text: Services are available at their shelter at the Midwest City Community Center, 100 Midwest Blvd. Red Cross workers are also driving through affected areas in disaster relief trucks. Call 228-9500. Clothing The Choctaw Seventh Day Adventist Church, 14950 NE 3, will hand out clothing from 9 a.m. to 5 p.m. Storage U-Haul of Oklahoma City is giving 30 days of free storage to people who had to evacuate because of the fires. Storage is available at eight metro locations and two state locations. Metro area: U-Haul Downtown, 100 SE 2, 235-9446. U-Haul Crossroads, 6027 S High Ave., 631-0491. U-Haul Center Quail Springs, 721 W Memorial, 751-2525. U-Haul Storage Hefner, 421 W Hefner, 755-0406. U-Haul MacArthur Park, 6500 NW Expressway Street, 721-0674. U-Haul Storage Lincoln, 2500 NE 36, 424-5442. U-Haul Southside, 3101 SW 29, 681-5327. U-Haul Storage Bethany, 2425 N MacArthur, 787-2450. Statewide: U-Haul Storage Stillwater, 5715 W 6, (405) 624-3434. U-Haul Center Cache Road, 1102 Cache Road in Lawton, (580) 248-8472. Boxes U-Haul is giving away free boxes for evacuees and others who have been displaced because of the fires. Donated boxes can be picked up at any U-Haul location. On the Web Also, the following Web resources are available to those who were evacuated and/or lost their homes to grassfires in Oklahoma Thursday: - Shelters for fire evacuees in Oklahoma: View a list of shelters for those forced to evacuate their homes due to grassfires. - Donate to the Oklahoma City Red Cross: How you can help victims of Oklahoma's grassfires. - Know It: Giving: Assist those in need, or find out how you can receive assistance.


text:
7 years of INMA video history20 August 2015
We all know video is where it's at. So here's a reminder of all the INMA video available to you on INMA's YouTube channel — from formal conference presentations to quick chats on the hottest topics, like this one from INMA CEO/Executive Director Earl J. Wilkinson on the print vs. digital question in ...... [more]
INMA report on media smartphone apps shines light on rapidly shifting discussions27 July 2015
The trials, tribulations, and aspirations of media companies trying to make smartphone apps work for their most loyal readers are the focus of a report by the International News Media Association (INMA), titled "Smartphone App Lessons for Media Companies."
- INMA members: Click here to download for free (username/password required).
- Non-members: Click here to order online.
The report offers 19 case studies of media companies in Asia, Europe, Latin America, North America, and the South Pacific, aiming to sync smartphone app plans to their local digital ecosystems.
Over and over across the case studies, media companies ...... [more]
30 INMA Award winners unveiled for sales and marketing excellence, El Colombiano takes top prize12 May 2015
Thirty of the world's best news media sales and marketing initiatives were honoured tonight by the International News Media Association (INMA), punctuated by El Colombiano taking the coveted "Best in Show."
The INMA Awards were presented at the closing dinner of the 85th Annual INMA World Congress at the Edison Ballroom in New York's Times Square before nearly 300 media executives.
The INMA Awards 2015 competition generated 578 entries from 190 market-leading companies in 38 countries. The competition was judged in February by an international jury of 33 executives from 15 countries representing the worlds of media and marketing.
Created in 1935, the INMA Awards competition is the news media industry's premier barometer for growing audience, revenue, and brand across platforms. Overall, 30 first place awards in 15 categories across two audience groups were presented to 26 media companies.
"Innovation ruled the winning entries in this year's INMA Awards competition," said Earl J. Wilkinson, executive director and CEO of INMA. "We live in a transformation era, and the stand-out initiatives contributed to that transformation – whether innovation processes, social media breakthroughs, or new digital products conceived in ...... [more]
Ottosson, Whitehead presented INMA Silver Shovel Awards for career achievement12 May 2015
Sweden's Bengt Ottosson and Australia's Robert Whitehead were presented the 2015 Silver Shovel Awards tonight by the International News Media Association (INMA) for lifetime achievement and contributions to INMA.
The awards were presented Tuesday evening before nearly 300 international media executives at the INMA Awards Dinner in Times Square's Edison Ballroom.
The long-time CEO of Swedish popular daily newspaper, Expressen, Ottosson was cited by INMA President Yasmin Namini "for a career dedicated to mentoring and for unselfish dedication to the media industry" in presenting the Silver Shovel Award, INMA's highest individual honour.
A past president of the Swedish Media Publishers Association (TU), Ottosson has served on the INMA ...... [more]
Storyful captures INMA Global Innovation Award worldwide prize12 May 2015
Seven companies were rewarded tonight for excellence in innovation by the International News Media Association (INMA), with social media curation company Storyful taking home worldwide first place in the Global Innovation Awards, presented by Newscycle Solutions.
The Global Innovation Awards were presented at the closing dinner of the 85th Annual INMA World Congress at the Edison Ballroom in New York's Times Square before nearly 300 media executives.
The second annual INMA Global Innovation Award competition rewards media company programmes that encourage ideation and incubation, change the corporate culture, attract young talent, and incentivises innovation mindsets.
The seven regional winners ...... [more]
17 media executives elected to INMA Board of Directors10 May 2015
Outgoing INMA President Yasmin Namini passes the gavel to incoming INMA President Mark Challinor at the association's World Congress May 12 at The TimesCenter in New York.
INMA elected new officers and directors today at its annual business meeting at the Marriott Marquis in New York.
As INMA's governing body, the Board of Directors is responsible for the strategy and direction of INMA worldwide.
Officers elected were:
Mark Challinor, a long-time London and Liverpool newspaper executive who today is managing director of United Kingdom-based Media Futures Ltd., was elected president for a two-year term.
Eduardo Garces, general manager of El Espectador in Colombia, was elected vice president.
Yasmin Namini, most recently senior vice president/chief consumer officer of The New York Times, becomes immediate past president of INMA.
Ross McPherson, managing director of McPherson Media Group in Shepparton, Australia, was re-elected to a three-year term as the association's treasurer.
Challinor began his newspaper career at the Liverpool Echo in the United Kingdom before serving in various marketing and promotion capacities for Trinity Mirror and Associated Newspapers. He later was managing director of two mobile consultancies, Buzz Mobile Marketing and g8wave Ltd., before spearheading the mobile strategy for Telegraph Media Group. Today, he heads up the digital consultancy Media Futures. Challinor has served ...... [more]
INMA becomes launch partner for Google's Digital News Initiative28 April 2015
INMA is a launch partner for the Digital News Initiative (DNI), designed to support high-quality journalism through technology and innovation in Europe. The Google initiative was announced Tuesday at the FT Media Conference in London.
Google will invest €175 million in the initiative over three years. The project's goal is to enable ongoing collaboration and dialogue between the tech and news sectors, to promote innovation in digital journalism, and help support a sustainable news ecosystem. The DNI will seek to extend its work to other European publishers and anyone involved in Europe's digital news industry will be able to ...... [more]
89 finalists selected in INMA Awards competition for best media sales, marketing initiatives02 March 2015
Eighty-nine (89) finalists in the INMA Awards 2015 competition were announced today, recognising global excellence in sales and marketing among media companies.
The INMA Awards 2015 competition generated 578 entries from 190 companies in 38 countries.
The 80th annual sales and marketing competition was judged in February by an international jury of 33 executives from 15 countries representing the worlds of media and marketing.
First-place recipients in the INMA Awards 2015 competition will be announced Tuesday, May 12, at the conclusion of the INMA World Congress in New York. The awards ceremony will be held at the Edison Ballroom in Times Square. In addition to the announcement of 30 first-place recipients, the INMA Awards dinner in New York will conclude with the presentation of the "Best In Show," representing the top sales and marketing campaign by a media company worldwide from the past year.
The INMA World Congress May 10-12 in New York's TimesCenter will focus on strategy, revenue, and transformation of media companies. It is designed for strategists, catalysts, audience-builders, marketers, and revenue executives from the world's leading news media companies.
The coveted INMA Awards, created in 1935, represent the pinnacle in media industry creativity to energize news brands, stimulate audiences, innovate in product development, and grow revenue in transformational times.
"The INMA Awards represent a snapshot of the creativity, passion, and soul of the news media industry," said Earl J. Wilkinson, executive director and CEO of INMA. "Finalists announced today have demonstrated ...... [more]
INMA Awards finalists to be announced later today01 March 2015
Finalists in the INMA Awards 2015 competition will be announced at 10 a.m. EST (New York) on Monday.
Please check back to INMA.org for the announcement, including links to ...... [more]
INMA announces 2nd-annual Global Innovation Awards for media companies05 February 2015
Fostering the idea of "innovating routinely" among news publishers is the focus of the 2nd Annual Global Innovation Awards announced this week by INMA.
The deadline for submitting entries is Friday, March 6.
Go to www.inma.org/innovation for complete rules and information about how media companies can participate.
INMA created the Global Innovation Awards to shine a light on the expanding body of work news media companies are contributing in the field of structured approaches to innovation:
- How do you systematically generate ideas from employees?
- How to you incubate ideas or start-ups before ...

subset: commoncrawl


text:
Tags: mozzarella
Sausage PieMay 18th, 2015
Ingredients2 lbs. sausage1 cup chopped onion10 eggs1 egg white1 package (10 oz.) frozen chopped spinach, thawed and drained1 lb. mozzarella cheese, grated2 cups ricotta cheese1 tsp garlic powderpastry for double crust1 egg yolk… more »
Four Cheese Turkey Pasta CasseroleMarch 9th, 2015
Grilled PizzaJanuary 19th, 2015
My step mother shared this grilled pizza recipe with us. It's a great alternative to traditional pizza, with a thin crust and whatever toppings you can dream up. Yield: 6 pizzasIngredients1 3/4 cups warm water4 1/2 tsp yeast1 tbsp molasses… more »
Slow Cooker Mac and CheeseSeptember 1st, 2014
Ingredients1 lb. dry macaroni, prepared al dente according to package directions2 cans (10.75 oz. each) cheddar cheese soup, undiluted2 cups milk4 oz. sour cream1 stick (8 tbsp) butter1 tsp onion powder1/2 tsp black pepper2/3 lb. sh… more »
Cheesy Artichoke DipMarch 20th, 2014
Ingredients1 can (14 oz.) water-packed artichoke hearts1/2 cup mayonnaise1/2 cup sour cream4 oz. shredded mozzarella cheese1 cup grated parmesan cheese, divided1 tbsp finely chopped onion1 tsp parsley1/4 tsp garlic salt2 fresh art… more »
Caprese ChickenMarch 10th, 2014
Ingredients12 bacon strips6 boneless chicken breasts1 tbsp oil1/2 tsp salt1/4 tsp pepper2 roma tomatoes, sliced1/2 tsp basil6 slices mozarella cheese Directions more »
Lemon and Basil ChickenSeptember 12th, 2013
Rigatoni PieApril 30th, 2012
Ingredients1 lb ground beef3 garlic cloves, minced1/4 tsp pepper1 can (28 oz.) crushed tomatoes16 oz. rigatoni, cooked1 cup grated parmesan cheese1/2 lb. grated mozarella cheese Directions more »
Cheesy BreadMarch 15th, 2012
IngredientsDough1 1/2 cups flour, divided1 tbsp sugar1 tsp salt1 1/8 tsp yeast1 1/2 tbsp oil1/2 cup warm waterToppings2 tbsp butter2 cloves garlic, minced1/2 cup shredded parmesan cheese1/2 lb. shredded mozzarella ch… more »
Spicy Chicken PizzaMarch 8th, 2012
Yield: 4 servings IngredientsDough 1 1/2 cups flour, divided1 tbsp sugar1 tsp salt1 1/8 tsp yeast1 1/2 tbsp oil1/2 cup warm waterToppings DirectionsFor the dough, combine 1/2 cup flo… more »
Pepperoni Pizza Monkey BreadJanuary 30th, 2012
IngredientsDough2 1/2 to 3 cups flour, divided1 tbsp sugar1 tsp salt2 1/4 tsp yeast3 tbsp oil1 cup warm water2 cloves garlic5 tbsp butter8 oz mozzarella cheese cut into small cubesPepperoni, thinly sliced. About 55 slic… more »
Pepperoni & Mushroom PizzaSeptember 1st, 2011
IngredientsCrustPizza Directions more »
Four Cheese and Chicken Baked ZitiAugust 25th, 2011
IngredientsAlfredo Sauce1/2 cup butter2 cups heavy whipping cream2 cloves garlic, minced3 cups grated parmesan cheese1/3 cup chopped fresh parsely1 package ziti2 chicken breasts8 oz. sour cream2 eggs, lightly beaten15 oz… more »
BBQ Chicken PizzaNovember 12th, 2010
Thick crust IngredientsPizza DoughSauce8 oz can tomato sauce2/3 cup BBQ sauce1 garlic clove, minced2 tsp chopped fresh parsley(if you like it spicy) Tabasco sauce, to taste1/2 lb mozzarella cheese2 chicken breasts, cooked, coo… more »


text:
CSWE Accreditation for Social Work Program!
Dr. Kwi Yun, Chair of Nyack's Department of Social Work announced a new accreditation from the Council on Social Work Education (CSWE). The CSWE is the national association for social work education in the United States of America, which oversees standards of courses and accreditation of bachelor's degrees and master's degree programs in social work.
Members of Nyack's Social Work Department team, who diligently contributed to the accreditation process, included Dr. Kwiryung Yun, Department Chair and Professor; Dr. Carol Awasu Deputy Chair and Professor; Prof. Mayra Lopez-Humphreys, Field Education Coordinator and Assistant Professor; and Prof. Scott Dixon, Faculty Member. Dr. Yun also acknowledges the contributions of Mrs. Percelene McLain, Division Secretary in Social and Behavioral Sciences; student worker and 2007 graduate, Janet Wu; and current student worker, Mia Basa Agubuya.
This prestigious achievement will be celebrated with a praise, worship, and dedication service on Thursday, March 27 at the 5:00 p.m. chapel on the Nyack New York City campus. A Rockland County campus service is being planned by Dr. Awasu.
President Michael G. Scales expressed praise to the team and added his thanks "for the perseverance and considerable investment of time, talent, and prayer."
Recent Posts
- Official Statement in Response to Media Announced Law Suit
- MA in Mental Health Counseling Online Approved by NYS Education Department
- School of Music Reunion with Dr. John McArthur
- OCT 17: Fall Fishing
- October 17: Homecoming Block Party!
- Woman: A Rite of Passage Initiation Ceremony Held
- Dr. Mark Nanos Welcomed to Nyack NYC for AJCO Colloquia Series
- Peter Irvine, 2015 School of Business and Leadership Keynote Speaker Coming October 13
- A HOMECOMING HIT! The Running Warrior 3K Walk & 5K Road Race
- Nyack on U.S. News & World Report 2016 Best Colleges Diversity List
- NYC Campus Library Gets a New Name
- The Names by Billy Collins
- ATS Alumnus/Author Dimas Salaberrios, a Fox & Friends Guest
- Homecoming 2015: Nyack Alumni, Prepare to Dine!
- The Loss of AGSC Colleague, Dr. James Chin
- Forum on Restorative Justice Features Nyack Professor
- Math Prof Conducts Research at Seoul International Christian Academy in Korea
- Inspiration for a New Academic Year at Nyack/ATS
- School of Music: Trading Textbooks for iPads
- Peter Rohdin: Responding to God's Call
- Women Warrior Teams Honored for Sportsmanship...the Ninth Straight Year
- Nyack/ATS Loses a Dear Friend
- Nyack College Represented in Journal News STEM Education Feature
- RELEASE: iSucceed at Nyack College
- TBN Segment With Nyack Students Airs on Homelessness in NYC
- Browse Blog Archive>>
- Feed


text:
Red Gem Lips Stud Earrings
(approx. $9.03 or €8.18)
- Out of Stock - Product Discontinued
- Product Type: Earring
- Product Code: 66205
Kiss your love goodbye with these cute gem earrings. In the shape of juicy red lips, these stud earrings will blow away your competition with glitz and glamour.


text:
If you want to find out how to fix a bike you have no need to go running to a professional repair shop if you harness the power of the internet! There are a lot of online bicycle repair sites out there desperately wanting your attention but I recommend you try the following three which […]
Archive | January, 2009
Join 9,241 fellow London Cyclists who receive our free weekly newsletter:
As mentioned in:
- Preparing for your first French cycle tour 04/10/2015
- Complete guide to safe cycling for cyclists and motorists 30/09/2015
- My eyes! New dhb Flashlight jacket and jerseys reviewed 29/09/2015
- How to cope with 3 panic inducing bike commuter experiences 24/09/2015
- 3 pannier options to commute undefeated in the rain 21/09/2015
- A 'Mini-Holland' for all? 18/09/2015
- 10 things I wish I'd known when I first started cycling 11/04/2013
- The best bike lock 21/11/2012
- Bicycle insurance 07/09/2011
- How to start cycling 20/01/2011
- Buying a second hand bike in London 25/08/2010
- 7 mistakes you are making with your cycling and how you can correct them 28/04/2010
- 35 London Cycling Routes with GPS 02/03/2010
- Chris: I'm all for people respecting rules put in place ...
- Darren: Got my suit jacket (that I wore once) back for the...
- Dave: Good for you Sarah! Fortune really does favour the...
- Sarah: Boris bikes, one year ago today. I had learnt to...
- Chris: What a great post! With night's getting darker t...
- SteveP: I believe many objective tests (i.e. plenty of dat...
35 London Cycle Routes with GPS
For just £9.95 you can discover 35 amazing cycling routes in London for training, days out with the kids and traffic free riding. The eBook also comes with GPS coordinates.
Click here to find out more now


text:
Aloha there at our free ringtones website, where it's possible to find ringtones for free for your smart phone. Today we have a ringtone of "Do You Feel Me" by Anthony Hamilton as well as 359 other ringtones by Anthony Hamilton. "Do You Feel Me" is the best track from the "American Gangster" album that was recorded and mixed by Anthony Hamilton at their studios together with other 1 tracks. You can listen to all 3 Anthony Hamilton – "Do You Feel Me" ringtone variations available here and download it for free to your PC. You can also take a glance at other 7 albums produced by Anthony Hamilton for all time. "Do You Feel Me" is referred to Soul, and you can download a huge amount of Soul collaborations absolutely for free. And finally, we have collected lyrics for this track and you can view it here as well. So feel free to browse, listen, download ringtones at Audiko.net. Make your phone sound cool!
Anthony Hamilton Do You Feel Me Ringtone
Similar Ringtones
Browse Genres
Neo Soul Neo-Soul R&B Rhythm And Blues Soul Urban
Albums by Anthony Hamilton
- Comin from Where Im From
- American Gangster OST
- American Gangster
- Aint Nobody Worryin
- Step Up
- Step Up Soundtrack
Top ringtones by Anthony Hamilton
New ringtones
- Unknown - Ame_-_Rej__HD
- Kersal - Kersal
- Martin Smith - Waiting Here For You (feat. Sarah Bird)
- Unknown - Neffa - Colpisci
- SKINS - Skins Theme
- David Guetta & Showtek feat. Magic! - Sun Goes Down
- taylor - Propa Ringtone
- The Warp Zone - Racking Stars
- Cкрябін - Мам
- Unknown - Felix Jaehn – Ain't Nobody feat. Jasmine Thompson Live @ Ene


text:
RJR.John Rocha Designer girl's navy pleated applique flower dress
Item No.2320202760
Item No.2320202760
Up to 70% Off - Save up to £23.80
Perfect for her occasion wear, this girl's navy designer dress from RJR.John Rocha has a pleated chiffon overlay with a pretty applique flower design on the top and concealed zip fastening at the back.
UK Home Delivery Free (UK orders over £30) or £3.49
Delivered within 5 working days
Next or Named Day Delivery
7 days a week between 8am - 6pm
Sunday to Friday - order by 9pm - £3.99
Saturday - order by 6pm - £3.99
Next or Named Evening Delivery
7 days a week between 6pm - 10pm
Monday to Sunday - order by Midnight - £6.99
Collect from store the next day - FREE
Order before 9pm for next day collection after 12pm midday
Show participating stores
Show full delivery details
Subject to exceptions, Debenhams is happy to exchange or refund your purchase within 28 days of delivery. Please check here for more details on our returns policy and exceptions.


text:
Mobile broadband's latest bidding war
Ben Johnson
Apr 21, 2014 Wireless carriers are preparing to battle for airwaves
By 2020, there will be 10 web-connected devices per human
David Brancaccio
Interview by
May 5, 2014 Dell CEO Michael Dell tells Marketplace his plans to meet future demand.
HTC goes low-end amid struggle to compete in smartphone market
Ben Johnson
Interview by
Feb 11, 2014 The Taiwanese phone maker considers new moves after a disappointing earnings report.
Can two TV stations share the same airwaves?
David Weinberg
Jan 30, 2014 Two TV stations in Los Angeles want to undertake an experiment: Share their airwaves so they can sell back, for wireless use, the part of the spectrum they don't use.
Can you hear me now? Not in rural areas
Dan Weissmann
Oct 29, 2013 In rural areas, one out of every 5 land-line long-distance calls doesn't go through.
Microsoft's Nokia deal: Modeled on Apple comeback?
Noel King
Sep 3, 2013 Microsoft acquires Nokia in a $7.2 billion deal that aims to make Microsoft a player in the mobile-phone market.
Will Ubuntu revolutionize mobile computing?
Molly Wood
Interview with
Aug 14, 2013 A startup seeks to make your smartphone into your PC.
Hacking the doors of the future
Ben Johnson
Interview by
Aug 13, 2013 "Smart homes" that can be unlocked by smart phones are around the corner, but so are hacks that will unlock the front door.
LG unveils the G2 smartphone
Ben Johnson
Interview by
Aug 8, 2013 LG's flagship smartphone has features that could make it stand out in a crowded market.
Is Samsung treading water until the Galaxy S5?
Shannon Mullen
Jul 26, 2013 Even though Samsung is still growing , its profits likely won't ease concerns the company is in a bit of trouble.


text:
Same-visit HIV testing in Trinidad and Tobago
1 Ministry of Health, Port of Spain, Trinidad and Tobago
2 Pan American Health Organization, Bridgetown, Barbados
3 George Street Health Center, Port-of-Spain, Trinidad and Tobago
4 Petit Valley, Port of Spain, Trinidad and Tobago
5 St. Anne's, Port of Spain, Trinidad and Tobago
6 Centers for Disease Control and Prevention, Atlanta Georgia, USA
BMC Public Health 2010, 10:185 doi:10.1186/1471-2458-10-185Published: 9 April 2010
The Ministry of Health (hereafter, Ministry) of Trinidad and Tobago is responsible for delivery of all health services in the country. The Ministry takes responsibility for direct delivery of care in the public sector and has initiated a process whereby those seeking HIV test results could obtain confidential reports during a single-visit to a testing location. The Ministry requested technical assistance with this process from the Caribbean Epidemiology Centre (CAREC). The United States Centers for Disease Control and Prevention (CDC) played an important role in this process through its partnership with CAREC.
Under the technical guidance of CAREC and CDC, the Ministry organized a technical working group which included representatives from key national HIV program services and technical assistance partners. This working group reviewed internationally-recognized best practices for HIV rapid testing and proposed a program that could be integrated into the national HIV programs of Trinidad and Tobago. The working group wrote a consensus protocol, defined certification criteria, prepared training materials and oversaw implementation of "same-visit" HIV testing at two pilot sites.
A Ministry-of-Health-supported program of "same-visit" HIV testing has been established in Trinidad and Tobago. This program provides confidential testing that is independent of laboratory confirmation. The program allows clients who want to know their HIV status to obtain this information during a single-visit to a testing location. Testers who are certified to provide testing on behalf of the Ministry are also counselors. Non-laboratory personnel have been trained to provide HIV testing in non-laboratory locations. The program includes procedures to assure uniform quality of testing across multiple testing sites. Several procedural and training documents were developed during implementation of this program. This report contains links to those documents.
The Ministry of Health has implemented a program of "same-visit" HIV testing in Trinidad and Tobago. This program provides clients confidential HIV test reports during a single visit to a testing location. The program is staffed by non-laboratory personnel who are trained to provide both testing and counseling in decentralized (non-laboratory) settings. This approach may serve as a model for other small countries.


text:
MONDAY, Aug. 8 (HealthDay News) -- Students attending high schools dominated by bullies are more likely to have lower standardized test scores, a new study shows.
In fact, researchers in Virginia found that schoolwide passing rates on three different standardized exams (Algebra I, Earth Science and World History) were 3 percent to 6 percent lower in schools where students reported a more severe bullying climate. The findings, they added, highlight the fact that bullying is a pervasive problem in schools.
"Our study suggests that a bullying climate may play an important role in student test performance," Dewey Cornell, a clinical psychologist and a professor of education at the University of Virginia, said in a news release. "This research underscores the importance of treating bullying as a schoolwide problem rather than just an individual problem."
In conducting the study, researchers compiled surveys about bullying from more than 7,300 ninth graders and about 3,000 teachers at 284 Virginia high schools. The researchers pointed out that even a 3 percent to 6 percent drop in test scores associated with bullying is significant.
Under the federal No Child Left Behind Act, students must receive a passing grade on these standardized tests to graduate. Moreover, in the state of Virginia at least 70 percent of a school's students must pass the tests for the school to keep its state accreditation.
"This difference is substantial because it affects the school's ability to meet federal requirements and the educational success of many students who don't pass the exams," said Cornell. "This study supports the case for school-wide bullying prevention programs as a step to improve school climate and facilitate academic achievement."
The researchers argued the poor academic performance was due to the fact that students are less engaged in learning when they are afraid about bullying. They also suggested bullying lead
|Copyright©2010 ScoutNews,LLC.
All rights reserved


text: Really enjoyed our stay in this Shepherd's hut on the campsite. Owner has two and is considering bringing a third on site. Hut has an electric heater, microwave, kettle and small fridge with freezer drawer, as well as a raised 'caravan' style bed area (if there are two of you and you're taller than 5ft 8", you may have difficulty... More


text:
|Publication number
|Publication type
|Application number
|Publication date
|Jan 20, 2004
|Filing date
|Aug 23, 2000
|Priority date
|Jun 22, 1998
|Fee status
|Publication number
|Gang Sun, Louise L. Ko, Takayuki Shibamoto
|Original Assignee
|The Regents Of The University Of California
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (11), Non-Patent Citations (2), Referenced by (1), Classifications (12), Legal Events (5)
|External Links: USPTO, USPTO Assignment, Espacenet
This Application U.S. patent application Ser. No. 09/102,525, filed Jun. 22, 1998, now U.S. Pat. No. 6,077,319 and U.S. Provisional Patent Application No. 60/151,667, filed Aug. 31, 1999, the teachings of which are incorporated herein by reference in their entirety for all purposes.
In general, this invention relates to methods for the protection against pesticides, and more particularly, this invention relates to processes for making articles capable of detoxifying pesticides.
Due to the toxicity of pesticides, protection of agricultural and farm workers against exposure and contact is highly desirable. Without proper protection, dermal exposure to pesticides can lead to skin sensitization, cancer, birth defects and even death. One effective means of protection of agricultural field workers is by using protective clothing. Currently, pesticide protective clothing is made of disposable and non-permeable synthetic materials. These materials cannot be comfortably worn in all seasons due to the generation of heat stress to agricultural workers. In addition to the discomfort and impermeable properties of these materials, synthetic materials are non-biodegradable, thus, serious environmental concerns exist.
In general, the movement of pesticides on fabrics used for protective clothing can be characterized in terms of permeation and penetration (see, Easter, E. P. and Nigg, H. N., Review of Environmental Contamination and Toxicology, Vol. 129, 1992, p 1-15). Permeation is the process by which a chemical moves through a material on a molecular level. Such movement includes the sorption of molecules of the chemicals into the contacted surface of the material, the diffusion of the adsorbed molecules in the material and the desorption of molecules from the inside surface of the material into the collecting medium. Penetration, on the other hand, is the flow of a liquid chemical through closures, porous material, and material imperfections on a non-molecular level. In both cases, a physical barrier can effectively prevent any movement of pesticides through the fabrics. Materials that are considered as physical barriers to chemicals are those that will not allow any measurable movement of pesticides through them. Oftentimes, these barrier materials are specifically referred to as chemically resistant materials. Being thick and heavy, these chemical resistant materials disallow permeation and respiration at the same time, hence, generating tremendous heat stress and physical discomfort to wearers.
Since the surface contact of pesticides with materials such as fabrics, occurs by both permeation and penetration mechanisms, new methods are needed to decontaminate the pesticides on the fabrics. Methods are needed that will restrict the movement and infiltration of pesticides on the surface of the textiles such as workers' clothing. The present invention fulfills these as well as other needs.
Due to the high toxicity of pesticides and the concomitant high dermal absorption suffered by farm workers, protection of agricultural and farm workers against pesticide exposure and contact is imperative. As such, the present invention provides a process for making an article, such as a textile material, capable of detoxifying a pesticide, the process comprising:
(a) immersing the article in an aqueous treating solution which comprises a catalyst, a wetting agent and a heterocyclic amine; and
(b) treating the article with a halogenated aqueous solution, thereby rendering the article capable of detoxifying a pesticide.
Surprisingly, the inventors have discovered that chemical detoxification of pesticides can be carried out on the surface of textile materials if a reactive chemical is permanently incorporated on the surface thereof. Consequently, the textile materials of the present invention provide outstanding protection as well as comfort.
The articles of the present invention include, but are not limited to, textiles such as cellulosic fabric, cellulosic yam, cellulosic fiber, cotton/polyester blends, cellulosic/synthetic blends, polymers such as synthetic polymers, wood products and the like. In a preferred aspect, the present invention provides shirt-weight cotton-containing apparel for field workers that are capable of detoxifying pesticides. The apparel that undergoes the processes of the present invention has the surprising advantage of being capable of detoxifying pesticides, thus rendering the apparel an excellent choice for farm workers. Moreover, the treated cotton fabrics are comfortable and breathable and thus, the workers' heat stress is also reduced.
In another aspect, the present invention provides a process for detoxifying a pesticide, comprising: contacting the pesticide with an article having an N-halamine attached thereto, thereby detoxifying the pesticide. As the pesticide comes in contact with fibrous materials of the articles upon permeation or penetration, chemical detoxification of the pesticides can be carried out on the surface of the treated textile materials or articles. In this aspect, a reactive chemical, such as a N-halamine, is permanently incorporated on the surface of the textile while maintaining integral textile properties. In certain aspects, the textile materials contain active functional groups such as chlorine, which have been discovered to be an excellent detoxifying agent in the decomposition of pesticides.
These and other aspects will become more readily apparent when read with the accompanied figures and the detailed description that follows.
FIG. 1 illustrates suitable heterocyclic amines for use in present invention.
FIG. 2 illustrates formation of a N-halamine on cellulosic fabric and the subsequent detoxification.
FIG. 3 Panel A illustrates the chemical formula of 1,3-dimethylol 5,5-dimethyl hydantoin (DMDMH); Panel B illustrates the chemical formula methomyl; and Panel C illustrates the chemical formula of aldicarb.
FIG. 4 illustrates the detoxification of methomyl by cotton/polyester fabrics treated with DMDMH.
FIG. 5 illustrates the detoxification of aldicarb by cotton/polyester fabrics treated with DMDMH.
FIG. 6 illustrates reduction of methomyl and aldicarb at 0.1% active chlorine content.
FIG. 7 illustrates detoxification of aldicarb on laundered fabrics that were treated with 6% DMDMH and 0.01% active chlorine content.
In certain embodiments, the present invention provides methods for making an article, such as a textile, capable of detoxifying a pesticide, comprising: (a) immersing the article in an aqueous treating solution which comprises a catalyst, a wetting agent and a heterocyclic amine; and (b) treating the article with a halogenated aqueous solution, thereby rendering the article capable of detoxifying a pesticide.
As used herein, the phrase "capable of detoxifying a pesticide" refers to the ability of the article to chemically convert the pesticide into a non-toxic fragment(s). Without being bound by any particular theory, it is believed that the article detoxifies the pesticide by a degradation mechanism, i.e., the articles that undergo the processes of the present invention are capable of chemically degrading the pesticides (e.g. by oxidation or oxidative hydrolysis). In preferred embodiments, the articles which undergo the processes of the present invention, have functional groups attached thereto rendering them capable of chemically reacting with the pesticides and thereby rendering the pesticide non-toxic. In certain instances, the pesticide is degraded into a:non-toxic derivative.
A wide variety of articles are suitable for use in the present invention. These articles include, but are not limited to, textiles such as cellulosic fabric, cellulosic yarn, and cellulosic fiber; polymers such as polyester and cellulose; cotton/polyester blends; cellulose/synthetic blends; wood materials such as wood pulp and paper; wood farming materials; tractor farming materials; garments such as shirts, pants, undergarments, coats, hoods, cloaks, gloves and protective garments. Those of skill in the art will know of other articles suitable for use in the processes of the present invention.
Using the methods of the present invention, the articles, such as textiles, offer protection against the toxic effects of pesticides, by for example, chemically oxidizing the pesticides. The article is immersed in an aqueous treating solution. The aqueous treating solution comprises a heterocyclic amine, optionally a wetting agent and optionally a catalyst. As used herein, "wetting agent" refers to a substance that increases the rate at which a liquid spreads across a surface, i.e., it renders a surface nonrepellent to a liquid. Examples of suitable wetting agents include, but are not limited to, TRITON� X-100 which is generically a polyoxyethylene (10) isooctylphenyl ether available from Sigma Chemical Co., St. Louis, Mo.; SEQUAWET� which is generically, a wetting agent containing nonionic surfactants available from Sequa Chemical Inc., Chester, S.C.; and AMWET� which is generically, a wetting agent containing nonionic surfactants available from American Emulsions Co., Dalton, Ga. Other wetting agents suitable for use in the present invention will be known to and used by those of skill in the art. As used herein, "catalyst" refers to a substance that augments the rate of a chemical reaction without itself being consumed. Suitable catalysts for use in the present invention include, but are not limited to, magnesium salts, zinc salts and ammonium salts. In a presently preferred embodiments, the catalysts include, but are not limited to, MgCl2, Mg(NO3)2, Zn(NO3)2 and NH4NO3.
After the article, such as a fabric, is immersed in the above-described aqueous solution, the article is thereafter treated with a halogenated solution, such as a halogenated aqueous solution. The halogenated solution can be a chlorine solution, a bromine solution, a solution containing free chlorine or bromine, combinations thereof, etc. In a presently preferred embodiment, the halogenated solution is sodium hypochlorite (e.g., a chlorine bleach solution such as CLOROX�), or trichloro isocyanuric acid or sodium dichloro isocyanuric acid. The treatment of the article with a halogenated solution renders the article capable of detoxifying a pesticide.
In certain aspects of the present invention, several steps can optionally be inserted between step (a) and (b) above. For instance, in certain preferred aspects, the method further comprises removing excess aqueous treating solution from the article before treating the article with a halogenated aqueous solution. In this aspect, the excess aqueous treating solution is removed by ordinary mechanical methods, such as by passing the article (e.g., textile) between squeeze rolls, by centrifugation, by draining or by padding. In a preferred embodiment, the excess aqueous treating solution is removed by padding.
In addition, the process optionally further comprises drying the article after removing excess aqueous treating solution to produce a dried article. In this aspect, the article is dried at a temperature ranging from about 50� C. to about 90� C. and, more preferably, at a temperature ranging from about 75� C. to about 85� C. for a period of time ranging from about 3 to about 8 minutes and, more preferably, for about 5 minutes.
Moreover, the dried article can optionally be cured to produce a cured article. The curing process is conducted at a temperature ranging from about 120� C. to about 200� C. and, more preferably, at a temperature ranging from about 140� C. to about 160� C. for a period of time ranging from about 3 to about 8 minutes and, more preferably, for about 5 minutes. The heating can be carried out in an oven, preferably one having a forced draft of air directed at the surface of the article and exhausting through a vent to remove fumes.
The cured article is then optionally washed to remove excess reagents. Washing of the treated article can be done with water. The covalent bonds formed are stable, insoluble, and durable to the mechanical agitation, spraying and rubbing that occurs in washing machines or in large scale continuous or batchwise textile washing equipment. In certain preferred embodiments, the process further comprises drying the washed article to remove water.
The article can optionally be dried before treating the article with a halogenated aqueous solution, to render the article capable of detoxifying a pesticide. Drying of the article, such as a fabric, can be carried out by any ordinary means such as oven drying, line drying or, tumble drying in a mechanical clothes dryer. A drying temperature of about 60� C. to about 100� C. is particularly preferred. Suitable drying times are generally less than 15 minutes in duration.
certain preferred aspects, the present invention provides a process for preparing an article capable of detoxifying a pesticide, comprising: (a) immersing the article in an aqueous treating solution which comprises a catalyst, a wetting agent and a heterocyclic amine; (b) removing the excess treating solution from the article; (c) drying the article; (d) curing the article; (e) washing the cured article to remove excess reagents; (f) drying the washed article to remove water; and (g) treating the cellulosic article with a halogenated aqueous solution, thereby rendering an article capable of detoxifying a pesticide.
The articles become capable of detoxifying pesticides by grafting a heterocyclic N-halamine structure on the article. With reference to FIG. 2, with incorporation of a halamine on a fabric such as cotton and subsequent halogenation, the article is thereby rendered capable of detoxifying a pesticide. "Heterocyclic amine," as used herein, refers to a 4- to 7-membered ring, having at least 3 members of the ring being carbon, and from 1 to 3 members of the ring being nitrogen, and from 0 to 1 member of the ring being an oxygen, wherein from 0 to 2 carbon members comprise a carbonyl group, and wherein at least 1 to 3 nitrogen atoms are substituted with a hydrogen or hydroxyalkyl group, such as —CH2OH, or a alkoxyalkyl group, such as —CH2OCH3. Suitable heterocyclic amines are set forth in FIG. 1. Those of skill in the art will know of other heterocyclic amines suitable for use in the present invention. After halogenation, at least one ring nitrogen has bonded thereto a halogen atom. In addition, the ring members can be further substituted with alkyl groups, such as methyl, ethyl, etc., or hydroxy groups. Heterocyclic N-halamines are generally disclosed in U.S. Pat. No. 5,490,983 issued to Worley, et al. on Feb. 13, 1996, the teachings of which are incorporated herein by reference for all purposes.
The preferred heterocyclic amines suitable for use in the present invention include, but are not limited to, monomethylol-5,5-dimethylhydantoin (MDMH), 1,3-dimethylol-5,5-dimethylhydantoin (DMDMH); monoalkylolated and dialkylolated derivatives of 2,2,5,5-tetramethyl- 1,3-imidazolidin-4-one, 6,6-dimethyl-1,3,5-triazine-2,4-dione, 4,4,5,5-tetramethyl-1,3-imidazolidin-2-one, cyanuric acid and 5,5-dimethylhydantoin; and monoalkoxylated and dialkoxylated derivatives of monoalkylolated and dialkylolated derivatives of 2,2,5,5-tetramethyl-1,3-imidazolidin-4-one, 6,6-dimethyl-1,3,5-triazine-2,4-dione, 4,4,5,5-tetramethyl-1,3-imidazolidin-2-one, cyanuric acid, 5,5-dimethylhydantoin, 2,2,5,5-tetramethyl-1,3-imidazolidin-4-one and mixtures thereof. Preferably the heterocyclic amine is monomethylol-5,5-dimethylhydantoin (MDMH), and 1,3-dimethylol-5,5-dimethylhydantoin (DMDMH) (see, FIG. 1).
Those of skill in the art will readily appreciate that the concentration of the various components of the aqueous treating solution can be widely varied depending upon the particular components employed and the results desired. Typically, the heterocyclic amine is present at a concentration of at least about 0.2%. More typically, the heterocyclic amine is present at a concentration ranging from about 0.2% to about 20%, more preferably at a concentration ranging from about 0.5% to about 10% and, more preferably at a concentration ranging from about 1% to about 5%. It will be readily apparent to those of skill in the art that higher heterocyclic amine concentrations (e.g., 50%) can be employed, but such higher concentrations are not required to impart pesticide-detoxifying activity. Again, suitable pesticide detoxifying activity can be imparted using a heterocyclic amine concentration as low as about 0.2%. The wetting agent is typically present at a concentration ranging from about 0.1% to about 3% and, more preferably, at a concentration ranging from about 0.2% to about 1%. The concentration of the catalyst employed will depend on the concentration of the heterocyclic amine employed. Typically, the ratio of heterocyclic amine to catalyst present will range from about 10:1 to about 5:1. The pH of the aqueous treating solution will typically range from a pH of about 2 to about 6 and, more preferably, from a pH of about 2.5 to about 4.5.
Those of skill in the art will readily appreciate that other additives can optionally be incorporated into the aqueous treating solution to impart favorable characteristics to the pesticide resistance articles. Such additives can include softeners and waterproofing agents that are known to and used by those of skill in the art. Examples of softeners which can be added to the aqueous treating solution include, but are not limited to, MYKON� and SEQUASOFT� both of which are commercially available from Sequa Chemical Inc. (Chester, S.C.). Examples of waterproofing agents which can be added to the aqueous treating solution include, but are not limited to, SEQUAPEL� (Sequa Chemical Inc., Chester, S.C.), SCOTCHGARD� (3M, St. Paul, Minn.) and other water repellent finishing solutions used by those of skill in the art.
Without being bound by any particular theory, it is believed in certain instances, that an active halogen, such as the N-halamine on a fabric, detoxifies the pesticide by chemical oxidation. The chemical oxidation occurs by contacting the pesticide with the N-halamine. For example, in the case of an N-halamine, the active halogen atom can effectively oxidize functional groups on pesticides, thereby detoxify the pesticide in the process. It is believed that the contact of pesticides with an article (e.g. textile materials) occurs by both permeation and penetration of the pesticides on the fabrics. Therefore, the fabric materials provide opportunities for chemical detoxification on the surface of the materials. As the pesticide is in contact with fibrous materials upon permeation or penetration, a large surface area of the fabric allows for the detoxification to occur. Thus, chemical detoxification of pesticides can be carried out on the surface of textile materials if a reactive chemical or functional group is permanently incorporated on the surface of the fabrics.
Using the methods of the present invention, it is possible to detoxify pesticides (e.g., methomyl and aldicarb; see, FIG. 3B-C) by contacting the pesticide with a grafted N-halamine structure on an article (e.g., cotton/polyester fabrics). For example, in the detoxification of methomyl, both the concentration of active chlorine present on the article and the concentration of methomyl being exposed to the article effect the detoxification efficiency. It is believed that the amount of active halogen on the fabric is directly proportional to the amount of pesticide reduced. Therefore, in certain aspects, for efficient detoxification of methomyl, it is preferable to graft DMDMH on the cotton/polyester fabric at a high add-on rate (e.g., 6%) with high active chlorine treatment (e.g., 0.1%).
As such, in another embodiment, the present invention provides a process for detoxifying a pesticide, comprising: contacting the pesticide with an article having an N-halamine attached thereto, thereby detoxifying the pesticide. A wide variety of pesticides can be detoxified using the methods of the present invention. These pesticides include, but are not limited to, herbicides, fungicides, rodenticides, insecticides and mixtures thereof. More particularly, suitable pesticides include, but are not limited to, methomyl, aldicarb, carbofuran, and carbaryl. Other pesticides which are detoxified using the processes of the present invention include, but are not limited to:
A. Benzo-2,1,3-thiodiazin-4-one-2,2-dioxides such as bentazone;
B. hormone herbicides, particularly the phenoxy alkanoic acids such as MCPA, MCPA-thioethyl, dichlorprop, 2,4,5-T, MCPB, 2,4-D, 2,4-DB, mecoprop, trichlopyr, fluroxypyr, clopyralid, and their derivatives (e.g. salts, esters and amides);
C. 1,3-dimethylpyrazole derivatives such as pyrazoxyfen, pyrazolate and benzofenap;
D. Dinitrophenols and their derivatives (e.g. acetates such as DNOC, dinoterb, dinoseb and its ester, dinoseb acetate;
E. dinitroaniline herbicides such as dinitramine, trifluralin, ethalfluralin, pendimethalin; and oryzalin;
F. arylurea herbicides such as diuron, flumeturon, metoxuron, neburon, isoproturon, chlorotoluron, chloroxuron, linuron, monolinuron, chlorobromuron, daimuron and methabenzthiazuron;
G. phenylcarbamoyloxyphenylcarbamates such as phenmedipham and desmedipham;
H. 2-phenylpyridazin-3-ones such as chloridazon and norflurazon;
I. uracil herbicides such as lenacil, bromacil and terbacil;
J. triazine herbicides such as atrazine, simazine, aziprotryne, cyanazine, prometryn, dimethametryn, simetryne and terbutryn;
K. phosphorothioate herbicides such as piperophos, bensulide and butamifos;
L. thiolcarbamate herbicides such as cycloate, vemolate, molinate, thiobencarb, butylate, EPTC, triallate, diallate, ethyl esprocarb, tiocarbazil, pyridate and dimepiperate;
M. 1,2,4-triazin-5-one herbicides such as metamitron and metribuzin;
N. benzoic acid herbicides such as 2,3,6-TBA, dicamba and chloramben;
O. anilide herbicides such as pretilachlor, butachlor, alachlor, propachlor, propanil, metazachlor, metolachlor, acetochlor and dimethachlor;
P. dihalobenzonitrile herbicides such as dichlobenil, bromoxynil and ioxynil;
Q. haloalkanoic herbicides such as dalapon, TCA and salts thereof;
R. diphenylether herbicides such as lactofen, fluroglycofen or salts or esters thereof, nitrofen, bifenox, acifluorfen and salts and esters thereof, oxyfluorfen and fomesafen; chlornitrofen and chlomethoxyfen;
S. phenoxyphenoxypropionate herbicides such as diclofop and esters thereof such as the methyl ester, fluazifop and esters thereof, haloxyfop and esters thereof, quizalofop and esters thereof and fenoxaprop and esters thereof such as the ethyl ester;
T. cyclohexanedione herbicides such as alloxydim and salts thereof, sethoxydim, cycloxydim, tralkoxydim and clethodim;
U. sulfonyl urea herbicides such as chlorosulfuron, sulfometuron, metsulfuron and esters thereof; benzsulfuron and esters thereof such as the ester thereof methyl, DPX-M6313, chlorimuron and esters such as the ethyl ester thereof, pirimisulfuron and esters such as the methyl ester thereof, DPX-LS300 and pyrazosulfuron;
V. imidazolidinone herbicides such as imazaquin, imazamethabenz, imazapyr and isopropylammonium salts thereof, imazethapyr;
W. arylanilide herbicides such as flamprop and esters thereof, benzoylprop-ethyl, diflufenican;
X. amino acid herbicides such as glyphosate (ROUND-UP�) and glufosinate and their salts and esters, sulphosate and bilanafos;
Y. organoarsenical herbicides such as MSMA;
Z. herbicidal amide derivative such as napropamide, propyzamide, carbetamide, tebutam, bromobutide, isoxaben, naproanilide, diphenamid and naptalam;
AA. miscellaneous herbicides including ethofumesate, cinmethylin, difenzoquat and salts thereof such as the methyl sulfate salt, clomazone, oxadiazon, bromofenoxim, barban, tridiphane, flurochloridone, quinchlorac and mefanacet;
BB. examples of useful contact herbicides include bipyridylium herbicides such as those in which the active entity is paraquat and those in which the active entity is diquat.
CC. Pesticides developed for application over the top of genetically engineered crops (e.g., ROUND-UP� READY SOYBEANS).
It has been reported that the penetration of pesticides is influenced by a variety of factors. These factors include, geometrically oriented capillary forces, relative interfacial tensions between fabric surfaces and pesticide emulsions, polymeric composition of the fibers and total pesticide load on the fabrics. Amongst these factors, penetration and permeability are notably dependent on pesticide load on the fabrics (see, Obendorf, S. K. et al., Archives of Environmental Contamination and Toxicology, Vol. 21, 1991, p10-16). Consistent with these findings, a decrease in detoxification of certain pesticides (e.g., methomyl) was observed with an increase in pesticide concentration being loaded onto the fabric. Thus, in a preferred embodiment, the halamine is loaded using a high add-on rate.
In certain aspects, the concentration of the pesticide (e.g., methomyl) that was exposed to the fabric was proportional to the percent reduction of the pesticide. Without being bound by a particular theory, it is believed that the pesticide/halamine ratio is more critical to reduction than the actual contact time of the pesticide with the fabric. A pesticide to halamine ratio of about 10:1 to about 1:10 is suitable for the present methods, preferably, a ratio of about 5:1 to about 1:5 is used and, more preferably, a ratio of about 1:10 to about 1:1 is used. Table 1 sets forth various halogen ratios and percent reductions of various pesticides.
Pesticide/Chlorine Ratio
Pesticide Reduction (%)
In certain other aspects, the pesticide protective articles, such as pesticide protective clothing, possess regenerable and durable properties. For instance, after effective detoxification of a pesticide is obtained, the article can be rendered capable of possessing detoxification properties again. As illustrated in FIG. 2, the detoxification process on treated fabrics is completed after removal of the degraded pesticides on the surface of fabrics by laundering. In order to verify the mechanism as set forth in FIG. 2, re-bleached fabrics that were previously exposed to pesticides, demonstrated the ability to detoxify pesticides again. The previously exposed fabrics exhibited pesticide detoxification potential after laundering and re-bleaching, and therefore, it is concluded that the functional finishing is regenerable. As such, using the processes of the present invention, detoxifying properties are imparted onto articles, such as textiles, and these properties are regenerable.
Furthermore, the detoxifying properties imparted onto articles are durable. The durability of the process and its potential to continually detoxify pesticides was demonstrated through the percent reduction of pesticides of the article (e.g. finished fabrics) after laundering. A high percent reduction of pesticides (e.g. aldicarb) by fabrics that were laundered fifty times indicated that the detoxifying properties that were imparted were durable. Thus, the functional finishing on the cotton/polyester fabric is durable, surviving fifty equivalent regular machine washes without compromising its detoxification potential. This finished fabric can therefore provide optimum protection as well as comfort to the wearers.
The following examples are offered to illustrate, but not to limit the claimed invention.
The selected textile materials were 65%/35% polyester/ cotton (see, Table 2) blended fabrics, #7436 Dacron/cotton (available from Testfabrics Inc. Midlesex, N.J.). The compound used in fabric finishing was 1,3-dimethylol 5,5-dimethyl hydantoin (DMDMH) (Lonza Inc., Fairlawn, N.J.) (see, FIG. 3A). Sodium hypochlorite solution, was used in the halogenation (chlorination) of the: finished fabrics. The targeted pesticides were carbamates: methomyl (see, FIG. 3B) [S-methyl N-(methyl carbamoyloxy) thioacetimidatel] or Lannate�, (E.I. du Pont Nemours & Co. Inc., Wilmington Del.); aldicarb (see, FIG. 3C) [2-mesyl-2-methylpropionaldehydeO-methylcarbamoyloxime] (Riedel-de H�en). AATCC detergent 124 was used for all laundering. All other chemical reagents were purchased from Fisher Scientific.
Fabric Weight
Fiber Content
plain weave
Vapor Pressure
mm Hg
Toxicity, mg/kg
(LD50, male rats)
5 � 10−5
1 � 10−4
Polyester/cotton fabrics were washed in a domestic washing machine at 50� C. prior to the actual treatment of the functional compounds. The halamine functional compounds on the fabrics were achieved in two major steps: grafting a hydantoin ring onto the fabrics as the backbone for the functional compounds, followed by halogenation (e.g., chlorination) of the fabrics with hypochlorite bleach (e.g., CLOROX�).
The grafting of hydantoin ring onto the cotton/polyester fabrics was carried out using a wet finishing process. The weighed fabrics were submerged into an aqueous 6% (w/w) DMDMH solution for 5 min. and then wringed through a padder to secure a wet pickup of 70-100% through a 2 dip-2 nip cycle. These wet fabrics were then oven-dried at 85� C. for 5 min. and cured at 150� C. for 5 min. Following this, the fabrics were washed in water at 50� C. for 30 min. to remove any excess chemicals on the surface of the fabrics.
After the wet finishing process, the treated fabrics were bleached with solutions containing 0.01% and 0.1% (w/v) active chlorine content. The treated fabrics were submerged into aqueous bleach solution at one of the specified concentrations at 25� C. for 15 min. Then, the fabrics were air dried and stored at standard condition (25� C., 65% relative humidity). The chemically finished fabrics were then cut into 3�3 inches square swatches for exposure to pesticides in the subsequent testing.
Methomyl and aldicarb were dissolved in methanol at three different concentrations: 250, 500 and 1000 ppm. One mL of one of these pesticide solutions was directly loaded onto a fabric swatch. A contact time of 5 min. was allowed before the exposed fabric was extracted in organic solvent for detoxification assessment and degradation analysis. Fabrics that were not treated with DMDMH and bleach were also used as control samples.
The extraction of the exposed swatches was done by soaking a swatch into an initial volume of 50 mL ethyl acetate for 15 min. with vigorous agitation. The extraction was repeated with another 50 mL of ethyl acetate; the combined 100 mL of the extracted solvent was reduced to 2 mL in volume by rotor-evaporation under partial vacuum at 40� C. To this 2-mL sample, 1 μL of 2-ethyl-5-methyl pyridine was added as an internal standard for quantitation during the chromatographic analysis. After which, 1 μL of the extracted sample was injected into a gas chromatograph.
Gas chromatography was performed on a Hewlett Packard 5890 series II GC, equipped with a nitrogen-phosphorus detector (NPD), using a 15 m�0.25 mm I.D. DB-1 column, 0.25 μm film (J&W Co.). The temperature program was initially set at 100� C. for 3 min., raised at a rate of 7� C./min. to 250� C. and held for 5 min. The injector and detector were set at 250� C. and 280� C. respectively. Helium was used as the carrier gas at a flow rate of 0.84 mL/min; hydrogen flow rate was 2.98 mL/min; nitrogen flow rate was 29.16 mL/min. A split injection was used at a split ratio of 25:1. The responses of the resulting peak areas and relative peak areas were integrated and recorded using a HP 3396 II integrator. For each sample, at least three or more repetitions at each condition were carried out.
The laundering tests were carried out using the Launder-O-Meter from Atlas Electric Devices Co., following AATCC #61-1994 (American Association of Textile Chemists and Colorists, Technical Manual, AATCC, Research Triangle Park, N.C., 1996, pp 92-95). Each sample (that was exposed to 1000 ppm aldicarb solution) was laundered at 25� C. for 45 min. using 0.225 g AATCC detergent 124 and 150 mL distilled water. Then, the sample was rinsed with distilled water and air dried before re-bleaching. Re-bleaching of a sample was done by using a bleach solution containing 0.01% active chlorine content prior to exposure to 1000 ppm aldicarb solution in the subsequent testing. After which, these samples were laundered four more times using the same method and identical conditions, air dried and re-bleached using the same bleach solution before exposing them to 1000 ppm aldicarb again. Finally, these samples were laundered five more times, air dried and re-bleached using the same bleach solution prior to the last exposure to 1000 ppm aldicarb solution. The total number of washes done on each sample equated to ten. The amounts of aldicarb reduction at each laundering interval were used to show the durability of the functional finishing on the fabrics.
This Example illustrates the detoxification of three different concentrations of methomyl by halamine structures on fabrics.
Using the materials and methods sets forth above, three different concentrations of methomyl were detoxified by halamine structures on the fabrics. The results are summarized in FIG. 4. Relative peak area response factors (peak area response of pesticide divided by peak area response of internal standard) of the control fabrics were used to determine the original amount of pesticide on the fabrics at 0% reduction. The subsequent relative response factors at the various pesticide concentrations and active bleach contents were subtracted from this original vahle to calculate the amount of pesticide being decomposed by halamine compounds on the fabrics. After this difference was divided by the original amount, it was expressed as the percentage reduction of pesticide at those various concentrations.
As shown in FIG. 4, the concentration of active chlorine treatment affected the reduction of methomyl in two of the three concentration levels of 250 and 1000 ppm levels respectively. Higher concentration of active chlorine treatment led to increased reduction of methomyl on the fabrics. At the 250 ppm level, the percentage reduction of methomyl with the 0.01% active chlorine treatment (9.35%) was almost half ofthat at the 0.1% active chlorine treatment (19.90%). Similarly, the percentage reduction at 1000 ppm with 0.1% active chlorine treatment (11.63%) was almost three times as much as that of 0.01% (4.43%). This could be explained by the fact of a high concentration of chlorine i.e., more amine (nitrogen-hydrogen) groups on the hydantoin can be converted to active nitrogen-chlorine. Thus, more chlorine would be available on the fabric, increasing the amount of active moieties, which detoxify the methomyl on contact. Methomyl was found to disappear rapidly in aqueous solution at a chlorine/methomyl ratio of 10 to 1(see, Miles, C. J. and Oshiro, W. C., Journal of Environmental Toxicology and Chemistry, Vol. 9, 1990, p 535-540).
The effect of methomyl concentration could also be seen in the results. The reduction of methomyl and methomyl concentration were found to be inversely related. With the exception of the 500 ppm level, there was a decrease in the reduction of methomyl from the 250 to 1000 ppm levels in both of the 0.01% and 0.1% active chlorine treatments. With the chlorine content being held constant at both levels while the concentration of methomyl was increased from 250 to 1000 ppm, the ratio of chlorine to methomyl was actually decreased, leading to slower degradation of methomyl. This is reflected in the decrease in reduction of methomyl. The percentage reduction of methomyl at 250 ppm, 0.01% active chlorine treatment (9.4%) was more than double the reduction at 1000 ppm (4.4%). Similarly, at 0.1% active chlorine treatment, the percentage reduction of methomyl at 250 ppm (19.9%) was the highest, followed by that of 500 ppm (18.6%) and 1000 ppm (11.6%) showed lowest reduction. Since the chlorine/methomyl ratio was gradually decreased with increasing methomyl concentrations, the active chlorine moieties were also decreased, thus, retarding the degradation process (see, Miles, C. J. and Oshiro, W. C., Journal of Environmental Toxicology and Chemistry, Vol. 9, 1990, p535-540). With the gradual increase in methomyl concentration from 250 to 1000 ppm, the percent reduction at the 0.1% active chlorine treatment level slightly decreased.
This Example illustrates chemical detoxification of aldicarb using methods of the present invention.
The results of a percent reduction of aldicarb by halamine structures on the fabrics are summarized in FIG. 5. The results from the detoxification of aldicarb showed a slight increase in the percentage reduction as the concentration was increased from 250 to 500 ppm for both active chlorine treatment. At the 250 ppm level, the percentage reduction of aldicarb for the 0.01% and 0.1% active chlorine treatment were close: 79.6% and 74.0%. In fact, effective detoxification and degradation of aldicarb could be achieved at 0.01% active chlorine content. Although higher levels of active chlorine treatment is also effective, from an economical point of view, the lowest possible concentration that yields comparatively effective results is most desirable.
In comparison, the percent reduction of aldicarb at all three concentrations was found to be much higher than that of methomyl. This difference in percent reduction became more apparent in FIG. 6, as the percentage reduction of the two pesticides was compared. The degradation of aldicarb by the halamine compound has proven to be more efficient than that of methomyl. The degradation of both aldicarb and methomyl begins when the molecules are broken down into smaller fragments. One such possibility is through oxidation.
The chemical structures of aldicarb and methomyl (see, FIG. 3 B and C), apart from the presence of an additional methyl group on aldicarb, the major difference between the two structures is the location and environment of the sulfur atoms. Without being bound by any particular theory, it is believed that being separated by two single bonds, both sulfur and carbon-nitrogen double bonds may become more vulnerable to chlorine oxidation. In the case of methomyl, delocalized lone pairs may be less attractive to chlorine on the halamine. However, in the case of aldicarb, the chlorine could possibly be drawn by both lone pairs on the sulfur as well as the nitrogen atoms, leading to the simultaneous break-down of aldicarb. Hence, the oxidation of this stabilized sulfur atom on methomyl would be slower than that on aldicarb, leading to slower degradation and lower reduction of methomyl.
Compared to the detoxification of methomyl, the reduction of aldicarb at all concentration levels (250, 500, 1000 ppm) was more effective and efficient. Over 70% reduction of aldicarb was attained at all pesticide concentrations for both levels of active chlorine treatment. Even at the lower level of 0.01% active chlorine content, almost 80% reduction was achieved at all pesticide concentrations. Due to the higher aldicarb reduction at this lower active chlorine treatment than the higher one, it can therefore be concluded that the concentration of active chlorine treatment is not as critical in the detoxification of aldicarb as in methomyl. Moreover, from an economical perspective, it could be suggested that an active chlorine treatment of 0.01% would be adequate for effective detoxification of the 1 mL aldicarb inoculation on cotton/polyester treated in 6% DMDMH solution.
Durability of the Functional Finishing
Results of the percentage reduction of aldicarb on laundered fabric samples are set forth in FIG. 7. The percentage reduction of aldicarb on all laundered fabric samples still remained well over 90%. This indicates that the relatively high reduction attained in the previous testing could be maintained even after laundering. According to the AATCC technical manual, one Launder-O-Meter wash is equivalent to five regular machine washes (see, American Association of Textile Chemists and Colorists, Technical Manual, AATCC, Research Triangle Park, N.C., 1996, pp 92-95). Also, a functional finishing that is considered durable on fabric is one that lasts for at least fifty regular machine washes. Hence, the treated fabrics showed excellent durability as well as outstanding pesticide detoxification potential even after fifty equivalent regular machine washes. This confirms that the fabric could indeed be considered as a regenerable, detoxifying pesticide protective clothing material, proving the initial hypothesis in the previously presented FIG. 2 to be valid.
It is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application and scope of the appended claims. All publications, patents, and patent applications cited herein are hereby incorporated by reference in their entirety for all purposes.
|Cited Patent
|Filing date
|Publication date
|Mar 14, 1945
|Apr 26, 1960
|William W Prichard
|Anti-vesicant coating composition
|Jan 3, 1972
|May 15, 1979
|Imperial Chemical Industries Limited
|Fluorinated compounds containing functional groups
|Jun 13, 1979
|May 6, 1980
|The United States Of America As Represented By The Secretary Of The Army
|Novel fabric containing microcapsules of chemical decontaminants encapsulated within semipermeable polymers
|Nov 18, 1987
|Nov 28, 1989
|Southwest Research Institute
|Polymeric decontamination composition
|Feb 19, 1993
|Dec 6, 1994
|Ciba-Geigy Corporation
|Selective herbicidal composition comprising 1,5-diphenylpyrazole-3-carboxylic acid safeners and sulfonylurea herbicides
|Jul 28, 1994
|Feb 13, 1996
|Auburn University
|Polymeric cyclic N-halamine biocidal compounds
|Sep 13, 1996
|Mar 16, 1999
|The Regents Of The University Of California
|Durable and regenerable microbiocidal textiles
|Jun 6, 1996
|Jan 25, 2000
|Troy Technology Corporation, Inc.
|Method of stabilizing biocidal compositions of haloalkynyl compounds
|Apr 15, 1999
|Sep 26, 2000
|Troy Technology Corporation, Inc.
|Method of stabilizing biocidal compositions of haloalkynyl compounds
|Dec 6, 1997
|May 8, 2001
|Isagro S.P.A.
|Fungicidal compositions based on (N-phenylacetyl-N-2,6-XYLYL)methyl alaninate
|Mar 11, 1994
|Sep 15, 1994
|Univ Auburn
|Novel polymeric cyclic n-halamine biocidal compounds
|Database WPI, Section Ch, Week 199436, Derwent Publication Ltd., London, GB; AN 1994-291518, XP002157475 & KR 9 309 035B (Res Inst Nat Defence Sci), Sep. 22, 1993 abstract.
|Database WPI, Section Ch, Week 199436, Derwent Publication Ltd., London, GB; AN 1994-291518, XP002157475 & KR 93 0009 035 B1 (Res Inst Nat Defence Sci), Sep. 22, 1993 abstract.
|Citing Patent
|Filing date
|Publication date
|Mar 23, 2012
|Jul 1, 2014
|Eastern Michigan University
|Antimicrobial fabrics made using sol-gel/N-halamine chemistry, and methods of making same
|U.S. Classification
|8/115.51, 514/478, 8/189, 8/190
|International Classification
|Cooperative Classification
|European Classification
|Jan 17, 2001
Owner name: REGENTS OF THE UNIVERSITY OF CALIFORNIA, THE, CALI
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SUN, GANG;KO, LOUISE L.;SHIBAMOTO, TAKAYUKI;REEL/FRAME:011476/0088;SIGNING DATES FROM 20001109 TO 20010109
|Jul 20, 2007
|Fee payment
Year of fee payment: 4
|Aug 29, 2011
|Maintenance fee reminder mailed
|Jan 20, 2012
|Lapse for failure to pay maintenance fees
|Mar 14, 2012
|Expired due to failure to pay maintenance fee
Effective date: 20120120