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Square Deal Coin Purse
Roll over image to zoom in
It's most definitely hip to be square when you're toting a beautiful accessory with even more beautiful origins. Each satin pouch is handcrafted using glass beads and square pieces of shell by artisans from the Nam Dihn province of Vietnam. Working from their homes, artisans are able to care for their families and raise funds to care for handicapped orphans in the community, all while earning a living wage.
- Satin, glass & shell beads
- 3" H x 5" W (7.6 x 12.7 cm)
- Handmade in and fairly traded from Vietnam
Created to help women worldwide gain economic security for themselves and their families by earning fair wages for their handiwork, Global Girlfriend sources women-made, fair-trade imported, eco-friendly products. By supporting long-term partnerships with the artisans, it fosters equal employment opportunities, healthy and safe working conditions, technical assistance, and development strategies to help reduce poverty, one community at a time. Become a "Global Girlfriend" and help build a brighter future for girlfriends around the globe!
For bulk pricing on these and other items, please contact our Customer Service department at email@example.com.
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Recent reviews:
May 29, 2015 - I bought the brown and absolutely love it. As others have said, it's well made and the photo doesn't do it justice. I wanted a change purse that would accommodate bills and cards as well. It's perfect (and pretty).
April 18, 2015 - I like a large coin purse that I can get my fingers into and this is the one to have! Very good quality and attractive.
April 9, 2015 - Very sweet little coin purse, beautifully crafted!
January 16, 2015 - I gave a couple of these as gifts. They are so well made and attractive, I wish I had gotten one for everybody.
December 7, 2014 - The pictures don't do these purses justice. I got the white, red and gold ones and they are quite beautiful and well made.
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Customer Reviews
Read reviews for this product
Posted 10/28/2014 at 4:17 AM by Catherine
Arrived in timely manner, and in perfect condition. All ornaments were well packaged. Very happy with all.
Sending the same ornament to different places? If you order more than one of an item and want them shipped to different addresses, please order them individually. We will ask you for the individual shipping addresses later in the ordering process.
Teddy Bear with Presents Christmas Ornament
Personalized Christmas Ornament
This teddy bear is all ready for Christmas with a stack of presents in front of him. A nice ornament for a new baby boy or child who is as sweet as their favorite teddy bear toy.
Material: Glass
Ornaments shown on our site are personalized, as examples only, so you can see where we put the words/names you give us. Some ornaments allow you to select hair or uniform color. If there is no color choice, it is not available on that particular ornament. We will do everything possible to catch any mistakes in spelling, etc., but are not responsible if we do as you request, and it is then not correct. The ornament you see above is the way it will look when you get it, except for the personalizing instructions you give us and any optional attributes you select.
Read what our customers say about our Personalized Christmas Ornaments and their shopping experience!Hover over testimonials to stop scrolling
8/16/2014 - "I was excited awaiting my three orders, I always get that way, when waiting on my ornaments to arrive. As usual, they were even more beautiful, then they looked on line. I've been shopping the Ornament Shop for years started shortly after they opened for business. Never have had one I needed to return. They are fantastic, and the people who receives them as gifts, look forward every year to what I'm going to give them. Paulette P."
8/27/2014 - "I use this company every year! Love everything they have! Tamra P."
10/24/2014 - "Great high quality ornaments! I purchase these every year for our clients who purchase homes from us. They love them! Deb C."
9/25/2014 - "I have been purchasing ornaments for the past 7 years from OrnamentShop.com and I love their ornaments and the great selection. Robert H."
11/27/2014 - "Dear Ornament Shop, I just received my ornaments (in 4 days!!!!) and once again, am so pleased with your wonderful products and speedy service. I have been a loyal customer for (I believe) 6 years now and have never been disappointed with my purchases. Thank you again! Sincerely, Jill L"
8/27/2014 - "This is my 3rd time ordering ornaments from the OrnamentShop.com. They even send you a reminder to order in August. I'm all ready with my special family ornaments, which is now off my Christmas list! Love them! Holly S."
12/31/2014 - "Loved every single one of the ornaments that I ordered, and each came in the nick of time for Christmas. Thank you so much. Will not hesitate to order again. Janet F."
10/20/2014 - "The ornaments are beautifully detailed and personalized. I ordered 5 as gifts and all of them exceeded my expectations. They are more beautiful in person! Judy H."
5/24/2015 - "I do all my ornament shopping at OrnamentShop and have for a number of years now. I am 94 years of age and hope I will be ordering next year. Ann Z."
10/21/2014 - "I have ordered ornaments from you for years. I have always been very happy with my purchases. My Grandchildren love them. Sincerely Bonnie D."

subset: commoncrawl


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Season 2, Episode 5 Used, Abused and Unenthused
First Aired: April 23, 2006
Beth deals with a demanding, politically incorrect client (David Clennon); Huff has a high old time with a colleague (Anjelica Huston); Teddy gets a job as an overnight security guard at a flower shop; Beth finally agrees to go to couples therapy; a law-firm partner gets a line on Russell's drug problem.
Guest Cast
Cheryl Carter Cheryl Carter Kira Riley
Christopher Curry Christopher Curry Matt Stewart
David Correia David Correia Ray Martinez
Ned Schmidtke Ned Schmidtke Allen Meeks
Jack Laufer Jack Laufer Homeless Hungarian
Sam McMurray Sam McMurray Dr. Hoffman
David Clennon David Clennon Braden Marter
Billy Lush Jake Stewart
Sebastian Tillinger Sebastian Tillinger Max Wheeler
Jason Beghe Darren Hadleck
Sarah Jones Leah
Anjelica Huston Dr. Lena Markova
Ken Howard Walt
Cast & Details See all »
- Premiered: November 7, 2004
- Rating: TV-MA
- User Rating:
- Premise: A psychiatrist questions his choice of profession as he deals with problems at home and at work. At the office, a procession of troubled patients keeps him hopping, while at home he has a teenage son feeling his oats and a wife constantly banging heads wit… (more)
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Huff - Season 2 (3 Discs)
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definition of technologically competent
IT Planning: A Corporate Mantra
Aligning IT with business objectives has long been a mantra of corporate directives. But organizations often fall short of publishing quality documents and
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Begins , Planning Process Definition , Planning Process Guide , Planning Process Management , Planning Process Model , Planning Process Page , Acquisition Planning Process , Based Planning Process , Benefits Planning Process , Business Planning Process , Comprehensive Planning Process , Continuing Planning Process , Development Planning Process , Enhanced Planning Process , Entire Planning Process , Formal Planning Process , Implementation Planning Process , Information Technology Planning Process ,
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Last update: Wednesday 19 September 2012 [14 news items]
Intel Medfield struggling against ARM platforms, say Taiwan makers
Sep 19, 01:00
Although Intel's smartphone platform, Medfield, and has won adoption from several vendors including Orange, Motorola Mobility, Lenovo, ZTE and Lava International, it is struggling...
Lenovo and Motorola delay launch of Intel-based tablets
Jul 26, 01:25
Although Intel has been aggressively promoting the combination of its Medfield platform with Android for the smartphone and tablet PC markets, the recent decisions of the company's...
Intel aggressively planning for the smartphone industry
Jun 21, 01:20
Intel's Medfield platform-based smartphones have recently received attention from handset players and telecom carriers such as Orange, Lenovo, Motorola Mobility, ZTE and India-based...
Intel to push StudyBook tablet PC for emerging markets
Apr 3, 01:15
Intel is set to push a tablet PC product codenamed StudyBook to target emerging markets and will adopt the same sales model as its Classmate PC, according to sources from PC players...
Intel Medfield to heat up competition in entry-level smartphone market
Mar 20, 14:47
The adoption of Intel's Medfield processors by China-based vendors including Lenovo and ZTE for the production of entry-level smartphones may heat up competition in the segment, according...
ARM not worried about Intel foray into handheld device platforms, says ARM executive
Jan 20, 12:13
ARM is not under competitive pressure from Intel's move into processor platforms for handheld devices, because Intel does not let clients know the value of adopting its platforms...
Intel to adopt TI, Broadcom wireless chips for Medfield, Clover Trail-W platforms
Dec 30, 12:24
Intel will adopt the Texas Instruments-developed (TI) WL1283 Wi-Fi/Bluetooth/GPS chips for its Medfield platform to be launched in the second quarter of 2012 and Broadcom-developed...
Intel to launch Medfield platform in 2Q12, Clover Trail-W platform in 4Q12
Dec 29, 14:16
Intel plans to launch its Medfield platform running on Android 4.0 (Ice Cream Sandwich) OS in the second quarter of 2012 and then release its Clover Trail-W platform running on Windows...
Intel to struggle to see general adoption of Medfield in 2H12, say Taiwan makers
Dec 16, 14:10
Intel will launch 32nm Medfield specifically for use in smartphones and tablet PCs in the first half of 2012, but will struggle to win general adoption of the platform by vendors...
Intel to launch new CPUs for tablet PCs in 2012
Nov 11, 01:15
Intel reportedly plans to overhaul its product roadmap for 2012, with its Medfield CPUs focusing on handset applications, while developing a new CPU lineup exclusively for tablet...
Intel expected to offer 3rd-generation MID platform Medfield in 3Q11
Feb 23, 16:20
Intel, in order to compete with ARM architecture devices which are prevailing in the tablet PC industry, has had Medfield, its third-generation MID platform, enter testing by Taiwan-based...
IDF San Francisco: Intel unveils new mobile chips and technologies
Sep 24, 16:02
David Perlmutter, executive vice president and general manager, Architecture Group of Intel has debuted three new Intel Core i7 processors for notebooks based on Intel's Nehalem microarchitecture...
Intel to unveil new product roadmap at IDF San Francisco
Jul 17, 12:28
Intel is expected to unveil its new product roadmap as well as new technology innovations at the upcoming IDF to be held in San Francisco from September 22-24, according to market...
MID sales a lot lower than Intel estimates, say MID makers
Jun 5, 10:58
Global sales of Intel-based mobile Internet devices (MIDs) since the launch of the Menlow platform have been less than 30,000 units, a lot lower than Intel's estimate of 150,000-200,000...
- Touch panel suppliers step up shipments for new iPhone
- Acer passes down Stationary Computer and Display BU management to younger executives
- Notebook component makers shift to server applications along with ODMs
- ASE expects to post revenue growth through 4Q15
- UMC slows 28nm ramp
- Electronic dictionary vendor Global View sets up business incubator in Beijing
- Taiwan IC design houses expect orders for handsets to pick up in August
- Acer pushing investments in startups
- MediaTek posts lower revenues and profits for 2Q15
- Sharp plans to stop in-house production of a-Si thin-film PV modules, says Nikkei News
- Digitimes Research: China smartphone AP shipments to grow 23.5% in 2H15
- Adlink posts 1H15 net EPS of NT$1.77
- TPK revenues slip due to decline in handset touch panel shipments
- LED to account for 19% of transportation lamp revenues in 2015, says IHS
- Coretronic reports 2Q15 performance
- Taiwan market: Chunghwa Telecom sees 4G user base increase to 2.9 million
- Energy management revenues for healthcare markets expected to reach US$2.2 billion by 2024, says report
- Hua Hong Semiconductor, QST announce 3-axis gyroscope SoC
- Digitimes Research: Taiwan 2Q15 small- to medium-size panel shipments drop 0.4%
- GCL-Poly Energy has no plans to produce solar cells
- China imports 10,942 tons of polysilicon in June
- Silicon Motion to offer solutions for 3D XPoint devices
- Taiwan promoting recycling of household wastewater for industrial use
- FET arranges stake investment in CNS via buying corporate bonds
- Innolux to merge with CMEL
- Releases
- White papers
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- GrassWonder Selfie Robot opens up a value chain full of creativity
- Imagination joins 5G Innovation Centre to drive development of next-generation mobile data networks
- Conexant preps for growth in Asia Pacific region, expands into new facility
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- Got The Message? Ensuring efficient and reliable delivery of content across a mission critical digital signage network
31-Jul-2015 markets closed
|TSE electronic
|OTC electronic
- China shares continue to slide after massive sell-off (Jul 28) - BBC News
- New York backs down in Uber fight (Jul 23) - BBC News
- Imagination appoints industry veteran to lead its expanding China operations (Jul 22) - Company release
- Toshiba chief executive to resign over scandal (Jul 21) - BBC News
- Jet.com takes on Amazon with the promise of lower prices (Jul 20) - TechCrunch
- Micron does not believe deal with Tsinghua is possible (Jul 20) - Reuters
- Corning announces US$2 billion share repurchase program (Jul 15) - Company release
- Crystalsol announces development of fully printed flexible photovoltaic film using silver nanowires from Cambrios (Jul 14) - Company release
- Digitimes Research: Shrinking tablet market prompts China touch panel supply chain to look for growth elsewhere
- Digitimes Research: Apple to push forward with In-Cell touch technology in 2015 but highly considering G/G for 2016
- Digitimes Research: Tsinghua Unigroup acquisition of Micron faces difficulties, but is a must for China for further development
- Digitimes Research: Qualcomm to push inexpensive mobile device market with Microsoft and Allwinner solutions
- Digitimes Research: Touch IC developers turning to fingerprint sensors
Security a must for IoT market: Q&A with NXP EVP Steve Owen
The acquisition of Freescale by NXP Semiconductors will make NXP the world's second largest MCU supplier...
Gigabyte to stay competitive in VGA market with new technology: Q&A with Eddie Lin, associate vice president of Gaming Product Business Unit
Competition in the graphics card market has grown fierce as demand for graphics cards from the gaming...
Japan startup Socionext aiming big in IT industry
Socionext, a Japan-based corporation focused on the design, development, and sales of system-on-chip...
TCA chairman optimistic about Taiwan ICT industries despite challenges
Computex has evolved into one of the biggest and most important ICT trade shows in the world since...
- Smartphone and tablet industry: The view from Taiwan - May 2012
Taiwan-based companies have a long and successful history of involvement in the supply chain for mobile devices, which for the purposes of this article consist...
- Taiwan motherboard industry overview - May 2012
The year 2011 saw the motherboard industry reverse its trend of declining shipments year-on-year, to post a slight 0.2% growth. This upturn in fortunes was expected...
- Notebook market overview - Jun 2011
The notebook industry in 2010 experienced several major events that significantly changed the industry's ecosystem for the year and the industry is also believed...
- LCD TV overview - Jun 2011
Growth of the global LCD TV market was not as strong as expected in 2010 as the market continued to feel the aftershocks of the economic recession that had hit...
- Wireless broadband developments in Southeast Asia markets
As of 2013, the 10 ASEAN nations had a total of over 700 million mobile subscriptions, with the CAGR from 2003-2013 reaching 24%. This Digitimes Research Special Report analyzes the various mobile broadband markets in ASEAN and looks at the respective trends in 4G LTE development for those markets.
- 2015 global tablet demand forecast
This Digitimes Research Special Report provides a 2015 forecast for the global tablet market and analyzes the strategies of key market players such as Google, Apple, Intel, and Microsoft.
- 2015 China smartphone panel trend forecast
This Digitimes Research Special Report analyzes the strategies of key China-based major panel makers BOE, Tianma and IVO for attacking the different market segments through technology and pricing, and their relationship to local vendors Huawei, Lenovo, ZTE, Xiaomi and Coolpad.


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Large rug
Large rug in a toffee colour. Will accept nearest offer. Good condition
Large rug in a toffee colour. Will accept nearest offer. Good condition
crochet rug custom made hand named single piece. In perfect condition. Size: 90cm X 45cm Thanks for look
Luxury black rug silky shaggy style black very soft and shiny cost a small fortune
Very good quality Woollen rug made in India Bokara design 195cm v 140cm Cotton warp (fringe) at both ends Guarantee note of origin and material on the reverse side. Last image attached is reverse side No stains, burns etc i.e. very hard wearing
* Immaculate condition * non smoking house * 200 x 290cm in size * Figaro Brand * Black & Red * Thick Quality rug * Retails at £144 I have two of these, both mint. 3 months old. Delivery is possible at £1 per mile. Location Chelmsford Essex. Em
This genuine part was a replacement for a missing part which was then found....so consequently unused, brand new. Normally £30. Slots onto end of hose easily, clips in. Fits Sebo Automatic X4 Anti-allergy hospital grade S Class. Collection only
Brand new carpet measuring 15 ft by 2.9, soft and luxurious feel but is hard wearing, brand new in immaculate condition
120cm x180 cm medium size rug ;striped design brown,beige ,cream,light blue going across width of rug ;new unused factory reject due to damage on reverse of rug the size of 50p piece (see photo), other than that ,no other fault;woollen rug ;perfect
Green rug 270cm x90cm new unused ;part of job lot of factory imperfect seconds bought;colour is definitely green but looks grey in photos;the edging on this one is not very neat and tight ;100%woollen rug ;part of job lot of factory imperfect/second
Hi I have 8 packs of 12mm top quality lamanite flooring in a classic oak , from bml scratch prof ideal for kids & pets. 9.6m2 I can also quote for fitting Please call or text 07473293344
Aqua coloured rug 265cm x186cm ;new/unused factory imperfect/seconds/not A grade-part o a job lot bought; one side of the edgings on this rug has not been edged neatly
A new/unused decorative rug in brown and light blue 120cm x180cm ;solid hard backing so will not crease under foot;rolls up for storage and transport
I am selling this Moroccan rug as we are moving house. It's in great condition. It was originally from Tangiers, Morocco and I paid £100. 32 inches x 150 inches Will accept £60. Ideally collect from Leyton. Delivery £25.
Green 100 % woollen rug 180cm x120 cm;new and unused factory imperfect,seconds,not A grade ;part of job lot bought;colour is forest green -does not show clearly in photo;the edging on this one is not very neat;
Part of job lot bought to sell;as explained above;this is a large rug 180cm x266cm;rolls up and folds up to take away
Brand New / Tags Still On Jute Mat /Rug 100% Natural 5ft x 3ft / 150cm x 90cm Absolute Bargain Delivery Possible £20 Contact: 07722246431
Perfect condition as seen in pictures. Selling due to redecoration. £90 ONO
large rug only £15.00 collection is from clacton on sea near town
Some whole and offcuts of multi coloured natural slate tiles. Various sizes and cuts, some in 4 unopened boxes though a few may have cracks. Unopened boxes not inspected. All are leftovers from a recent indoor floor project. These look fabulous when
Made especially for laminate floors to do the following: level out uneven floors. Provide extra leveling effect on uneven subfloors - ideal for historic homes or older wooden floors Specially impregnated wood fibers conform to uneven subfloo
New rug. Grey patchwork, easy to clean and to carry Size : 160x230
Beautiful large rug 180x270 in excellent condition tiny rip in one corner shown in picture above black brown and cream pattern. Collection only email or txt only 07535348893
Lovely grey rug- been used in spare room so is virtually brand new. Not sure on brand as it was a house warming present, but I have a beige one almost identical from ikea. Collection only East Ham (isn't very heavy so could be rolled and taken on p
Large jute rug. 240cms x 160cms Creased as it was stored folded for the last 2 years, but reverts to flat in a short while when spread on a flat floor.
In as new condition - The very high pile dampens sound and provides a soft surface to walk on. - Durable, stain resistant and easy to care for since the rug is made of synthetic fibres. - The high pile makes it easy to join several rugs, witho
Fabulous opportunity to purchase this stunning vintage large 2m+ colourful aztec handwoven wool reversible runner rug with intricate detailing. A real statement rug this beautifully designed and manufactured piece of textiles is of superb quality.
Ikea ADUM rug 133cm x195cm(4'4" x 6'5")used shaggy rug in cream/light beige;in very good condition;this size rug in this ADUM range is currently £50 in Ikea;
Hi I have 11 packs of quality 12mm lamanite flooring in smokey oak from bml scratch prof ideal for kids & pets. 13.8m2 I can also quote for fitting Please call or text 07473293344
Hi I have 7 packs of 12mm quality lamanite flooring in walnut from robusto scratch prof ideal for kids & pets. 9.051m2 I can also quote for fitting Please call or text 0747293344
Hi I have 13'packs of 12mm dark oak lamanite flooring this is a quality lamanite floor scratch prof ideal for kids & pets. 17.29m2 I can also quote for fitting Please call or text 0747293344
Needs some hoovering and maybe a little wash but otherwise is in very good condition. Collection times: from 8:30 to 19:30 (you choose)
Hey, I'm selling my new fake fur cream carpet. Collection only. Send me an email / text message.
120cm x180 cm medium size rug ;striped design brown,beige ,cream,light blue going across width of rug ;new unused factory reject due to damage on reverse of rug the size of 50p piece (see photo), other than that ,no other fault;woollen rug ;perfect
Green 100 % woollen rug 180cm x120 cm;new and unused factory imperfect,seconds,not A grade ;part of job lot bought;colour is forest green -does not show clearly in photo;the edging on this one is not very neat;
Large light cream 100%woollen rug 264cm x184cm;part of job lot of factory seconds bought;thoroughly vacuumed ;grade A quality in these ,retail for around £150;this is a factory second so is priced at £20;part of big batch of factory imperfect/second
Large rug 255cm x 187cm with green,white,cream speckled striped lines going across rug;brand new unused ;part of job lot of factory rejects due to not meeting grade A product bought;;about 6 different rug designs bought
Zebra print rectangle rug available for sale It's in excellent condition and from a smoke and pet free home Require an urgent sale so I'm open to reasonable offers Collection preferred but may deliver for a charge if it's local
Part of job lot bought to sell;as explained above;this is a large rug 180cm x266cm;rolls up and folds up to take away; new/unused rug -factory imperfect/seconds/not A grade
1-year old IKEA dark grey carpet excellent condition Has to go before 31 July Please contact me if interested
Traditional Quality Rug Red background 100% polypropylene Size: L170cm, W120cm Made in Belgium Very good condition Buyer collect
Hi I have 12 packs of chrome white 12mm lamanite flooring a really good quality floor scratch prof ideal for kids & pets, I also have other colours available listed I can also quote for fitting 16.625 m2 Please call or txt 07473293344
Children's car town city road map carpet for sale large good condition pet free & no smoking free home
Stop your rugs from moving on the floor. An unused roll of very good quality German made Rug Underlay for Smooth or Hard Floors (parquet, laminate, tiles, stone, marble, cork, PVC floor coverings). Beige colour. The roll is 30 meters long x 1.2 met
Shaggy Rug in natural Very good condition, size 200cm 250cm...no marks in clean condition
This short pile rug has had light use, in a bedroom and is in good condition. It measures 230 x 170cm. It was bought in IKEA approx 10 years ago and as the label shows, is 100% Polypropylene.
Thick quality carpet underlay in new condition taken out of wrapper. Also quality laminate flooring underlay in wrapper.
Laminate flooring to cover a large lounge, big bedroom bedroom and hallway. Flooring is in good condition, these were laid in my house for four weeks then removed as I moved home but have no use for it in my new home. I also have the strips (beading
Really good condition No stain From pet free smoke free home Pick up in E16UW
Milleken Carpet tiles One box contains 20 tiles (4.18 m2 / 44.99 ft2) Quantity: +2000 available Colour: Blue Tile size: 457.2 x 457.2 mm (18" x 18") The Essentials Collection is a range of cushion backed, tufted loop pile modular carpet whic
Can fit any laminate flooring can also do other flooring such as carpet and liner. Will beat any quote!! If interested contact Imran on 07802691328
Agnes small multi-coloured cotton rug, in good condition. Dimensions: 120 x 180cm. Bought for £65 from Habitat. Available immediately for pick up | Cash only
Beautiful maroon/cranberry and cream Belgian rug. Really thick , very good quality. 330 cms x 195 cms Missing fringe at one end! From pet and smoke free home Cash on collection only please


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How to deal when you and your BFF are crushing on the same dude
From fashion intern to fashion model: How I followed my dreams and landed a spot in GL's latest issue
The CW is taking the YA novel Little Women to the next level
Celebrate the end of summer with these sweet strawberry dishes
It's official: *Skylar Stecker* is our 2015 Fashion Bash headliner!
Hit the hallways with naturally gorgeous highlights
Is your #OOTD ruining your health?
Sneak a peek at our August/September issue starring Dove Cameron!
GL's Exclusive Look at Sunday's Best Friends Whenever
More Friends = More Fun
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AN HOUR AGO Are you and your bestie crushing on the same cutie?: http://t.co/96PRHavjrA pic.twitter.com/MXT0QTPS1F
2 HOURS AGO Fashion intern by day, fashion model by night?: http://t.co/8R049GFjJe pic.twitter.com/TMBzY3FGSB
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So pretty!
by rainyseattlegirl on 5/15/2012 1:53:46 PM
I think GL should use younger girls for samples of makeup, because although Drew's makeup is gorgeous, it's more suitable for older women who want a sophisticated, mature look. I don't think any teen I know would want to show up with dark red lips and tons of blush. Simpler, natural-looking makeup is the way to go!
by lemontwist213 on 5/15/2012 11:22:10 AM
Win, read and review one of these *amazing* new novels!
Calling all book-loving babes: We want Y-O-U to enter to win one of four incredible new reads from Houghton Mifflin Harcourt! Winners will review their novel for the chance to be featured in an upcoming issue of GL.
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Adult logo with Maxi-casual wear
Made of thick cut and sewn fabric with peace of mind,irony (irony)In one piece. Hooded design became U-neck neckline; Breast large "IR" logo is depicted in the Raper print in three dimensions.
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Welcome To the Association Of Corporate Advisers And ExecutivesThe Association of Corporate Advisers & Executives was formed as a society in 1960 by 30 founder members with the main objectives of providing a common forum for person engaged in or interested in corporate laws, taxation, audit, accounts etc.
The membership strength has crossed the number of 1000 members. The Association feels pride in claiming to be one of the few of its kind in the country in which the members hail from various diverse professions like Chartered Accountants, Company Secretaries, Cost Accountants, Advocates, etc.
The Association made a modest beginning but made a consistent progress in the field of imparting knowledge to its members and non-members by holding regular meetings, seminars, group discussions, lecture meetings, conferences etc. Eminent profession
Forthcoming Events
- 19th August 2015
Lecture Meeting on TDS on payments to Non-Residents - Section 195 and Section 9 of the Income-tax Act, 1961
- 10th August 2015
Lecture Meeting on Income Computation and Disclosure Standards - Analytical Study
- 13th August 2015
Group Discussion on FAQ on Reent Amendments and notification of Companies Act, 2013 and on Director's Report
- 14th August 2015
Lecture Meeting on (1) International Trade Law and WTO (2) How to Manage Clients and Office using Information Technology? Get Smart! Get Automated !
- 17th August 2015
Group Discussion on all aspects of HUF and its taxation
- 24th August 2015
Group Discussion on Implication of Service Tax on Reimbursements, Service Tax Registration Procedure, Amendment in Registration, Centralised Registration and Surrender of Service Tax Registration


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Perkins: Homeless Gillick could settle in nicely with Blue Jays
Pat Gillick sold his house in Toronto a couple of years ago, so by Gillick's brand of logic, it makes perfect sense for him to rejoin the Blue Jays as a wise old head.
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The word is out that Gillick might well latch on to a senior consulting role in Toronto similar to the one he took when he retired as GM of the Philadelphia Phillies after they won the 2008 World Series. Or put it this way: The Jays would love to have him – as much as tampering rules allow.
Two things about this make excellent sense. The first is that Paul Beeston believes in having experienced executives around to help reveal baseball's many ingrained truths. Bobby Mattick filled this role in Beeston's first term as team president. Sam Pollock also joined on, sharing his decades of executive experience. Beeston swears by this kind of stuff.
The second reason has to do with Gillick now living in Seattle. Apparently, he never lives where he works any more. When he left the Blue Jays to work in Baltimore, he kept his home in Toronto. When he left the Orioles to go to Seattle, he built a home in Prince Edward Island. He left Seattle for Philadelphia, but later built a home in Seattle while keeping his place in Toronto.
Eventually, he and wife Doris sold their Cabbagetown home and now that he is "retired" from the day-to-day stuff in Philly, he has moved into the Seattle home, while still keeping the place in P.E.I.
So why not work with Toronto, since he no longer has a home here?
Adding Gillick should be nothing but positive for Alex Anthopoulos, the newly minted GM. It would be one more experienced sounding board. Gillick has a tremendous scout's eye, can evaluate talent and has helped build winners everywhere he has gone.
A team, in any sport, wins when it has a lot of good players. You can't have too many. That idea should extend to the front office, too. Every top executive has front-office people whose opinion he trusts. Adding one more for Anthopoulos, especially one that might well be bound for Cooperstown one day, makes too much sense not to at least try to make it happen.
MY BAD: The PGA Tour's season-opening event in Kapalua now is the SBS Championship and no longer the Mercedes.
ON THE CORNER: The subject is wise old heads in the front office and there's none better than Jimmy Devellano, who helps keep watch over both the Red Wings and Tigers when he isn't busy watching out for kids at Christmas. Once again, the Jimmy Devellano Children's Foundation has mailed $5,000 to the Jim Proudfoot Corner of the Star's Santa Claus Fund. That will take a nice chunk out of the $1.5 million required to buy the 45,000 gift boxes for kids across the GTA.
Former Star photo guru Bill Lennon mails in $50 in memory of his brothers Frank, Donald and Gerald. More fifties: Armond DiFebo of Scarborough, Diane and Wilf Marshall of Pickering, Bryan Marsh of Thornhill and from George De Flece of Islington in memory of Josephine De Flece.
There are $25 bumps from Jozsef Papp of Bowmanville and Bob Haskill of Etobicoke, while retired Star man Morris Duff adds $30 in memory of former colleague Tom Kerr. Another $30 drops from Whitby's David McGregor for granddaughter Quinn.
One of the great Corner envelopes annually arrives from Scarborough's Alf Smith, who adds $250 for the kids with a nod to the fond memories of East Riverdale, Eastern Commerce and the East End Canadians soccer team.
The Corner
The Jim Proudfoot Corner, part of the Star Santa Claus Fund, is a great way for sports fans to help out needy children during the Christmas season. If you can help, please send a cheque – payable either to Jim Proudfoot Corner or to Star Santa Claus Fund – and mail it c/o Dave Perkins, Toronto Star Sports Dept., One Yonge St., Toronto, M5E 1E6. Tax receipts are issued for amounts $10 and above.
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Mendis, de Lange added to Amazon Warriors squadSri Lanka allrounder Jeevan Mendis and South Africa fast bowler Marchant de Lange have been confirmed as injury replacements in the Guyana Amazon Warriors squad ESPN Cricinfo, 1 month ago
TT Red Steel among the favourites as CPL T-20 starts today - Trinidad and Tobago's Newsday, 1 month ago
Caribbean Premier League 2015: Fixtures, Venue, Dates, Timings for T20 Carnival - International Business Times India, 1 month ago
Developing Sri Lanka's Budding Entrepreneurs
All 11 Finalists move forward to explore opportunities with an International Panel of Investors Jeevan Gnanam, CEO, Orion City, Hanif Yousuf, Group CEO, ExpoLanka, and Jeremy Huxtable, Group Chief Officer, Dialog Enterprise, with Buddika Witharana ...Sri Lanka Sunday Leader, 1 month ago
SLSBC organises top business delegation to Singapore
The Sri Lanka-Singapore Business Council (SLSBC) of the Ceylon Chamber of Commerce will be organising a Trade and Investment Promotion Mission to Singapore from 29 July-1 August. The mission is planned to coincide with the IE-SBF Seminar on ...DailyFT, 4 days ago SLSBC organizes top business delegation to Singapore Sri Lanka Daily News, 4 days ago
Tallawahs hunt third straight home win
JAMAICA Tallawahs will be seeking to keep their perfect home record intact when they take aim at leaders Barbados Tridents in the Hero Caribbean Premier League (CPL) match at Sabina Park today. The game is scheduled to begin at 6:00 pm. ...Jamaica Observer, 3 weeks ago
Pollard says Tridents will use small break to regroup
Captain Kieron Pollard says Barbados Tridents must regroup and seek to improve their form, following their second defeat in three outings in the Caribbean Premier League here on Monday. The reigning champions struggled to 135 for eight at Warner ...Caribbean Broadcasting Corporation, 3 weeks ago
Sri Lanka vs Pakistan 2015: Hosts Announce Squad for Five-Match ODI Series
Sri lanka would look to come up with a better performance in the ODIs unlike the Test series. Reuters The Sri Lanka Cricket selectors announced a 15-man squad for the upcoming ODI series against Pakistan on Tuesday. They have also picked up two ...International Business Times India, 3 weeks ago Sri Lanka announce squad for the ODI … Yahoo! India, 3 weeks ago
Aggressive Zouks exact revenge over reigning champions
BASSETERRE, St Kitts (CMC) -- St Lucia Zouks produced an aggressive batting display to post the tournament's highest score this season, as they gained revenge over Barbados Tridents with a 30-run victory in the Caribbean Premier League here Friday ...Jamaica Observer, 4 weeks ago Pietersen Fletcher power Zouks to victory MSN News US, 4 weeks ago
Patriots clip Tridents' wings by 1-run in...
The Barbados Tridents lost for the first time in this year's Hero Caribbean Premier League as they were defeated by the St Kitts and Nevis Patriots. A superb innings of 82 from Keiron Pollard was not enough to see the Tridents to victory as they ...RJR News Online, 4 weeks ago Emrit, Shoaib pioneer Tridents' win Caribbean Broadcasting Corporation, 4 weeks ago Emrit, Malik star in Tridents win Frontier Post, 1 month ago CPL: Barbados Tridents beat St Lucia Zouks;getting closer to CPL final Dominica News Online, 1 month ago
Tridents brush aside Red Steel to extend winning start
New Story 1. Tridents celebrate the fall of a Red Steel wicket during their CPL clash on Thursday. (Photo courtesy CPL) BRIDGETOWN, Barbados (CMC) Reigning champions Barbados Tridents continued their imperious start to the defence ...Antigua Observer, 1 month ago
T&T Red Steel bent out of shape
THE BARBADOS TRIDENTS bent the Trinidad and Tobago Red Steel into submission on Thursday night with an emphatic eight-wicket win for their third straight victory in the Hero Caribbean Premier League Twenty20 cricket match in front of a sold-out ...Barbados Daily Nation, 1 month ago Tridents chasing 96 for victory over Red Steel Barbados Daily Nation, 1 month ago
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Good Samaritan Regional Health Center
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St. Mary's Hospital Foundation Names 2015 Golf Tournament Sponsors & Chairman
Dr. Ralph Latta Earns 2015 Patient's Choice Award
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If These Household Chemicals Can Harm Wild Birds, What About Your Pet?
Florida Green Lizards Develop Stickier Feet in Just 15 Years
Lost Bear Cub Cries for His Mom
Dr. Becker Talks About Osteosarcoma in Dogs
Dr. Becker: How Is Chagas Disease Transmitted?
Dr. Becker's Cube Steak Biscotti: A Treat for Your Pets
View All Pet Videos
The delightful days of spring can also bring hidden dangers for your pet - ones you might never imagine. For your pet's sake, please check out these 6 important tips. It could mean the difference between life and death for your beloved companion.
This handsome orange kitty knows green is his color.
Well-meaning pet owners have taken to the Internet in search of the wildlife they need to feed their dog or cat a prey model diet. What they don't know: online shopping for wild game can result in a $500 fine and jail time.


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The food is extraordinary!! the staff are really nice and helpful. Had a lovely bottle of Rioja to go with the meal. you have got to go to this restaurant!
3 Days in Liverpool
Guide to Liverpool for Families
Must do's in Liverpool
The staff here and the food are brill what more can I say , will definitely be back can not wait to cost Liverpool again !!!!!
Looked at the menu and was a bit mystified as tapas is rather new to me in Uk. However I was thrilled to say that I thoroughly enjoyed all six dishes shared with my partner under a heated section outside. The sea bass was to die for as was the chicken. Soup tasty and filling and the veg/ salad we...
Visited for tapas prior to catching our train home. Very central and a good bustling atmosphere. Knowledgable staff about both menu and wines. We had 3 dishes and sourdough from the £11.90 lunch menu..(before 6.00pm) and 3 from the dinner menu. Good quality stuff and strongly recommend.
Visited for our Wedding Anniversary recently. We were greeted with a complimentary glass of bubbly on arrival which was a lovely touch. The food was fantastic and great selection of drink choices available too! Love the Gin Bar options! The staff were so friendly and helpful, particularly Jose who was very attentive and really made us feel welcome. Will definitely...
Love this place, food is amazing and we were served by a young Australian lad who really knew his stuff, he gave us great advise on the specials.
We never heard of this Restaurant before, but we are glad we decided to walk in! Everything was excellent from the atmosphere, through the staff and the Food which was fantastic. A very nice surprise after several disasters in Liverpool's Restaurants...
Wandering around the harbour side area, I think that its called Liverpool 1, after shopping and feeling hungry. There are a large number of eateries of all types, some busy, some not so busy. Salt house was busy and we could see what the food looked like from the diners outside, everything looked good, well presented and good portion size....
Staff are very friendly and well trained, food is served in a unusual way when ordering 3 plate tapas (one dish at a time in no particular order) but is faultless. Top quality food, quality presentation and for a reasonable price. Would highly recommend over other close by restaurants.
The staff found me and my husband a table despite not booking on a busy Friday night. We don't really do tapas as we normally find it expensive and the dishes abit bland...we definitely were proved wrong here.all dishes were so tasty, especially the lamb shoulder with feta. The whole experience was topped off by the staff who were all...
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Is Matt Prior the best wicketkeeper?
The Chuck Fleetwood-Smiths praise Prior and see what the MCC members are wearing. Sam Collins and Jarrod Kimber are your hosts.
- Players/Officials : Stuart Broad | MS Dhoni | Matt Prior
The Chuck Fleetwood-Smiths praise Prior and see what the MCC members are wearing. Sam Collins and Jarrod Kimber are your hosts.
Anwar Ali's heroics helped Pakistan chase down 173 against Sri Lanka with four balls to spare, sealing the series for the visitors | Aug 1, 2015
Melinda Farrell is joined by George Dobell and Jarrod Kimber to discuss what they learnt after the third Investec Ashes Test at Edgbaston. | Aug 1, 2015
From James Anderson's six-for to Adam Voges clinging onto Alastair Cook's pull shot here are the top five moments from Edgbaston | Aug 1, 2015
George Dobell and Melinda Farrell discuss England's decision to bring in Mark Footitt and Liam Plunkett and continue with Adam Lyth for Trent Bridge | Aug 1, 2015
England head coach Trevor Bayliss spoke about putting defeat at Lord's behind them and the support from the Edgbaston crowd | Aug 1, 2015
Nepal captain Paras Khadka talks about his side's performance in the World Cricket League so far and how the squad is coming together after a poor Ireland tour | Aug 1, 2015
Melinda Farrell is joined by George Dobell and Jarrod Kimber to discuss what they learnt after the third Investec Ashes Test at Edgbaston | Aug 1, 2015
Virat Kohli on India's upcoming tour to Sri Lanka, playing for India A against Australia A, and working with Rahul Dravid | Aug 1, 2015
Australia A captain Usman Khawaja discusses their gameplan and adapting to sub-continent conditions | Aug 1, 2015
Sri Lanka fail to find their 'Marlon Samuels', surreal Gayle, West Indian fans get 'tired' of celebrating, Australia Women win - the Two ...
Chris Gayle never leaves, Shane Watson never turns up and the two chucks prove how genius they are
Sri Lanka defeat Pakistan despite Dilshan, England ease past New Zealand and ESPNcricinfo's nephew wrote this. Your hosts are Sampson Col...
India and Dale Steyn go home, Watson and Kohli fail, and Pakistan rejoice. Your hosts are Sampson Collins and Jarrod Kimber.
Samit Patel shows he can play, Ajantha Mendis has a bad day and West Indies look confused until they face Tim Southee. Sam Collins and Ja...
India superpower, South Africa supersucky and Shane Watson. Your hosts are Sampson Collins and Jarrod Kimber.
Johnson Charles fails for the West Indies, Ross Taylor has not turned up yet and Ajantha Mendis is passable as England fight back and Sri...
Pakistan stutter but edge past South Africa, and India fail to turn up against Australia
The World T20 gets a Super Over on the first day of the Super Eights


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Overall Experience:
I love my college very much. I met new people and professors who are helping my reach my degree. I also play a sport at my college and glad that I got recruited. The small campus and classes were a bonus plus the many activities going on the campus.
Party Scene:
The houses are a safe and fun environment to party. They are always looking out for the safety of the people at their parties. The best parties were Margaritaville at the ADG house. I think the party scene had a positive impact on the student experience because it gave the students a chance to socialize and let loose in a safe environment.
Off-Campus Dining:
I was surprised that most places did not give student discounts. However, the best places to eat were momma Goldbergs and Fried Green Tomato. All food options are convenient.
Off-Campus Housing:
The off campus housing is not available. All students must live on campus. On campus living is expensive. LaGrange wants to give all students the opportunity to gain the ultimate college experience.
The school is very helpful and they want you succeed. They are always there for you when you need help. At LaGrange you are not just a number, but an actual person. The Honor Code is very strict. We have to sign a contract stating that we will not cheat. There is also a social and honor council.
LaGrange cost more than most colleges, but they offer a lot financial aid. I was able to get half of the cost covered by scholarships and grants. Tips that I would give anyone that wants to get more financial aid at this school is to go into the office and talk to them. They are willing to work with you.
Campus Food:
I think the quality of food could be better. We play a lot of money to go to the school, so there is no reason the food should be bad all the time. The food choice is a wide variety, however, I found myself eating in the grill a lot. If I was not eating at the grill, I had to go out to eat because I missed caf hours or the food was just bad.
Campus Housing:
LaGrange is a great school. It has quality dorms. There is also a pool inside and outside. The gym is also has everything I need to exercise. There is one on campus and one off campus near the athletic fields. The cost of this school is overly expensive, but the level of education is worth it.
Off-Campus Dining:
Good choices but not enough buffets available.
Apply early to get funds needed
Campus Housing:
Like the apartment style living
Off-Campus Dining:
All the good places cost too much for a student, but it's all great food.
I would say it's perfect, but I got a parking ticket, because I accidentally parked in a lot commuters can't use. I personally think that commuters should have all the parking priveleges of residential students.
They gave me plenty of aid.
Campus Food:
The food is pretty good, but it cost too much. So, I stopped using it.
Off-Campus Dining:
The places really close are either really expensive or really cheap. There is no in between, it's the same fast food or restaurants as always.
The Administration is helpful and fair. They try to get along with everyone and they treat everyone really fair. They understand we are college students.
Party Scene:
The Party Scene is really controlled, it never gets out of hand.
Financial Aid is a struggle, no matter what you feel like you do not have enough money. The school helps out a lot, but still having to pay money out of pocket is terrible.
Campus Food:
It's not the best, nor is it the worst. If you know what you're doing then you are fine.
Campus Housing:
Dorms are very spacey. No matter what dorm you live in. If you prefer cooking, it'd be best to live in Candler or Hawkins Hall. Due to the fact it is required to have a meal plan brings you to a disadvantage. There are three meal plans options. 15 meals a week, 10 meals a week or, of course, unlimited meals per week. There is only about a $200 difference between the three which saves you little to nothing when we're talking about money in the 2,000s. Considering the cost of tuition and housing ... the fact we can only have our thermostats set to a specific (and inconvenient) temperature throughout the seasons, it's not worth the money.Not too much diversity here at LaGrange College.
Campus Food:
The food is delicious and you can have as much as you want.
Campus Housing:
The dorms are very nice and I enjoy them.
Local Area:
LaGrange needs major updates and hot spots
Campus Quality:
Wish I could get more help, more living space, better food
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Manuel Pellegrini praised Manchester City for maintaining their performance levels over 90 minutes in the 7-0 victory over Norwich City.
City cruised to a 4-0 half-time lead in the Premier League clash courtesy of a Bradley Johnson own goal, as well as efforts from David Silva, Matija Nastasic and Alvaro Negredo.
Yaya Toure, Sergio Aguero and Edin Dzeko completed the rout after the break, as pre-match speculation surrounding Joe Hart's eventual omission was quickly forgotten.
And Pellegrini was pleased that his players did not take their foot off the gas in the second half.
"I think that the team played really well during the 90 minutes," he said. "Winning 4-0 in the first half - normally, in the second half, most teams stop playing.
"I think the team continued playing exactly the same and that's very important for me.
"It was important to see the team play the way I want them to play.
"They are very good technical players and when they move the ball quickly, it's very difficult for our team not to score, so we must continue in the same way.
"I think Norwich is a very good team. I didn't expect to score seven goals, but I think the team played to do it so it's great for me."
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"Artoo in Love" tells the story of R2-D2 falling in love and then getting his heart broken — by a mailbox.


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Infrared Physics & Technology 53 (2010) 434–438 Contents lists available at ScienceDirect Infrared Physics & Technology journal homepage: www.elsevier.com/locate/infrared FTIR spectroscopy as a tool for nano-material characterization Charles Baudot a,⇑, Cher Ming Tan b, Jeng Chien Kong a a STMicroelectronics Asia Pacific Pte Ltd., 5A Serangoon North Avenue 5, Singapore 554574, Singapore b School of EEE, Nanyang Technological University, Block S2, Nanyang Avenue, Singapore 639798, Singapore a r t i c l e i n f o a b s t r a c t Article history: Covalently grafting functional molecules to carbon nanotubes (CNTs) is an important step to leverage the Received 10 June 2010 excellent properties of that nano-fiber in order to exploit its potential in improving the mechanical and Available online 22 September 2010 thermal properties of a composite material. While Fourier Transform Infra Red (FTIR) spectroscopy can display the various chemical bonding in a material, we found that the existing database in FTIR library Keywords: does not cover all the bonding information present in functionalized CNTs because the bond between FTIR characterization the grafted molecule and the CNT is new in the FTIR study. In order to extend the applicability of FTIR Carbon nanotube to nano-material, we present a theoretical method to derive FTIR spectroscopy and compare it with Covalent functionalization Epoxy fillers our experimental results. In particular, we illustrate a method for the identification of functional mole- cules grafted on CNTs, and we are able to confirm that the functional molecules are indeed covalently grafted on the CNTs without any alterations to its functional groups. Ó 2010 Elsevier B.V. All rights reserved. 1. Introduction load transfer and heat transfer between the epoxy matrix and CNT fillers, covalent bonding between the polymer and the nano- Infrared spectroscopy is a crucial tool to characterize the struc- tubes must be present. Consequently, we intend to apply FTIR to ture of matter at the molecular scale. Based on the singular reso- examine the presence of such covalent bonds. nant vibrational modes of different branches or body parts of a Blake et al. [8] demonstrated that there is indeed a covalent molecule, one can reveal its constituting elements and its bonding bond between functional molecules and CNTs by grafting silicon arrangement. The reverse process is also exploited because a spe- and tin based molecules on the nanotubes and by looking for cific molecule possesses a unique infrared spectrograph equivalent C–Si and C–Sn vibration modes in the FTIR spectrum. However, to a finger print which can unveil its identity. FTIR spectroscopy such an affirmation cannot be done if purely carbon based func- analysis is a method based on the principle of infrared spectros- tional molecules are grafted as it is the case in our present study. copy, and it has extended its area of application to the study of C–Si and C–Sn vibrations occur in a very specific narrow range, nano-scaled objects during the last decade. almost independently of the remaining molecular structure, A common approach to exploit the unique properties of nano- because of the relatively big difference in atomic masses of the particles and to improve its workability is to functionalize the sur- two atoms. However, carbon to carbon bonds exist in a very wide face of the latter [1–6]. However, the application of FTIR in the range of wavenumbers due to the huge amount of existing organic characterization of functionalized nanoparticles could be difficult molecules and their various configurations. Coleman et al. [9] used because it may not reveal the chemical bonds between the nano- another alternative to demonstrate the presence of covalent bond- particles and the functional molecules based on a database of ing. They grafted thiolic functional molecules on the CNTs and known vibrational frequencies. This is because the chemical bond dispersed gold nanoparticles in a solution containing the function- between the functionalized molecules and the nano-material is alized CNTs (f-CNTs). Then, using an atomic force microscope to usually novel, and thus, a strategy must be developed in order to scan a sample of the dispersed f-CNTs on a surface, they showed provide evidence about the resonant vibrational information be- the CNTs decorated with nanoparticles. However, this method is tween the grafted molecules and the nano-sized particles. only usable to demonstrate that covalent bonds indeed occur on In this work, we study the covalent grafting of epoxide mole- CNTs. It is a destructive method that alters the characteristics of cules on CNTs [7]. This strategy is for the exploitation of CNTs as the functional molecules and it is only compatible with the grafting fillers in epoxy composite materials for its mechanical and heat of functional groups that can bond to nanoparticles which do not dispersion enhancements. In order to ensure a better mechanical necessarily suit the targeted application. The method that we present here is a combined experimental ⇑ Corresponding author. Tel.: +65 6427 7368; fax: +65 6427 7379. and theoretical FTIR analysis of f-CNTs to unveil the occurrence E-mail address: firstname.lastname@example.com (C. Baudot). of a chemical covalent bond between functional molecules and 1350-4495/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.infrared.2010.09.002 C. Baudot et al. / Infrared Physics & Technology 53 (2010) 434–438 435 Once n-butyllithium reagent starts attacking the CNTs, a natural dispersion of the functionalized nanotubes occurs by electro- repulsion. After stirring the homogeneous solution for 2 h, epichlorohydrin is added in controlled amount while stirring is continuing. During this reaction, while lithium chloride is formed as a by-product, epoxide branches are grafted on the CNTs by nucleophilic substitution. Thus, each functionalized site contains two branches, namely a butyl branch and an epoxide branch as shown in Fig. 1. Fig. 1. Sketch showing the grafting of functional molecules on the side wall of a The butyl branch contributes in producing unevenness on the carbon nanotube. CNT surface that reduces considerably the bundling effect which is due to both the Van der Waals forces of attraction and the high CNTs. Pristine CNTs show very weak resonant frequencies in the aspect ratio of the nanotubes. Moreover, the epoxide branch con- infrared spectrum in the 400–4000 cmÀ1 range. However, once tributes in improving the solubility of the CNTs in epoxy resins. molecules are grafted on it, we observe differential infrared Furthermore, the epoxy ring contained in the grafted functional absorption response due to the functional sites. The purpose of this molecule participates in the polymerization of the composite when work is to provide evidence that the observed differential response the curing agent is added. Thus a covalent bond is believed to be is not due to either adsorbed molecules, wrapping molecules or created between the CNT and the composite matrix. any other such kind of residual particles which are not covalently Using a Perkin–Elmer System GX 2000 FTIR spectrometer, an bonded to the CNTs, but it is indeed due to the covalent bonding extensive FTIR analysis is performed on samples of f-CNTs. The of the grafted molecules to the CNTs. samples are prepared by taking a small amount of f-CNTs in pow- der form and mix it with potassium bromide to make several thin and semi-transparent discs. The discs are then analyzed in the 2. Experimental spectrometer under ambient conditions using different wavenum- ber resolutions. First, a broad scan of the sample is performed from The chemical procedure for the grafting of the functional mole- 400 cmÀ1 to 4000 cmÀ1 with a step of 4 cmÀ1 (Fig. 2). Among the cules to CNTs consists of two steps in a one pot reaction. The first various peaks present in the spectrum, several are already clearly step consists of initiating reactive sites on the CNT walls by using a identifiable as belonging to the functional molecules. For example, lithiated alkyl and the second step, bonding functional molecules we observe a peak at 830 cmÀ1 which corresponds to a mono- containing oxirane rings. The detailed reaction path and methodol- substituted epoxide ring vibration. We also observe peaks corre- ogy is described elsewhere [7]. The CNTs that are used for this sponding to the straight chain alkanes or branches of the epoxide experiment are high purity multiwall nanotubes from Nanothinx molecules. The list of known wavenumber ranges obtained from S.A. The use of organo-metallic agents to initiate reaction sites on FTIR databases [13] is listed in Table 1. In order to obtain more de- CNTs has already been reported [10–12] and n-butyllithium is used tailed spectra of the sample, a higher precision FTIR analysis on a in our work here. This organo-lithium molecule is obtained from narrower range of 800–1800 cmÀ1 is performed with a step of Sigma–Aldrich at a concentration of 2 M in cyclohexane. The sol- 0.1 cmÀ1 (Fig. 3). In order to visualize the peaks that are masked vent in which the reaction takes place is high purity anhydrous because of the convolution, a first order derivative of the spectrum cyclohexane from Sigma–Aldrich. The reactions are done at room is performed (Fig. 4). The information collected in those spectra re- temperature under inert atmosphere to prevent the very reactive veal peaks which are not identifiable in the database of the pure butyl alkyl from reacting with the humidity present in air. The initial constituents such as the peaks at wavelengths of glove box used during the experiments consists of an argon atmo- 1401 cmÀ1 and 1470 cmÀ1, but they are believed to be of crucial sphere with a humidity level of less than 0.1 ppm and an oxygen importance for the characterization of the grafting of functional level of at most 2 ppm. molecules on CNTs. Fig. 2. Experimental FTIR spectrum of the functionalized CNTs showing the changes in transmittance of the IR signal over the range of 400–1800 cmÀ1 (inset 2500– 4000 cmÀ1). 436 C. Baudot et al. / Infrared Physics & Technology 53 (2010) 434–438 Table 1 3. Theoretical calculations List of know IR resonant vibrations related to straight chain alkanes, epoxide rings and water. In order to identify the significance of each peak, a model of the Wavenumber Deformation type Fragment f-CNTs must be done and the different vibrational modes of the de- range (cmÀ1) signed macro-molecule must be compared to the experimental re- 445–825 Water O–H out-of-plane bending sults. As CNTs are almost chemically inert, a chemical reaction is vibration more likely to occur on the reactive defect sites of the CNT walls. 455–455 Straight chain alkanes C–C skeleton vibration 485–540 Straight chain alkanes C–C skeleton vibration 805–880 Mono-substituted Ring vibration epoxide ring 1060–1150 Saturated aliphatic esters C–O asymmetric stretching 820–1140 Saturated aliphatic esters C–O symmetric stretching 1370–1390 R–CH3 C–H symmetric deformation vibration 1440–1480 –CH2– C–H scissor vibration 1475–1500 Mono-substituted CH2 deformation vibration epoxide ring 1595–1710 Water O–H in-plane bending vibration 2865–2885 R–CH3 C–H symmetric stretching vibration 3000–3700 Water O–H stretching vibration Fig. 5. (a) Positions 1 and 2 are the locations of the binding sites for the functional 3230–3550 Water Intermolecular hydrogen bond molecules on the C30 and (b) Cluster model of the functionalization of a C30 molecule. Fig. 3. High resolution FTIR spectrum of the functionalized CNTs over the range of 800–1800 cmÀ1. Fig. 4. First order derivative of the FTIR spectrum shown above over the range of 1300–1550 cmÀ1. C. Baudot et al. / Infrared Physics & Technology 53 (2010) 434–438 437 Fig. 6. Optimized configurations of the three conformers created by grid scan technique for the functionalized half-fullerene. Table 2 Table 3 Theoretical results of the covalently grafted bond states for different orientations. Vibrational modes comparison between experiment and theoretical work. Configuration B.E. (eV)a L(CCNT–Cbutyl) (Å)b L(CCNT–Cepoxide) (Å) Wavenumber (cmÀ1) Fragment deformation 6a 2.58 1.685 1.836 Experimental Theoretical 6b 6.61 1.581 1.571 489 493 Straight chain alkanes C–C skeleton vibration 6c 6.47 1.577 1.577 830 843 Epoxide ring Ring vibration a Binding energy (absolute value). 1401 1403 CCNT–Cepoxide C–C stretching b Bond length, L. 1470 1475 CCNT–Cbutyl C–C stretching 1504 1504 Epoxide ring CH2 bending Thus, the most probable location to find grafted molecules on the ration 6a remains at its original position, leading to an unstable CNTs will be a place where defects naturally occur, that is, the arrangement with a B.E. of about 4 eV less than the two other con- tip of the CNT. Therefore, the model that we develop consists of formations. Correspondingly, the calculated L (CCNT–Cepoxide) in 6a grafting molecules on both CNT tips and on lateral defect sites is somewhat larger than 6b and 6c by about 0.26 Å and this also re- and the different vibrational modes of the resulting structure are flects a much weaker covalent bonding in that configuration as then computed. compared to those in the 6b and 6c arrangements. Therefore, to The first cluster model consists of half a fullerene (C30) to which model the covalent functionalization of CNTs, the configuration are attached a butyl molecule and an epoxide molecule placed on 6b is chosen in order to determine the IR spectrum of the f-CNTs. atomic sites where the most active binding regions are deemed We examine the vibrational spectrum of the f-CNTs by means of to be located. Such locations are found at the junction between cluster models with methods based on the density functional the- pentagonal and hexagonal rings (Fig. 5). In order to avoid any ory (DFT) within the generalized gradient approximation (GGA) geometry reconstruction at the hemi-spherical edge, the dangling with the Perdew, Burke and Ernzerhof (PBE) correlation functional bonds are saturated with hydrogen atoms. After performing a [17]. Our calculations are closed shell and are performed using the relaxation of the cluster, the Hessian matrix is calculated in order Dmol3 module of Materials Studio from Accelrys. The electronic to evaluate the resonant vibrational frequencies of the molecular wavefunctions are expanded in atom-centered basis functions de- model [14]. The second model consists of a 7-5-5-7 Stone Wales fined on a dense numerical grid. The chosen basis set is double defect site found on the side wall of a CNT [15] on which the same numerical plus d-polarization (DND). DND is an all-electron basis molecules are grafted and the same procedures are performed. set composed of two numerical functions per valence orbital, sup- We first investigate the most stable configuration of the models. plemented with a polarization d-function on all the non-hydrogen For example, in the case of the functionalized half-fullerene, we atoms. Each basis function is restricted to a cut-off radius. A global study the optimal arrangement of the molecule displayed in real space cut-off is selected as the maximum value of the cut-offs Fig. 5b. Grid scan conformer search technique [16] is employed specific for every element of the system. Real space cut-offs for by fixing the half-fullerene and the butyl molecule while rotating atomic species are optimized by considering total energies of the epoxide ring at three different angles with respect to the butyl atoms. The chosen cut-off values lead to atomic energies with an molecule. The same procedure is then repeated for side-wall func- accuracy of 0.1 eV/atom, allowing calculations without a signifi- tionalization. Three configurations are created and geometrically cant loss of accuracy. The self consistent field (SCF) convergence optimized for each model. The final configurations of the function- has been tested and a convergence threshold less than 10À6 Ha alized half-fullerene are shown in Fig. 6. has been evaluated to be satisfactory to achieve the structural The binding energy (B.E.) and the length (L) of the C–C bond optimization. linking the butyl molecule to the C30 (CCNT–Cbutyl) and the epoxide From the simulation of Dmol3, the harmonic wavenumbers ob- molecule to the C30 (CCNT–Cepoxide) are summarized in Table 2. The tained are listed in Table 3 together with the corresponding exper- values of B.E. are calculated based on the following equation: imental results. In agreement with the theoretical results, the B:E: ¼ EðC30 þ butyl þ epoxideÞ À EðC30 Þ À EðbutylÞ À EðepoxideÞ covalent bond formation of the epoxide molecule on C30 is dis- closed by the wavenumber 1403 cmÀ1. Also, the covalent bond for- ð1Þ mation of butyl molecule on C30 is attributed to the CCNT–Cbutyl where E(C30 + butyl + epoxide), E(C30), E(butyl) and E(epoxide) are stretch at around 1475 cmÀ1. Besides the two crucial wavenum- the respective total energies of the indicated systems. bers, we also observe that the theoretical results are in agreement The conformations 6b and 6c in Table 2 are very close to each with the experimental vibrational frequencies of the functional other in both the B.E. and L. The carbon atom located at position molecules such as the ring oscillation and the alkyl stretching. 1 for these two configurations is distorted and a tetrahedral sp3 However, there are still some peaks that have not been identified hybridization contributing to the overall structural stability is such as the peaks at 873 cmÀ1, 1297 cmÀ1, 1333 cmÀ1 and formed. On the other hand, the same carbon atom in the configu- 1358 cmÀ1. We believe that it is because the attachment of the 438 C. Baudot et al. / Infrared Physics & Technology 53 (2010) 434–438 molecules occurs on various defect sites bearing different molecu- [4] C.J. Tang, A.J. Neves, M.C. Carmo, Infrared absorption study of hydrogen incorporation in thick nanocrystalline diamond films, Appl. Phys. Lett. 86 lar configurations and hence it is not feasible to unveil all of them (2005) 223107. using this method since we do not know the molecular structure of [5] J.M. Abad, S.F.L. Mertens, M. Pita, V.M. Fernndez, D.J. Schiffrin, all the grafted sites that actually exist. Moreover, the water content Functionalization of thioctic acid-capped gold nanoparticles for specific in the KBr powder has a masking effect on the peaks that would lie immobilization of histidine-tagged proteins, J. Am. Chem. Soc. 127 (2005) 5689–5694. within the intervals of 445–825 cmÀ1, 1550–1750 cmÀ1 and 3000– [6] L. Armelao, H. Bertagnolli, D. Bleiner, M. Groenewolt, S. Gross, V. Krishnan, C. 3700 cmÀ1 [18,19]. Sada, U. Schubert, E. Tondello, A. Zattin, Highly dispersed mixed zirconia and hafnia nanoparticles in a silica matrix: first example of a ZrO2–HfO2–SiO2 ternary oxide system, Adv. Funct. Mater. 17 (2007) 1671–1681. 4. Conclusions [7] C. Baudot, C.M. Tan, Solubility, dispersion and bonding of functionalised carbon nanotubes in epoxy resins, Int. J. Nanotechnol. 6 (2009) 618–627. [8] R. Blake, Y.K. Gun'ko, J. Coleman, M. Cadek, A. Fonseca, J.B. Nagy, W.J. Blau, A In this work, we have successfully demonstrated the use of the generic organometallic approach toward ultra-strong carbon nanotube combination of an experimental FTIR analysis and a theoretical polymer composites, J. Am. Chem. Soc. 126 (2004) 10226–10227. FTIR model to characterize the functionalization of nano-sized ob- [9] K.S. Coleman, S.R. Bailey, S. Fogden, M.L.H. Green, Functionalization of single- walled carbon nanotubes via the Bingel reaction, J. Am. Chem. Soc. 125 (2003) jects. We successfully unveil the identity of the molecular confor- 8722–8723. mations present on the f-CNTs and prove the presence of covalent [10] A. Pénicaud, P. Poulin, A. Derré, E. Anglaret, P. Petit, Spontaneous dissolution of bonding between the grafted molecules and the CNTs. a single-wall carbon nanotube salt, J. Am. Chem. Soc. 127 (2005) 8–9. [11] G. Viswanathan, N. Chakrapani, H. Yang, B. Wei, H. Chung, K. Cho, C.Y. Ryu, P.M. Ajayan, Single-step in situ synthesis of polymer-grafted single-wall Acknowledgments nanotube composites, J. Am. Chem. Soc. 125 (2003) 9258–9259. [12] S. Chen, W. Shen, G. Wu, D. Chen, M. Jiang, A new approach to the This research work is done in collaboration between the School functionalization of single-walled carbon nanotubes with both alkyl and carboxyl groups, Chem. Phys. Lett. 402 (2005) 312–317. of Electrical and Electronic Engineering of Nanyang Technological [13] Science and Fun Infrared Spectrum Database. <http://www.science-and- University and STMicroelectronics Asia Pacific Pte. Ltd. We would fun.de/tools/>. like to thank Dr. Andrea Di Matteo and Dr. Francesco Buonocore [14] F. Pascale, C.M. Zicovich-Wilson, F. López Gejo, B. Civalleri, R. Orlando, R. Dovesi, The calculation of the vibrational frequencies of crystalline compounds from STMicroelectronics for their help in developing the FTIR mod- and its implementation in the CRYSTAL code, J. Comput. Chem. 25 (2004) 888– el of the f-CNTs. 897. [15] A.J. Stone, D.J. Wales, Theoretical studies of icosahedral C60 and some related species, Chem. Phys. Lett. 128 (1986) 501–503. References [16] Accelrys Materials Studio Product Datasheets. <http://accelrys.com/products/ datasheets/conformers.pdf>. [1] D. Roy, J. Fendler, Reflection and absorption techniques for optical [17] J.P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made characterization of chemically assembled nanomaterials, Adv. Mater. 16 simple, Phys. Rev. Lett. 77 (1996) 3865–3868. (2004) 479–508. [18] A. Lasagabaster, M.J. Abad, L. Barral, A. Ares, FTIR study on the nature of water [2] V.K. Parashar, J.B. Orhan, A. Sayah, M. Cantoni, M.A.M. Gijs, Borosilicate sorbed in polypropylene (PP)/ethylene alcohol vinyl (EVOH) films, Eur. Polym. nanoparticles prepared by exothermic phase separation, Nat. Nanotechnol. 3 J. 42 (2006) 3121–3132. (2008) 589–594. [19] M.A. Munoz, C. Carmona, M. 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