seem new and challenging to a Western-minded gardener. Let's explore the Japanese garden and discuss a few concepts that make this approach so enduring.
Motomi Oguchi writes in Creating Your Own Japanese Garden: A Practical Guide that Japanese designers create according to the following principles:
1.) Each part of the garden should evoke how nature would present itself.
2.) The garden should be a new, creative design that is mindful of past masters' works.
3.) Create gardens of harmony that recall beautiful scenes in nature.
4.) Be flexible with site conditions, current needs, desires and self-expression. From a Japanese perspective, the human role in the garden is one of participation rather than conquest.
This stroll garden located in Kyoto, Japan, demonstrates shakkei or "borrowed scenery" by allowing views of mountains in the distance.
Formal design principles such as order, unity and rhythm are utilized in Japanese garden design as they are in any other form of design in any culture. The difference is where the Japanese place emphasis.
Plant materials in Japanese gardens are mostly evergreen. Deciduous trees, such as this weeping cherry tree, provide dramatic accents.
A slab bridge in the Hagiwara Tea Garden in California extends a pathway across a stream.
One emphasis is on combining objects in groups of three, often in triangular form for trees and stones. In such a grouping, the larger object is placed in the middle with the smaller ones to the left and right. The grouping forms a triangle and is asymmetrically balanced by varying the distance of the left and right objects depending on their visual weight. The composition is also staggered, attempting to achieve visual balance from multiple perspectives. Another point of emphasis in Japanese garden design is asymmetry. Asymmetrical visual balance suggests a natural setting and contrasts with the design symmetry found in Western formal gardens.
Other design principles in Japanese gardens are more familiar, but with distinct cultural application. Gardens are typically enclosed with a neutral background that interrupts the line of sight. Traditionally, the interior of a Japanese garden was considered sacred and the outside profane. The enclosure sets the garden space apart visually. In the ancient Shinto religion, gods were nature spirits. Therefore, the Japanese perception of the garden as a place to worship nature is not surprising according to Alvin Horton in Creating Japanese Gardens. Japanese gardens are designed for viewing from verandas or inside the residence, not recreation like Western landscapes. The landscape is often composed like a painting with roof eaves, columns and lower tree limbs framing the views. The sky is minimized by deep overhanging roof eaves and screening. The emphasis is on the horizontal plane, low and wide, rather than the vertical.
Shakkei or "borrowed scenery" is a universal design principle found in Japanese gardens in which distant shapes are echoed in the garden design, trees inside the garden blend with those outside the garden and overall garden design harmonizes with its surroundings.
Miekakure or "hide and reveal" is another common principle in which the garden is revealed to visitors gradually and can't be seen entirely from one vantage point. The principle of fuzei or "wind feeling" is unique to Japanese design. It is the visual perception conveyed when garden features suggest the effect of natural forces, like wind, on the landscape over time. A shaped pine suggests years of strong coastal winds. A moss-covered stone conveys the patina of age.
Top: A stepping stone pathway leads the garden visitor through a traditional entry gate.
Far Left: Bamboo is a natural choice for enclosing a Japanese garden.
Left: Shaped, rugged pines suggest the effect of wind over time.
Certain elements occur consistently in Japanese garden design. The combination of these, along with guiding design principles, can infuse your landscape with a Japanese feeling. Consider enclosure materials such as stone, wood, evergreen hedges and bamboo. Water, either actual or abstract, is an important component. Constructed waterfalls, streams and ponds echo the surrounding Japanese landscape within the garden walls. Raked sand is used to suggest water in other situations. Decomposed granite particles are used because their angular shape holds the precise raked patterns. The patterns suggest ripples around miniature islands of set stones. Functional bridges extend pathways over water or dry streams in the Japanese garden. Bridges are usually constructed of single slab stones or planks.
Water basins and stone lanterns are common elements found in Japanese gardens. They contrast subtly with the natural surroundings.
Utilitarian and decorative stonework is typically granite and schists in shades of gray and soft colors. No pure white or decorative colors are used in stonework. Water basins made of granite in both natural and cut shapes are found in many Japanese garden styles. Ishi-doro (stone pedestal lanterns) are utilized along pathways or in courtyards. Lanterns were popularized by Zen priests and traditionally incorporated into Japanese tea gardens. Stone lanterns are the most common feature found in Japanese gardens today. Their primary use is to subtly contrast with the surrounding natural elements.
Traditionally, plant material has been flowering and non-flowering broadleaf evergreens, conifers, shaped pines and mounding shrubs. Deciduous trees and moss are also important components, though mostly as accents.
Japanese design requires restraint and simplicity; by adhering to these rules your landscape could honor these ancient traditions and provide a respite from the outside world.
A version of this article appeared in a March 2012 print edition of State-by-State Gardening.
Photography courtesy of Loren Madsen.


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Blame Nicki Minaj For This Ignorant Ish: Suck My D*ck With A Mothaf**kin Condom!
In the Bronx. Some guy wildin out in school. - Tiny
Magic.D(Primus) who got the video popular on youtube. Amere Bryant is the main 1 in the video then we have Chris Scarlett, Denzel Robinson, and Gerardo
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text: Tomk 2 Posted December 23, 2007 okay so here goes: last friday out mingn, at chinese laundry the drum n bass room was going off had a chat with a few randoms few crazy arm twitch grabs and crazy eye contact the usual , so anyways after it finished i went back to chicks unit and she was a great person she was soooo friendly and down to earth!, so was her flatmate and my mate ben, and there was another guy to but he crashed out, so anyways, its 5am we are at there unit, we walk in to see these madddd settup gadgets, a projector aimed at the wall, and dear god no wha, wha really? are they! Pioneer cd decks? YES! so anyways we toked had a few chill out tracks some drum n bass break beats trance all that, and we all had a go at mixing, now i came up and sucked simply because it was my first go but was getting used to it faster than i anticipated, and i loved it! it was a feeling of learning something new that i hadn't felt for so long (simply because my job has so much repetition in it! So i sat back peaking and we ended up forming a 3 guys 1 girl human jigsaw puzzle lying over each others bodies and making contact and listening to the music and speaking some deep shit once in a while about lost friendships etc etc it was so great, and then the first step I took up to the decks was pure bliss, it felt insane just having the power to shift and change and make the tracks your own in a sense. It was such an amazing feeling! im a big music fiend and since that night mixing on pioneer 1000's DJM 800 mixer in a coffin case with good monitor speakers, I just had to have some! So im putting a order in for around 6 grand settup if no high 5gs. 2X pioneer 1000s 1X DJM 800 mixer 1X monitor speakers anything with a 1-1.25 inch tweet and 8.25 woofer or there abouts that hopefully is kevlar coated 1X pioneer Dj head phones enclosed of course. I cannot wait, infact as I am writing this im listening to one of the most gorgeous trance tracks ever created! ARMIN VAN BUUREN- Burned With Desire Feat. J suissa Cant wait to start guys Any feed back? or anyone else on this site dj id love to add you or add me (firstname.lastname@example.com) to msn as im becoming a big audiophile head hahaha cant blame me!? dads a sound techo/recordist his cousin produces krix speakers which are high quality for hoyts cinema apps and now home use as well. so maybee its a direction I could face even as a serious hobby of mine? I know it sounds queer or what ever but When i stood up at those decks just this insane feeling of power came to me, not one of Greed or attention whoring, but just such power at my disposal to change and manipulate songs into awesome mixes and create something new thanks guys! Wuv you all long tyme. Tom k Share this post Link to post Share on other sites


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Helping you find natural childbirth providers
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Birth Song Midwifery Services
I am a traditional midwife... I like that title. I have earned a CM in Michigan and a CPM through MANA. These help validate the training through apprenticeship and ongoing health education.I also have earned a B.S. in Biology. My daughter and son were both born at home. As they walk away to form their own lives, I am reminded of the importance of choices and support. I have been a midwife since 1981. I am over the 1600 baby mark. I have signs of good wear. Is it worth it? Incredibly so. Those babies are our future. Our thread to natural birth with dignity. My role as a midwife to families is to provide support, education, monitoring and counsel. I hope to help and encourage women and their families to be active participants in their pregnancy and birth.
I practice in the Grand Rapids area and a one hour circumference. My services include availability, prenatals, lending library, classes, home visits, Birth, postpartum care, birth certificate filing, and newborn screening. Please call for package fee information. The birth fee is to be paid by the birth, unless other arrangements have been made. Some insurances are covering Birth Song's services. I do request an initial interview before working with a family. This is important for education, clarification of services and informed consent.
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The Long Way is a sci-fi first person shooter game. This game is about a very big political conspiracy, which went out of control and had a very bad consequences on Earth and people.
Only registered members can share their thoughts. So come on! Join the community today (totally free - or sign in with your social account on the right) and join in the conversation.
TLW Concept01 Demo is released! (will be available soon from the downloads)


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First Time Riders
Welcome, Rookie Riders!
First and foremost, YOU ARE NOT ALONE!
Bike MS is an accessible and fun ride for nearly every skill level. Many Bike MS cyclists are participating for the first time. For that reason, we work hard to cater to your needs.
Here are some simple tips to make sure you'll be well prepared for the ride and have fun during ride weekend:
- Start fundraising today
- Train with someone who's cycled before - let them be a mentor to you
- Join one of the local recommended rides
- Set realistic goals
- Keep track of your mileage
- Drink before you become thirsty
- Don't forget to hydrate and eat
- Have your bike inspected at a local, sponsoring bike shop
- Buy padded shorts, gloves and a helmet
- Make sure your bike has been tuned and that it is properly fitted
- Start with short rides
- Keep your first few rides of the year short and easy. Don't worry about speed or distance on these rides. The purpose is to become comfortable on the bike and gain basic cardiovascular fitness.
- Add in occasional longer rides
- After becoming comfortable with riding for an hour or so, attempt an endurance day of two or more hours once a week.
- For more advanced training, add hill intervals.


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Call for Appointment.
A luxury community located in Travelers Rest, SC.
Current Incentive:
$5,000 in Savings for Homes Over $200,000
$3,000 in Savings for Homes Under $200,000
Savings Can Apply Toward: Closings Costs, Upgrades, Total Price
Some exclusions apply. Incentive valid with full price offers using our recommended Lender and Attorney. Not applicable in all communities or when building on your own property.
The information contained on this page is reliable, but not guaranteed. Prices and plans are subject to change without notice. Renderings, photos, and floor plans may show optional upgrades. And any listed square footage is approximate.
304 Cherokee Vally Way, Travelers Rest, SC 29690
Travelers Rest, SC 29690


text: zeelog 408 Report post Posted September 12, 2012 (edited) ::::This is my experimental build of ParanoidAndroid 2+::::: CURRENT VERSION PA BLADE 2.81 This is not just tablet mode To be honest, this is not tablet mode at all, it has nothing to do with silly build.prop hacks. This is the first and only Android rom to feature true Hybrid mode. This rom lets you scale and project every app, every widget, even systemcomponents individually. Remember, android is modular, everything is an app: Lockscreen, navigationbar, dialogs, popups, keyboards, widgets, and your regular apps of course. Apps have the capability to switch into various designs or layouts according to the device they run on. This can result in a complete new experience as many apps will transform to the better. Now for every element that you like chose a mode (PhoneUI, Phablet, TabletUI) and/or a size. You are 100% independent of the system DPI which runs nicely in whatever value it has been assigned to. You do not need to boot your phone into a certain DPI. Neither will most of the changes you apply require a reboot. You will not suffer from the myriads of troubles which normally haunt you under build.prop tablet mode. Your market, phone, etc. will all work, apps won't shrink on you unless you shrink them yourself. This project will entirely transform your device, but retain the aesthetics and the feel of your phone. Based on CM10 4.1.2 JellyBean MINIMUM Partition: 160MB Use at your own risk, I'm not responsible for any data loss,etc etc, always TAKE A FULL BACKUP before trying out a new ROM!! As stated above, this is an experimental build. LATEST DOWNLOAD: Version 2.81 ROM: http://goo.im/devs/z...0330-125942.zip CHANGELOG: Fix graphical glitches in navbar/statusbar Fix switching off FM audio in some cases Update Effem (bugfixes, in-call muting) (thanks to daemond for the above) Limit number of hidden apps Added CM File Manager Version 2.80 ROM: http://goo.im/devs/z...0318-154719.zip CHANGELOG: Added new FM RADIO application (Effem)+ RDS Fix photo editor crashes Fix camera crashes (Credit to daemond) Version 2.70 ROM: http://goo.im/devs/z...0227-153956.zip CHANGELOG: Fix corruption in Trebuchet's icon label rendering Added FM radio support Libpower tunings Updated KGSL from CAF, fixes GPU out of memory issues (Credit to Daemond for above fixes) Updated SuperSU to multiuser edition Version 2.66 ROM: http://goo.im/devs/z...0202-170204.zip CHANGELOG: Prefer RGB565 pixel for opaque surfaces & bitmaps Renable 16bpp drawing cache Use RGB565 pixel format for wallpaper (Credit to Daemond) Version 2.65.1 ROM: http://goo.im/devs/z...0127-154909.zip CHANGELOG: Fixed Panorama Mode Version 2.6.5 ROM: http://goo.im/devs/z...0124-165429.zip CHANGELOG: Enabled hardware vsync Project Butter complete (Credit to Daemond) Version 2.6.4 ROM: http://goo.im/devs/z...0120-141145.zip CHANGELOG: Disabled WebGL Fix audio routing (SIP audio, notifications with headphones) Various fixes for hwui to avoid possible leaks and screen corruption Fix messed up u/v plane alignment in some videos All the above fixes: Credit to daemond Version 2.6.3 ROM: http://goo.im/devs/z...0116-163536.zip CHANGELOG: Added Native WiFi Tethering support (Credit: daemond) Added WiFi AP Tethering Toggle Version 2.6.2 ROM: http://goo.im/devs/z...0113-140157.zip CHANGELOG: Fixed FC when hiding battery icon Fixed 2G/3G toggle Added option to move tablet status bar on top (thanks C3C0) Fixed Camera preview glitches ADB Sideload support Enabled wma audio hw decoder Fixed charger detection mode Fake vsync events Set correct permission for boostpulse Version 2.6.1 ROM: http://goo.im/devs/z...0102-115358.zip CHANGELOG: Fixed camera panorama mode Fixed native USB tethering (credit WaylandACE,KonstaT) Version 2.6.0 ROM: http://goo.im/devs/z...2012-150614.zip CHANGELOG: Fixed video hw decoding playback (youtube hq support) video playback improvements (credit Ganster, KonstaT) Version 2.5.5 ROM: http://goo.im/devs/z...2012-110612.zip CHANGELOG: Fixed Video Recording & Playback (Credit KonstaT) Removed tethering toggles Added ability to switch off settings button Version 2.5.4 ROM: http://goo.im/devs/z...2012-122600.zip CHANGELOG: Fixed FC (on 2.5.3) on camera panorama mode Fixes phablet mode buttons CM updates Version 2.5.3 ROM: http://goo.im/devs/z...2012-140155.zip CHANGELOG: Fixed Toggles Section (AutoRotate toggle back) Per App Color Fix Expanded Desktop Fix Some kernel updates (Credit KonstaT) Version 2.5.2 ROM: http://goo.im/devs/z...2012-213840.zip CHANGELOG: Added PA Colors Preset in PA Settings Added Ability to change Status Bar Color per APP Added Color Scheme for Toggles Update SuperSU Version 2.5.0 ROM: http://goo.im/devs/z...2012-184201.zip CHANGELOG: Updated PA Settings (Extras) Per-App COLOR (newest PA invention) Ability to change softkey colours per each app Added navigation bar colours (softkeys) Added Status Bar colour changing (StockUI) Added Text Only Battery Style Added Day & Month option in status bar Further trimming on bootanimation (reduced by ~2MB) Use Updated GAPPS 4.1.2 (17.10) - by KonstaT Version 2.22.9 ROM: http://goo.im/devs/z...2012-132744.zip CHANGELOG: Fixed ParanoidAndroid Settings StockUI Added PA preset in PA Settings Remerged battery status bar Version 2.22 ROM: http://goo.im/devs/z...2012-150414.zip CHANGELOG: New Paranoid Settings Layout New Circle Battery Mods (CM) Added new toggle layout (multi row) Added Day & Month option in Status Bar Added zRAM support - Credit KonstaT Embedded Camera in Gallery App - Credit KonstaT Hide Center Clock in TabletUI Use Updated GAPPS 4.1.2 (17.10) - by KonstaT Version 2.21 ROM: http://goo.im/devs/z...2012-155238.zip CHANGELOG 2.21 Now based on CM JellyBean 4.1.2 Added more toggle styles Ability to adjust toggles to fit to screen layout More bugfixes [PA] + Latest CM commits ** AutoRotate toggle still missing, not fixed yet Version 2.18 ROM http://goo.im/devs/z...012-184614.zip CHANGELOG 2.18 Added more toggles Fixed DnD toggle (from 2.17.9) Added Do not disturb option (to disable ticker animation & sound for incoming notifications) General fixes to TableUI toggles more bugfixes (PA) Removed PA Wallpapers(we need space on our Blade!) Enabled Changelog from GOO app Version 2.17.1 ROM http://goo.im/devs/z...012-142130.zip CHANGELOG 2.17.1 Added Notification Toggles Styles (works also in tablet mode) Fixed default sounds in buildprop Other CyanogeMod latest commits Version 2.16 ROM http://goo.im/devs/z...012-202348.zip CHANGELOG 2.16 Status Bar Transparency Fix Fixed double entries in settings menu (my bad) Applied latest patches from KonstaT device config Version 2.15 ROM http://goo.im/devs/z...012-194902.zip CHANGELOG 2.15 Nothing much...Lock Screen See Through Version 2.14 ROM http://goo.im/devs/z...2313.zip CHANGELOG 2.14 Added Partition Info (Settings) Credit KonstaT Added Disable Boot Animation (Performance Settings) Credit KonstaT Re designed PA Wallpapers App - Credit PA team Added Status Bar Transparency option SuperSU instead of SuperUser Version 2.13 ROM http://goo.im/devs/z...012-221617.zip CHANGELOG: v 2.13: Now supports GOO.IM Update Manager Added some tweaks for smoother UI Fixed Camera Panorama Mode Most of ZTE Blade patches to date have been merged Added Split Button in Tablet Mode Version 2.11 ROM: https://hotfile.com/...84116.zip.html CHANGELOG 2.11 Initial Release GAPPS 4.1.2 (17.10.2012) - http://tinyw.in/tVM3 Thanks to KonstaT INSTALLATION INSTRUCTIONS: Download ROM, GAPPS on your SDCARD Boot into Recovery, Clockwork. Optionally, but HIGHLY RECOMMENDED: BACKUP YOUR CURRENT ROM Wipe Data/Factory Reset (Mandatory if you're coming from any other ROM!) Wipe Cache Mounts/Storage > Format System (Mandatory if you're coming from any other ROM!) Advanced > Wipe Dalvik Cache Install from zip > Select downloaded ROM Install from zip > Select download GAPPS Reboot (might take a while,pls be patient!) If you're coming from the initial release, then it's recommended that you take a backup of your PA Settings, Download latest version, install ZIP from SDCARD Install GAPPS from SDCARD Wipe Dalvik Cache Reboot CREDITS: KonstaT - without him, this wouldn't be possible. BIG Thanks! Ganster Daemond C3C0 Utacka ParanoidAndroid Team CM Team SOURCES: Device / Kernel / Proprietaries / Base Edited July 12, 2013 by zeelog 14 Quote Share this post Link to post Share on other sites


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Anales de la Asociación Química Argentina
Print version ISSN 0365-0375
An. Asoc. Quím. Argent. vol.94 no.1-3 Buenos Aires Jan./July 2006
Effects of intramolecular interactions on NMR J(13C,1H) spin-spin coupling constants. A DFT-B3LYP calculation and exprimental study
1Taurian, O. E.; 2Contreras, R. H.; 2De Kowalewski, D. G.
1 Physics Department, FCEFQyN, University of Río Cuarto, Ruta Nacional 36, Km 601, 5800 Río Cuarto, Argentina.
Section of Physical Chemistry, FQByF, University of San Luis, Chacabuco and Pedernera, 5700 San Luis, Argentina.
FAX: +54 358 4680280, E-Mail: firstname.lastname@example.com
2Physics Department, FCEyN, University of Buenos Aires and CONICET, Ciudad Universitaria, P. 1, (C1428EHA) Buenos Aires, Argentina.
Received March 3rd, 2006. In final form May 28th, 2006
Dedicated to Prof. Imre G. Csizmadia on the occasion of his 75th birthday
Two different types of interactions affecting both 1J(C,H) and longer range nJ(C,H) spin-spin coupling constants, SSCCs, are studied from a theoretical point of view in model compounds. The study, based on the DFT methodology, was supplemented with measurements of several nJ(C,H) couplings. The studied interactions are, on the one hand, those of electrostatic origin caused by proximity of either an electronegative atom or of an H atom and a C—H bond on the corresponding 1J(Csp2,H) SSCC. In agreement with previous observations it was determined that the former interaction yields an increase while the latter a decrease in the corresponding 1J(C,H) SSCC. Both of these changes are notably shielded by the dielectric effect of the solvent. On the other hand, the influence of the strong negative hyperconjugative interactions that take place in the aldehyde moiety on the corresponding 1J(Cc,Hf) and 2J(C,Hf) SSCCs, are studied. These negative hyperconjugative interactions are inhibited by, for instance, the intramolecular hydrogen bond in salicylaldehyde, the dielectric effect of the solvent, or the electrostatic effect of a proximate electronegative atom close to the formyl proton of the Hf—Cc bond.
En el presente trabajo se estudian compuestos modelos, desde un punto de vista teórico, dos tipos de interacciones diferentes que afectan las constantes de acoplamiento spin-spin, SSCCs, 1J(C,H) las de mayor rango nJ(C,H). El estudio, basado en metodología DFT, fue complementado con la medición de varios acoplamientos nJ(C,H). Las interacciones estudiadas son, por una parte, aquellas de origen electrostático causadas ya sea por la proximidad de un átomo electronegativo o bien por un átomo de H y un enlace C—H en el correspondiente 1J(Csp2,H) SSCC. En acuerdo con observaciones previas, se determinó que la interacción nombrada en primer término, conduce a un incremento en el correspondiente 1J(Cc,Hf) SSCC mientras que la última causa disminución en el mismo. Ambos cambios están notablemente apantallados por el efecto dieléctrico del solvente. Por otra parte, se estudia la influencia de las interacciones hiperconjugativas fuertemente negativas que tienen lugar en la mitad aldehídica sobre los correspondientes 1J(Cc,Hf) y 2J(C,Hf) SSCCs. Las interacciones hiperconjugativas fuertemente negativas son inhibidas, por ejemplo, por el enlace hidrógeno intramolecular en aldehído salicílico, el efecto dieléctrico del solvente o el efecto electrostático de un átomo electronegativo cercano al protón formílico del enlace Hf—Cc .
Nuclear spin-spin coupling constants, SSCCs, as measured by high resolution NMR spectroscopy, are very sensitive parameters to many intra- and inter- molecular interactions. For this reason these parameters are considered to be excellent probes to gauge such interactions. However, to fully appreciate such a capability, it is important to understand how subtle changes in the molecular electronic structure affect SSCCs. To achieve such an understanding, it is important to calculate SSCCs with reasonable accuracy for some model compounds; however, for many years such a calculations were a difficult task for Quantum Chemistry. An important breakthrough took place during the last decade when the first attempts to calculate them within the framework of the Density Functional Theory, DFT, [1] were reported. It is now common to find in the literature papers where SSCCs are thus calculated in polyatomic compounds, with a good agreement between calculated and experimental values. It is important to recall that, according to the non-relativistic Ramsey's formulation, isotropic SSCCs, i.e. measured in isotropic phases, [2] are contributed by four terms, namely, Fermi contact, FC, spin-dipolar, SD, paramagnetic spin-orbit, PSO, and diamagnetic spin-orbit, DSO, eq. (1),
In many cases for light atoms like 1H, 13C and 15N, SSCCs are by far dominated by the FC term. However, to make a correct analysis all four terms should be included.
In previous papers it was reported that 1J(C,H) SSCCs are notably affected by electrostatic interactions[3,4,5,6] and by hyperconjugative interactions either from the corresponding C—H bond or its antibond. The main purpose of this paper is to get a deeper insight into how these effects operate, and how other nJ(C, H) SSCCs can also be used as excellent probes to investigate at least part of such interactions. To study 1J(C, H) SSSCs five mono- di- and tri-substituted benzenes are taken as model compounds, 1 to 5 (X=NO2). It should be noted that side chains in 1 to 4 correspond to substituents bearing compound 5(X=NO2). To study a few longer range nJ(C,H) SSCCs (n > 1), in adittion to compound 5, five additional 5-X-salicylaldehyde derivatives were selected, and a set of nJ(C,H) SSCCs were measured and calculated within the DFT framework. Within an aldehyde group, CHO, very strong negative hyperconjugative interactions [7] take place, corresponding to charge transfer interactions from the oxygen non-bonding electron pair of p symmetry into the (Cc—Hf)* and (Cc—C1)* antibonds [6]. The consequences of these negative hyperconjugative interactions on NMR parameters are really remarkable; for instance, this is the origin of the very large geminal SSCCs observed across a carbonyl group [8] and the present evidence indicates that such couplings show a strong dielectric solvent effect. The following three examples are typical of a geminal coupling through a carbonyl group (experimental values), e.g. in acetaldehyde 2J(C,H) = 29.74 Hz, in gas phase, and 2J(C,H) = 26.25 Hz in DMSO solution [9]; in formamide [10] 2J(15N,1H) = -20.14 and -15.30 Hz, for gas-phase and DMSO solution, respectively; |2J(17O,1H)| ≈ 40 Hz in methyl formate [11]. Such SSCCs originate mainly from the FC term and it is known that for geminal SSCCs, hyperconjugative interactions into the coupling pathway yield an algebraic increase in the FC term [12]. On the other hand, hyperconjugative interactions from the coupling pathway yield an algebraic decrease in such a term. It is also important to recall that negative hyperconjugative interactions are known to be slightly inhibited by the dielectric effect of the solvent [13,14]. This was also found to be the origin of the inhibition of the lone-pair orientation effect [15], and the solvent dependence of 2J(C,H) SSCC in acetaldehyde [16]. For this reason, in this work special attention is also paid to 2J(C1,Hf) SSCCs in 1, 3, 4, and 5(X), where X = H, OCH3, Br, Cl, OH, NO2. First of all, compounds 1 to 5, 1J(C,H) SSCCs were calculated where, for the sake of completeness, all four terms of eq. (1) were included. In compound 3, two different conformations were taken into account, a = 0° and a= 180°; similarly, in compound 4, two conformations were considered, b = 0° and b= 180°. Medium effects were taken into account by performing calculations on each isolated compound and considering a solvent with a dielectric constant of 46.7, which corresponds to an infinitely diluted dimethylsulfoxide, DMSO, solution. This choice was made since solutions of these polar compounds were prepared at high concentrations in a polar solvent, and therefore, when taking e = 46.7, it was not intended to reproduce qualitatively the experimental conditions, but to represent only a strong polar solution.
NMR measurements
All 1H and 1313C NMR spectra were recorded, using 5 mm sample tubes, on a Bruker AM500 instrument operating at 500.138 and 125.760 MHz. 64 K data points were acquired with a spectral width of 1939 Hz. FIDs were zero filled to 128K data points, corresponding to a digital resolution of 0.2 Hz. Samples were prepared using CD3CN as solvent, at concentrations ca. 80 % w/w. In order to identify the coupling nuclei in each J(C,H) SSCC, selective double resonance experiments were carried out on each of the ring proton signals. All spectra were recorded at the LANAIS NMR-500 facility in the Department of Physics, FCEyN, University of Buenos Aires. Compounds 5 (X= H, OCH3, Br, Cl, OH, NO2) were available commercially and their identities and purities were checked by recording their 1H and 13C NMR spectra.
DFT calculations
Geometry optimizations and calculations of all four terms of SSCCs, FC, SD, PSO and DSO, were carried out within the DFT framework. The CP-DFT [17,18] perturbative approach was used (as implemented in the Gaussian 03 package of programs [19]) for calculating all the three second-order terms of SSCCs, i.e. FC, SD, and PSO; the DSO term was evaluated as an expectation value over the electronic ground state. The functional employed is the hybrid B3LYP of Lee et al. [20], where the exchange part is treated according to the Becke's three parameter approach [21,22]. For geometry optimizations the 6-311G** basis set was employed, while for calculating SSCCs the EPR-III basis set [23] was chosen, with triple-zeta quality including diffuse and polarization functions. The s part of this basis set is enhanced with tight s functions to better reproduce the electronic density in the nuclear regions; this point is particularly important when calculating the FC term. It is important to stress that coupling constants calculated at the B3LYP/EPR-III level are close to their basis-set converged values [24]. Dielectric solvent effects were taken into account using the SCRF-PCM version of the polarization continuum model, PCM, of Tomasi et al. [25,26,27]. Calculation of SSCCs including dielectric solvent effects were performed using optimized geometries obtained within the SCRF-PCM model. All DFT calculations were carried out with the Gaussian 03 package of programs. Hyperconjugative interactions were studied using the NBO approach [28,29].
Results and Discussion
A good starting point to study how different interactions affect 1J(Csp2,H) SSCCs is to consider such couplings in benzaldehyde, 1, and in phenol, 2. For these two compounds, total calculated 1J(C,H) SSCCs considering two different solvents, e = 1 and e = 46.7, i.e. an isolated molecule, and an infinitely diluted solution in dimethylsulphoxide, DMSO, are compared in Table 1 with the respective experimental values, taken from Ref.[30]. It should be recalled that in 1 and 2 both planar rotamers are equally populated and, therefore, experimental 1J(C,H) SSCCs for ring positions 2 and 6, and for 3 and 5, correspond to their respective average value. It is expected that for the former two, i.e ortho positions, the inductive and resonance effects be almost the same; a similar assertion should hold for the latter two, meta positions. Therefore, the large differences between 1J(C2, H2) and 1J(C6, H6) SSCCs, D(1Jo) = 7.6 Hz in 1, and D(1Jo) = -6.8 Hz in 2, Table 1, suggest that they originate mainly from an electrostatic effect arising from the proximity between the side chain and the ortho protons. It is to be noted the opposite sign for calculated D(1Jo) in 1 and 2, i.e. in 1 the proximity of H2 to the oxygen O=C is similar to that of the oxygen O—H in 2, and vice versa. To estimate such an effect, in this Table the NBO natural atomic charges on the H atoms are also shown. In this study it will be neglected any effect from s-hyperconjugative interactions involving the respective side-chain and the (C—H)* antibond. As observed previously, [5] in aromatic compounds the proximity of an oxygen atom to an H—C bond yields an increase in the FC term of its 1J(C,H) SSCC. On the other hand, the proximity between two H atoms yields a decrease in the corresponding 1J(C,H) SSCC [32,33]. It is important to note that in 1 and 2 solvent effects on 1J(C,H)o (ortho to the side-chain) SSCCs are of opposite signs. This trend is consistent with the fact that differences D(1Jo) in both compounds are of electrostatic origin, and dielectric solvent effects should shield such interactions. A similar conclusion is reached comparing the NBO atomic charges at H2 and H6; it is also interesting to note that for calculations in a very polar solvent both atomic charges tend to give the same value. The asymmetry between 1J(C3,H3) and 1J(C5,H5), D(1Jm), is small both in 1 and 2; however, a slight difference between their solvent effect is still observed, which is assumed to originate on the opposite electrostatic effects of the side–chain on both C3—H3 and C5—H5 bonds. In the same Table 1 it is observed that in 1 the LP(Op)—>(Cc—Hf)* negative hyperconjugative interaction is inhibited, due to the dielectric effect of the solvent, by 2.7 kcal/mol. It is also noted that the SSCC where the largest solvent effect takes place is 1J(Cc,Hf); although the inhibition of such an interaction yields a direct increase of this coupling, the total effect should also originate in the inhibition of the LP(Op)—>(Cc—Cl)* negative hyperconjugative interaction.
Table 1: Comparison between calculated and experimental values of 1J(C,H) SSCCs (in Hz) in compounds 1 and 2. The NBO atomic charges on each proton are also shown (in 10-3 au). S.E. stands for solvent effect on calculated SSCCs and NBO atomic charges, it is given by the difference F(e = 46.7) – F(e = 1), where F stands for either J or QH.
a) Taken from Ref. [30]
b) Int stands for LP(Op)—>(Cc—Hf)* negative hyperconjugative interaction
In Table 2 calculated 1J(C,H) SSCCs are compared for conformers 3a and 3b; in 3a calculated SSCCs are also compared with experimental values. It is important to note that in 3b the intra-molecular hydrogen bond is broken. The behavior of 1J(C3,H3) SSCC can easily be rationalized since in 3a the C3—H3 bond is close to the in-plane electron pair of the hydroxyl-oxygen non-bonding and therefore a significant contribution to the calculated SSCC originates in this electrostatic interaction.
Table 2. Effect of the O—H conformation on 1J(C,H) SSCCs (in Hz) in (3). S.E. stands for solvent effect on calculated SSCCs and NBO
atomic charges (in 10-3 au), it is given by the difference F(e = 46.7) – F(e = 1), where F stands either for J or QH.
Therefore, when changing the O—H conformation this effect is "quenched" and a decrease in the 1J(C3,H3) SSCC is expected, which is further magnified since in 3b the hydroxyl-proton is close to H3. In this way a total decrease of 8.4 Hz is observed when calculations are carried out for an isolated molecule (e = 1). This rationalization is further supported by the following considerations: in 3a a solvent effect of only 1.4 Hz is observed for 1J(C3,H3). This is consistent with the effect of the oxygen proximity being partially shielded by the dielectric effect of the solvent.
Table 3. Effect of the CHO conformation on 1J(C,H) SSCCs (in Hz) in (4). S.E. stands for solvent effect on calculated SSCCs (in Hz) and NBO
atomic charges, QH, (in 10-3 au), it is given by the difference F(e = 46.7) – F(e = 1), where F stands either for J or QH.
a) Int stands for LP(Op)—>(Cc—Hf)* negative hyperconjugative interaction.
On the other hand, the "solvent effect", S.E., on 1J(C33,H3) in 3b is increased to 6.7 Hz, with a partial dielectric shielding of the proton proximity effect on 1J(C3,H3) SSCC. For an isolated molecule, (e = 1), the a—>b conformation change yields a change in 1J(C4,H4) SSCC of 0.9 Hz, and this difference is reduced to 0.1 Hz for e = 46.7. On the other hand, such a conformational change yields a change in 1J(C6,H6) of only 0.6 Hz (isolated molecule), which, although small, suggests that, in 3a the intra-molecular hydrogen bond somewhat inhibits the n(Op)—>(Cc—Hf)* interaction. When the hydrogen bond is broken, 3b, that negative hyperconjugative interaction is increased (from 20.9 to 24.0 kcal/mol), affecting the C6—H6---Hf—Cc proximity effect on 1J(C6,H6) There is a substantial change in the solvent effect on this SSCC, i.e. from 5.0 to 3.6 Hz, for 3a—3b. This trend is consistent with a dielectric solvent inhibition of the strong n(Op)—>(Cc—Hf)* negative hyperconjugative interaction, i.e. it seems that this is an indirect effect: when such hyperconjugative interaction is inhibited, then the C6—H6---Hf—Cc proximity effect is enhanced. In 3a this negative hyperconjugative interaction is also inhibited by the intra-molecular hydrogen bond; for e = 1 this inhibition goes from 24.0 kcal/mol (without the intra-molecular hydrogen bond, 3b) to 20.9 kcal/mol, when the hydrogen bond is operating, 3a, which is weakened by the dielectric effect of the solvent. For this reason it is not surprising to observe a decrease in the 1J(C6,H6) solvent effect in 3b.
In Table 3, calculated 1J(C,H) SSCCs for conformers 4a and 4b are compared. The effects of such a conformational change on 1J(C2,H2) and 1J(C6,H6) SSCCs are quite similar to the difference between 1J(C2,H2) and 1J(C6,H6) in 1. As it could be expected, 1J(C3,H3) and 1J(C4,H4) are only slightly affected. A change quite remarkable is observed for 1J(Cc,Hf) SSCC; as discussed previously, [5] it seems to originate from a "meta-NO2" electrostatic effect, which creates an electric field along the Cc—Hf of this polarity Cc(+)—Hf(-). This result is compatible with the strong solvent effect calculated for 1J(Cc,Hf) SSCC in 4a, S.E = 8.2 Hz, which is reduced to 4.4 Hz in 4b. According to results previously published [5], this observation can be rationalized on the following grounds. The electrostatic field produced by the NO2 along the Cc—Hf bond affects, on one hand, the electronic distribution along that bond, and, on the other hand, such an electric field inhibits the n(Op)—>(Cc—>Hf)* negative hyperconjugative interaction. As discussed previously through the model systems 7a and 7b, with q < 0, these two effects are intertwined and difficult to consider separately [6].
As noted previously, aromatic 1J(C,H) SSCCs calculated at the B3LYP/EPR-III level, appear to be overvalued. Following Helgaker et al., [34,35] and Oddershede et al. [36] the inclusion of nuclear motion effects, assuming such effects originating mainly in the Zero Point Vibrational correction, ZPV, the overall overvaluation seems to be about ca. 10 Hz. However, results displayed in Tables 1 and 2, suggest that for SSCCs undergoing electrostatic effects the ZPV correction could be smaller than for other C—H bonds without such a proximity interaction.
According to comments made in the Introduction's section, 2J(Cc,Hf) SSCCs in benzaldehyde derivatives could be sensitive to several interactions. These effects are compared in Table 4, for conformations a and b, calculated 2J(Cc,Hf) SSCCs for 3 and 4 compounds. The respective calculated LP(Op)—>(Cc—>Hf)* and LP(Op)—>(Cc—Cl)* negative hyperconjugative interactions as well as the occupancy of the respective (Cc—Hf)* and (Cc—Cl)* antibonds are also shown. The following features of data listed in Table 4 are worth noting. The intra-molecular hydrogen bond in 3a inhibits both the LP(Op)—>(Cc—Hf)* and LP(Op)—>(Cc—Cl)* negative hyperconjugative interactions, and the dielectric effect of the solvent yields a further inhibition of such interactions. No experimental 2J(Cc,Hf) SSCC is known for compound 4, nonetheless, it is observed that the dielectric effect of the solvent yields inhibitions slightly different than those observed for compound 3, and such inhibitions are somewhat stronger in 4b than in 4a.
Table 4. Side-chain conformation effect on 2J(Cl,Hf) SSCC (Hz) in compounds 3 and 4. The intensity of the negative hyperconjugative interactions of type LP
(Op)—>(Cc—Hf)* and LP(Op)—>(Cc—Cl)* are also shown (in kcal/mol). Occ. stands for the occupancy of the respective antibonding orbital (times 103).
In Table 5 several experimental nJ(C,H) SSCCs are compared for compounds 5(X=H, OCH3, OH, Cl, Br, NO2). For the last compound, X = NO2, theoretical values calculated for e = 1 and e = 46.7 are also shown. The important variation of 1J(Cc,Hf) SSCC along this series of compounds is in agreement with the important sensitivity of this SSCC to different interactions. The rather large solvent effect, 8.2 Hz, calculated for that SSCC is also in line with the meta electrostatic NO2 effect discussed in Table 3 for compound 4. 2J(Cl,Hf) SSCCs are also sensitive to a meta substitution, in agreement with discussions made above about this large geminal coupling defined mainly by the negative hyperconjugative interactions of types LP(Op)—>(Cc—Hf)* and LP(Op)—>(Cc—Cl)*. Experimentally, the 2J(C2,H3) SSCCs are only determined as absolute values; however, calculations for 5(X=NO2) indicate that this value is negative, it is also accepted, for all other compounds, that the coupling is negative. The vicinal couplings 3J(C2,Hf) and 3J(C6,Hf) correspond to trans and cis arrangements of their coupling pathway. These values are notably different from "normal" values for such coupling pathways [6]. Anomalous behaviors for vicinal SSCCs whose coupling pathways undergo strong negative hyperconjugative interactions were commented elsewhere. It is noteworthy how different are 3J(C2,Hf) and 3J(C2,H4) SSCCs for compounds displayed in Table 5; similar comments hold for 3J(C2,H6), 3J(C2,H4) and 3J(C5,H3) SSCCs. The two four-bond J(C,H) couplings, 4J(Cl,H4) and 4J(C6,H3) are calculated as negative in 5(X=NO2), and therefore the experimental values are assumed to be negative. It is interesting to remark that such values are compatible with couplings dominated by the FC term and transmitted through the p-electronic system [37].
Table 5. Selected nJ(C,H) SSCCs (in Hz) in 5(X=H, OCH3, OH, Br, Cl, NO2) experimental values measured as part of this work.
For X = NO2 they are compared with the corresponding calculated values for e = 1 and 46.7.
Concluding Remarks
Benzaldehyde (1) and phenol (2) are excellent model compounds to understand the electrostatic proximity effects on 1J(C,H) SSCCs for aromatic C—H bonds. The proximity to an electronegative atom brings about an increase of the coupling, while the proximity to an H atom (with positive charge) originate a decrease of the coupling. For an isolated molecule, the sum of the absolute value of both effects amounts to 7.6 Hz in (1) and 6.8 Hz in (2). These two values are notably reduced to 2.5 Hz and 1.3 Hz, respectively, when calculations are carried out in a polar solvent. These results suggest that the assumption commonly made about the ZPV correction for any aromatic 1J(C,H) SSCC, close to 5 Hz, could be notably wrong when the coupling under consideration is subject to a strong proximity effect. In general the study of the influence of nuclear motions on SSCCs is computationally demanding [34,35,36]; for this reason, calculations were carried out in some model compounds and results are thus generalized to bonds of similar hybridizations. The influence of strong electrostatic effects on the ZPV correction was not addressed.
1J(Cc,Hf) and 2J(Cl,Hf) SSCCs in benzaldehyde derivatives depend strongly on the LP(Op)—>(Cc—Hf)* and LP(Op)—>(Cc—Cl)* negative hyperconjugative interactions. These hyperconjugative interactions are affected by several factors like the C=O---H—O hydrogen bonds in compounds 3 and 5; dielectric effects of the solvent and proximity factors like the meta NO2 effect on 4a and 5(X=NO2). In this case it would also be interesting to carry out detailed studies on how the effect of nuclear motion strongly affects SSCCs and its dependence on negative hyperconjugative interactions like 1J(Cc,Hf) and 2J(Cl,Hf) in benzaldehyde derivatives. The combination of nuclear motion and the dielectric effect of solvent on SSCCs is a subject not yet dealt with in the literature.
Although longer range SSCCs were not studied in detail in this work, results presented in Table 5 suggest that vicinal J(C,H) SSCCs may take quite unusual values when part of the coupling pathway is involved in strong negative hyperconjugative interactions. This observation is consistent with some anomalous vicinal SSCCs commented in two recent reviews [32,33].
OET is grateful to SeCyT-National University of Rio Cuarto for financial support. RHC gratefully acknowledges financial support from CONICET (PIP 2140) and UBACyT (X-222).
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Votre titre Audible gratuit
The Long Tail
What happens when everything in the world becomes available to everyone? When the combined value of all the millions of items that may sell only a few copies equals or exceeds the value of the few items that sell millions each? When a bunch of kids with no profit motive can record a song or make a video and get the same electronic distribution for it as the most powerful corporation?
Chris Anderson, editor in chief of Wired magazine, first explored "The Long Tail" in an article that has become one of the most influential business essays of our time. Using the worlds of movies, books, and music, he showed how the Internet has made possible a new world in which the combined value of modest sellers and quirky titles equals the sales of the top hits. He coined the term "The Long Tail" to describe this phenomenon, a phrase that's since appeared in boardrooms and media around the world.
"In short, though we still obsess over hits," Anderson writes, "they are not quite the economic force they once were. Where are those fickle consumers going instead? No single place. They are scattered to the winds as markets fragment into a thousand niches."
Ce que les membres d'Audible en pensent
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- Jim
- 17/03/2007
Good Book, Flawed by Repition
I thought this was a good book that should have been about half the length that it actually was. It's too bad no abridged version is available. I agreed with the author's ideas, but about 3 hours in, I really felt that he was repeating himself unnecessarily.
6 personnes ont trouvé cela utile
- Kenneth
- 29/01/2007
My Pick for Book of the Year
This is the best book I've read in about a year.
It explains so much of the internet phenomena. It references all the best contemporary work on this subject but pulls it all together in a unified framework.
5 personnes ont trouvé cela utile
- Marker
- 21/05/2007
In depth solid material
The Long Tail is a well-presented, well-researched book describing the democratization of the means of producing and distributing goods and information. The long tail is what Chris Anderson calls the effect of aggregating vast numbers of like items and graphing them as hits and niches in such a way that the chart looks like a 'reverse hockey stick' with the handle being the tail.
In a digital age the cost and ease of producing niche products and media has both redeemed and made irrelevant Karl Marx? critique of capitalist society. We all can virtually own the means of production and we can independently have access to markets without capital, or very much of it.
In an age of search engines we have the ability to filter an unbelievable range of options so that markets can be made from the thinnest quantity of items and to the smallest niche number of consumers. The Long Tail, once irrelevant and inaccessible, now is driving the digital ecomony.
As a listen, the unabridged version can be a little more detail than you might need, but stick with it and the detail will payoff.
Unlike some books of this type, the audible version does not suffer because you cannot visually scan backward to review when the argument becomes too complex. The reader, Christopher Nissley does a great job.
4 personnes ont trouvé cela utile
- 04/01/2015
A Long (but worthy) Tale, About a Long Tail.
Provides a new component to business analysis; in that the tradition factors of marketing no longer provide a full market view. Sale of limited or unique market products can now be readily presented and supplied alongside dominant market products. Each having equal opportunity to reach and be purchased by other distributors and end market purchasers. The study further demonstrates "tail" products in mass can equal and surpass the dominant market products when conglomerated. Think Amazon.
A little dated, a little too redundant and a little too long but an essential understanding to anyone who seeks to market in today's arena; and especially marketing via the web. Don't let my ratings discourage those who need to consider how to sell a product in today's electronic world. It is not necessarily a fun read, but it is an educational read.
2 personnes ont trouvé cela utile
- Peter B. Sims
- 28/01/2008
Wow! A must listen!
I found this book to be interesting and dynamic. I could not turn it off. I have listened to it twice to make sure I did not miss anything.
Buy this book if you want to learn about the past, present and future of business.
2 personnes ont trouvé cela utile
- Lynne
- 07/02/2007
Food for thought
Being in the book industry, we found this thesis thought provoking. It was a challenging but much needed wake up call. Well illustrated with current business innovations and trends, it helped me to appreciate how quickly the world is changing and gave us some ideas on positioning ourselves for the future.
There is quite a following to this book and several websites are devoted to its discussion. Recommended for any business owner, across all industries! A worthy herald of sea-change.
2 personnes ont trouvé cela utile
- Audio Gra Gra
- 10/03/2011
Very good, but needs an update
A very interesting audiobook with just one flaw - because it largely draws upon technology and related businesses for its subject matter, it is already slightly dated. This is one of those books that would benefit from an update, not because anything in it is necessarily wrong, but because things in this sphere just move so quickly. For example, MySpace, which is mentioned excitedly in the book, is now a dying website...
1 personne a trouvé cela utile
- Stephan
- 20/03/2010
Great book ! Must read...
Nevertheless, it would help if Audible would process the audio file: the mastering is poor at the beginning. Should use a de-esser, an audio processor effect that removes the "S" consonant's higher frequency that makes for uncomfortable listening... at times it is almost unbearable...
1 personne a trouvé cela utile
- BrightLink Roots
- 25/12/2008
Change I believe in
As a small business owner, this book has changed the way I think about our product and services.
3 personnes ont trouvé cela utile
- Tim
- 08/03/2008
A bit long at first but overall a great listen...I would recommend
1 personne a trouvé cela utile
- salandragk
- 27/03/2016
Good book, slightly outdated!
It is an useful book to understand the nature of mainstream and niche distribution. Examples need an update though.


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Cause Celeb highlights a celebrity's work on behalf of a specific cause. This week we speak with musician Peter Gabriel as well as Graham Nash, David Crosby and Rodrigo y Gabriela about the influence the nonprofit human-rights organization WITNESShas had on them. Peter Gabriel was inspired to found WITNESS in 1992 while he was traveling with Amnesty International's Human Rights Now! Tour. He brought a camcorder with him to record the different stories he heard along the way. Twenty years later, WITNESS has trained and partnered with activists in more than 70 countries to use video and online technologies to document human-rights abuses and to raise awareness of abuses. Since becoming an independent nonprofit organization in 2001, WITNESS has launched the Hub, an online video community for sharing human rights videos.Gabriel is a singer and songwriter who rose to fame as lead vocalist for the band Genesis. He has since found success as a solo artist. In addition to being the co-founder of WITNESS, he is involved with a variety of other causes including Amnesty International.
Q: After starting WITNESS over 20 years ago, did you ever think that it would come this far?
Gabriel: I think what we didn't realize was that our dream of getting cameras to the world and particularly to activists and human rights groups was going to be (done) way more effectively by the phone companies than by us. That's changed everything in a way and it feels like this year, particularly with the Arab awakening, the whole thing has really blossomed because young people are using cameras on their phones and putting it up.
Blogging, tweeting, YouTube. It's going all over the place and you can connect them all. Building popular movements that are actually overthrowing governments. This is extraordinary and wonderful. It's not the end of the road because there is a lot of hard work such as in Egypt, which has brought us here tonight where getting a change in leader is one thing but building a stable government with a constitution and democracy is yet another. But at least the process is under way and it's very exciting.
Q: When you first started WITNESS you never realized how Facebook and Twitter would affect WITNESS. Has it made it easier?
Gabriel: Yeah, and in some ways also it's all over the place which makes it more difficult to focus, but I think it's all going the right way.
More on charity and philanthropy
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It was a very merry Christmas for a 9-year-old SoCal boy who successfully climbed the highest peak this side of the globe, a feat that makes him the youngest person to do so and raises awareness for a type of muscular dystrophy that only affects young boys. Full story
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Q: Is there anything you are particularly proud of from the last few years?
Gabriel: I think there's a lot of things. In the International Criminal Court, the prosecution opened with some WITNESS footage of child soldiers. There are laws that are being changed in Kenya, giving land rights to indigenous people there. When you see laws being changed and this evidence, it's really making a difference, and the young video makers that are blogging with this Arab awakening. I come in and out but they live it. They've got an amazing team. They live it and they've done an amazing job.
Graham Nash and David Crosby are better known for their folk rock group Crosby, Stills & Nash. The group has been inducted into The Rock and Roll Hall of fame twice. Nash and Crosby have been on tour together and more recently launched their own record label.
Q: Tell me a little bit about WITNESS and how you support it?
Crosby: The idea is that if you put a camera in someone's hand in a Third World country and some kind of abuse of human rights takes place, they can photograph it and 30 seconds later, it can be all over the world.
Nash: That's an incredibly powerful tool because people can't hide anymore.
Crosby: It means the world is watching right over your shoulder. Now, that really makes people who are abusing the populace and abusing their power,
Nash: Think twice.
Crosby: Think twice because they see the effect. It doesn't stop them, it hasn't stopped them in Sierra yet but it will. Because the entire world watches and starts making phone calls and I can't help but think that it's a great idea and will continue to have a positive effect.
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Nash: When Peter asked we said yes instantly because we completely agree with the idea. It's a fantastic idea and anything we can do to support it, we will.
Crosby: We can see a good idea when we see one.
Q: You guys preformed in Zuccotti Park a couple days ago, so is there any connection between the movement that's happening downtown and what WITNESS does?
Nash: It's all the same energy, isn't it? It's people reaching a saturation point and saying I've had enough.
Crosby: I'm going to stick up for what I believe in, I'm going to stick up for myself. I'm not going to be rolled over.
Mexican musical duo Rodrigo and Gabriela attended and performed at the 7th Annual Focus for Change Event hosted by WITNESS. Rodrigo and Gabriela specialize in playing fast, rhythmic acoustic guitars. Their newest album is"Area 52."
Q: Tell me a little bit about WITNESS and how you support the organization?
Gabriela: Human rights are in a recession of caring about all the issues in the world. [WITNESS] does it with the video, you can post it somehow. We got involved through invitation. They approached us and asked us to get a table and they invited us to play along here and give a little music because we are people who care about world issues.
Q: Why is it important for musicians like yourselves to support charities like WITNESS?
Rodrigo: I think for any entertainer it's a responsibility because you have access to a lot of people and you have a chance to share that information, something they don't know, that is important to the world. It's as simple as that really for anyone in the industry.
© 2013 NBCNews.com Reprints


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DUP leader, Arlene Foster, caused a bit of a stir on social media on Monday when she mistakenly congratulated Prince William instead of Prince Harry on the news of his engagement to girlfriend Meghan Markle.
The Fermanagh and South Tyrone MLA also misspelled Miss Markle's Christian name in the tweet.
Mrs. Foster tweeted: "Congratulations to HRH Prince William on his engagement to Megan Markle. Wonderful news this morning.
"Oh dear, I feel so bad for Arlene Foster. Everyone makes mistakes," Tweeted one woman.
"Well that's awkward.. DUP leader Arlene Foster congratulates wrong prince on engagement to Megan Markle," added another.
Mrs. Foster deleted the tweet and re-posted having made the correction.


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I signed into Familysearch.org and was unable to find how to get into Family Tree as you described. New.Familysearch.org requires you to be LDS. A search in Familysearch.org under Family Trees brought up items from Ancestral Files and Pedigree Resource with no indication that they could be edited, sourced, etc. Where to I need to go to access what you described?I will try to be as specific as possible.
Family Tree is a user submitted program seeded by data from New.FamilySearch.org. New.FamilySearch.org has had limited access, especially to those who are not members of The Church of Jesus Christ of Latter-day Saints. Family Tree, on the other hand, is available to anyone who registers for either an LDS Account or a FamilySearch Account. Access to all of the FamilySearch.org resources is entirely free.
You can follow the instructions below to sign in and register, or you can click the Sign In link in the upper right hand corner of the FamilySearch.org screen and follow the instructions.
Family Tree is available through a link on the FamilySearch.org website, but you have to initiate the link before it will appear. The instructions for gaining access to the program on a PDF file called Gaining Access to the FamilySearch Family Tree (pdf). Here are the instructions:
1. Go to http://www.familysearch.org/invite/familytree_tab.Please feel free to post additional questions about this topic.
2. Enter the required information in the fields provided.
Important: When you enter your user name and password, enter the same user name and password that you use on familysearch.org and new.familysearch.org. This lets you see your FamilySearch Family Tree and all of your changes as they appear in new.familysearch.org in the FamilySearch Family Tree.
3. Click Register.
The FamilySearch FamilySearch Family Tree appears. You are in the main position on the screen. To get to the FamilySearch Family Tree from now on, go to www.familysearch.org, and sign in. The link to the Family Tree appears in the upper-left corner of the screen, next to the FamilySearch logo.