text:
Romney May Roll Out Welcome Mat for Fannie and Freddie: Street Whispers
NEW YORK ( TheStreet) -- Government sponsored enterprises Fannie Mae (FNMA) and Freddie Mac (FMCC) may be Republicans' favorite villain, but if Mitt Romney makes it to the White House they could find themselves with a new ally.
According to a popular Republican narrative, the government forced banks to lend to people who couldn't possibly pay their mortgages, with Fannie and Freddie providing much of the capital. The result was a corrupt scheme to buy votes through dangerously risky home loans while lining the pockets of powerful Democrats.
The Obama Administration has signaled a desire to wind down the GSEs, though since they are pretty much single-handedly supporting the fragile U.S. housing market at the moment, no one wants to move too quickly. As a result, four years after the mortgage giants were placed under government conservatorship, we still have little more than a few vague proposals about what to do with them.
Anyone who thinks a Romney Administration would be faster to phase out the GSEs should think again, however, according to Brian Gardner, analyst at Keefe, Bruyette & Woods. Speaking at a KBW conference on Wednesday, Gardner argued Romney would most likely be slower than Obama to address the GSEs, since "no sitting President running for reelection is going to touch the issue."In other words, if Obama wins, he may have the courage to take on the GSE question because he won't have to face reelection, while if Romney were elected he would probably wait until his second term--assuming he has one--in 2017. Republicans who want the government out of the housing market will either have to reduce their expectations or vote for Obama. -- Written by Dan Freed in New York. Follow this writer on Twitter.
Select the service that is right for you!COMPARE ALL SERVICES
Action Alerts PLUSTry it NOW
Jim Cramer and Stephanie Link actively manage a real portfolio and reveal their money management tactics while giving advanced notice before every trade.
Product Features:
- $2.5+ million portfolio
- Large-cap and dividend focus
- Intraday trade alerts from Cramer
- Weekly roundups
TheStreet Quant RatingsTry it NOW
Only $49.95/yr
Access the tool that DOMINATES the Russell 2000 and the S&P 500.
Product Features:
- Buy, hold, or sell recommendations for over 4,300 stocks
- Unlimited research reports on your favorite stocks
- A custom stock screener
- Upgrade/downgrade alerts
Stocks Under $10Try it NOW
David Peltier, uncovers low dollar stocks with extraordinary upside potential that are flying under Wall Street's radar.
Product Features:
- Model portfolio
- Stocks trading below $10
- Intraday trade alerts
- Weekly roundups
Dividend Stock AdvisorTry it NOW
Jim Cramer's protege, David Peltier, identifies the best of breed dividend stocks that will pay a reliable AND significant income stream.
Product Features:
- Diversified model portfolio of dividend stocks
- Alerts when market news affect the portfolio
- Bi-weekly updates with exact steps to take - BUY, HOLD, SELL
Real Money ProTry it NOW
All of Real Money, plus 15 more of Wall Street's sharpest minds delivering actionable trading ideas, a comprehensive look at the market, and fundamental and technical analysis.
Product Features:
- Real Money + Doug Kass Plus 15 more Wall Street Pros
- Intraday commentary & news
- Ultra-actionable trading ideas
Options ProfitsTry it NOW
Our options trading pros provide daily market commentary and over 100 monthly option trading ideas and strategies to help you become a well-seasoned trader.
Product Features:
- 100+ monthly options trading ideas
- Actionable options commentary & news
- Real-time trading community
- Options TV


text:
For any comments and Suggestions: Tuning: Standard Intro: G-Am-F (2x) Verse I: G Am Currently disabled out of order F What should I do, what should I Keep G Am All my pride or my dignity F So few choices for the man on the street, G Am The way I look at the fire that burns F Never make the same mistake twice, G Am As we stumble and fall,And as time breaks and fall F I learn of things both here and beyond me Intro: G-Am-F (2x) Chorus: G Am F Little child I was once a little boy like you G Am But I grew up fast and I never did forget F The child that I once knew G Am Live as you have loved learn as you live F The higher power will give you what your money can't give G Am And as tomorrow becomes yesterday F I learn of things both here and beyond me, G Am F As tomorrow becomes yesterday (Do Cp: G-Am-F-G) It's a games of liability, a copyright of our own instability The seed of hich you plant out will sow It's that simple any farmer would know No slight of hand from no charlatan No political deceit from no politician And as tomorrow becomes yesterday I learn of things both here and beyond me. (repeat chorus) |================================================================| | Reminder/s: If you want to "Learn How To Read Tab" | | Just Send me a message on my Friendster or Text Me | |================================================================|
Popular Bamboo tabs & chords
Song lyrics
↑ Back to top | Tablatures and chords are parodies/interpretations of the original songs. You may use it for private study, scholarship, research or language learning purposes only

subset: commoncrawl


text:
86 773 2831999China Hotels Guangzhou Hotels Huan Shi Road East Hotels
Huan Shi Road East Hotels
There are 65 of Guangzhou Hotels near the Huan Shi Road East. Choose from the list below or just send us an email to email@example.com and get a quick reply within 2-12 hours.
Note: Please make sure you have "cookies" enabled on your browser before proceeding with your enquires on our website.
Nearby Places
AirportTrain Station
- Guangzhou East Railway Station
- Guangzhou Railway Station
- Guangzhou North Railway Station
- Guangzhou South Railway Station
Huajian Hotel
Location: Huan Shi Road East(1.78KM)
Peng Da Hotel
Location: Guangzhou Baiyun Airport(224M)
Jinjiang Inn Liwan Caihongqiao Dian
Location: Guangzhou Railway Station(2.09KM), Liuhua Complex
Motel 168 Panyu Pingkang Road
Homeinns Xiaoxiguan Inn
Location: Beijing Road(2.89KM)
New East Hotel Dongfeng Guangzhou
Location: Liuhua Complex(2.40KM), Huan Shi Road East, Guangzhou North Railway Station
Hanting Express Guangzhou Tianhe
Location: Guangzhou East Railway Station(284M), Tianhe Sports Center(284M)
Jinjiang Inn Guangzhou Liwan


text:
Good news! The energy crisis could soon be over! Yes, all of our energy problems may soon be… behind us. Because scientists from Nanyang Technological University have invented a toilet that turns human waste into electricity! Yes!
Manually separating waste for processing is time-consuming, expensive and gross, which is why waste-to-power technologies have so far failed to catch on. The main advantage to this...
The Everlasting Jelly-bot
If you created a robot, what would it be like? I would probably build a battery-powered android, because I think I would have the most fun with either a sassy maid-bot or a pretend-little-sister-bot. Scientists in Texas and Virginia were a little more creative, having built "Robojelly," a jellyfish robot that runs on hydrogen and oxygen!
This little swimmer currently gets its fuel from tubes connected...
- Museum Hours
- through January 3
Daily* from 9:30 a.m. to 5:30 p.m.
* 12/24, 12/31, 1/1—closing 4 p.m.;
Closed on Christmas Day
- through January 3
- Museum Location
Museum of Science+IndustryGetting Here5700 S. Lake Shore DriveChicago, IL 606371 (773) 684-1414
- Art and Culture (3)
- Attitude and Behavior (9)
- Chemistry (9)
- Computer and Digital Technology (7)
- Earth Science (6)
- Education and Policy (4)
- Energy (5)
- Engineering (8)
- Environment and Sustainability (9)
- Health and Medicine (17)
- Manufacturing and Industry (7)
- Math (2)
- Museums (2)
- Physics (8)
- Space and Astronomy (16)
- Technology (18)
- Transportation (3)
- Happening Now
Treasures of the Walt Disney Archives
Explore nine decades of The Walt Disney Company's history and artifacts.
D-Day: Normandy 1944
Seventy years ago, a historic landing changed the world.
Christmas Around the World and Holidays of Light
Celebrate with the entire family at the Museum's beloved holiday tradition.
- Coming Soon
Science Snoozeum
Enjoy a rare opportunity to visit the Museum after dark!
contact us
Write the team behind the blog with your questions or comments.


text:
Loading ...
White Water Learning Center of Georgia plunges people into raging rapids with its kayak, canoe, and paddle board classes and tours. Lessons teach paddlers how to navigate all classes of rapids in rivers and in the ocean. After learning how to explore local waterways, students can sign up for one of the learning center's excursions, or rent a canoe or kayak to take on a solo journey to the location where Atlantis' food court once stood.
Nestled in the salt marshes of northern Wilmington Island, Bull River Marina is an ideal launch pad for exploring the region's natural splendor. Experienced captains offer tours that find them steering their prow through the bottlenose-dolphin-inhabited waters off the shores of Savannah. Additionally, Bull River's captains lead crabbing and fishing charters that search the waters for everything from kingfish to sharks. The seasoned fishermen provide passengers with all the bait, tackle, and licenses they need to wrest trout and flounder from the refrigerators of submarine captains.
A family owned business for over 25 years giving access to & helping to protect the Broad River. We have tandem canoes and tandem & solo kayaks. We offer on site camping, hot food weekends / holidays & monthly Eco-tours. Reservations encouraged / not required. With beginner whitewater or mellow floats - Go with the BRO
We are a family-run resort and marina in the mountains of North Georgia on the beautiful Lake Chatuge. We offer lodging, boat rentals, boat sales and service, as well as a gift shop.
The courteous staffers at River Tubing pair up customers with comfortable, dual-chamber tubes perfect for warm days spent on the calm waters of the Chattahoochee River. Two-, four-, and six-hour tubing trips take place seven days a week on stretch of river between Rogers Bridge and Medlock Bridge populated with wildlife including beavers, turtles, and otters. Shuttles carry customers and their gear to the drop-in spot and return them to the rental station at the end of the trip. While on the water, guests can sip drinks from coolers, connect their tubes to those of friends, hop out and swim, or issue speeding tickets to fast-moving schools of trout.
Holiday Harbor Marina & Resort, which is located approximately 25 minutes north of Atlanta, rests on the shores of scenic Lake Allatoona in a wilderness escape teeming with family-friendly fun. Up to six people can spend a night in one of the resort's seven fully furnished cabins complete with two bedrooms, a lakeside porch, and a kitchen. Roast marshmallows over the communal fire pit, or grill burgers, hot dogs, and wookiee ribs on the group-use grills. Guests can reconnect with the concrete jungle via wireless Internet and satellite TV.


text:
14 No-Fuss One-Skillet Dinners
When you need to get a delicious dinner on the table in no time flat, there's nothing better than a one-skillet supper recipe. An easy way to use ingredients you have handy, a meal made in one pot is not only a delectable way to use common ingredients, it also guarantees quick cleanup, so you can spend time with the family when dinner's done.
Looking for more quick but satisfying family meals? Try one of these easy recipes.
Skillet Gnocchi with Shrimp and Asparagus
The gnocchi cooks right in the skillet, along with shrimp, shallots, asparagus, and Parmesan cheese, in this gnocchi recipe. Look for shelf-stable gnocchi near other pasta. Serve with baby arugula salad with vinaigrette and a glass of Pinot Grigio.
Recipe: Skillet Gnocchi with Shrimp and Asparagus


text:
Broadway's 'Hands on a Hardbody' to close
FILE – This file theater image released by The Hartman Group shows the cast during a performance of "Hands on a Hard Body," at the Brooks Atkinson Theater in New York and featuring songs co-written by Phish frontman Trey Anastasio. Producers said Monday, April 8, 2013 that "Hands on a Hardbody," based on a 1997 documentary, will close Saturday after playing less than 60 total performances. (AP Photo/The Hartman Group, Chad Batka, File)
NEW YORK (AP) — The new Broadway musical about a Login to read more
Related Posts
« Thatcher had profound effect on popular culture Cult Pizza decor images feature notorious leaders »


text:
Monday, 13th August 2012, 11:05:10
Alterations to algorithms are aimed at lowering the search ranking status of websites which violate copyright law.
categories: | Security | Online Marketing / Search |
Wednesday, 1st August 2012, 18:18:06
Having a sophisticated password strategy is essential for any organisation concerned about security..
categories: | Security |
Wednesday, 1st August 2012, 16:16:52
Highly sensitive data is particularly vulnerable when staff hand their notice in..
categories: | Security |
Monday, 30th July 2012, 14:52:06
Businesses must be prepared to protect sensitive data and professional reputations. .
categories: | Virtualisation / The Cloud | Security | Online Marketing / Search |
Thursday, 26th July 2012, 08:00:00
The government has launched a competition to find software writers who can deal with online attacks. .
categories: | Security | Online Marketing / Search |
Friday, 20th July 2012, 16:30:35
Research from Experian shows that the average Briton has 26 online accounts but only uses five different passwords to keep them secure.
categories: | Security |
Thursday, 19th July 2012, 10:39:01
Companies need to educate their staff, as humans are the "weakest link", according to an IT consultant.
categories: | Virtualisation / The Cloud | Security |
Monday, 16th July 2012, 09:45:05
One IT security expert has described current anti-cybercrime measures are 'prehistoric'.
categories: | Security | Ecommerce |
Monday, 9th July 2012, 16:31:30
Despite worrying about how to protect their data, more than half of web users have not changed their online passwords in the last 12 months.
categories: | Security | Ecommerce |
Friday, 6th July 2012, 10:30:19
Nearly half of London firms are concerned about how the iconic event will affect the workplace, a survey shows.
categories: | Virtualisation / The Cloud | Security |
Thursday, 21st June 2012, 14:49:55
The organisation has said that the case is "lawyer driven" and "without merit".
categories: | Security |
or just email our Sales Team if you have any questions about any of Hostway's services.
Read the latest headlines from these selected categories...
Previous headlines...
* All prices exclude VAT where applicable. All plans, packages and offers are subject to terms and conditions of sale available on the site.
© Hostway Corporation. All rights reserved.
A global web hosting leader, Hostway has strategic locations in the United States and Europe, including the Netherlands, Belgium, France, Romania and Germany, as well as Korea, India, and Australia.


text:
Our Favourite from laura j turnbull on Vimeo.
Time: December 31, 2010 at 11pm to January 1, 2011 at 7pm
Location: The Mason Jar
City/Town: Sussex
Website or Map: http://www.feelsgood.ca
Event Type: nye, party
Organized By: mumble
Latest Activity: Dec 18, 2010
Export to Outlook or iCal (.ics)
Come celebrate the grand re-opening of the Mason Jar as well as a step into a brand new year; both of which hold unlimited potential for love, laughter and maybe a pint or two!
We here at Gordon Gets Lost couldn't be happier to share these new beginnings with you all! The old Mason Jar had become one of our favourite places to play and it'll be great to kick off a new love affair in true maritime fashion!
Come jig with us!
Add a Comment
© 2014 Created by The Big 3.


text:
Year of publication
- English (127) (remove)
- Blockcopolymere (19)
- Polyelektrolyt (13)
- Nanopartikel (11)
- Polymere (8)
- Anionische Polymerisation (6)
- Polymerisation (6)
- Micelle (5)
- Selbstorganisation (5)
- Theoretische Biophysik (5)
- Chemie (127) (remove)
- Effect of Dopants on the Local Atomic Structure and Sintering Behavior of Bismuth Sodium Titanate (2014)
- The most commonly used piezoceramic is lead zirconate titanate Pb(ZrxTi(1-x))O (PZT). It possesses outstanding piezoelectric properties which can be modified for numerous applications by the addition of dopants. However, because of environmental and health concerns regarding lead, lead-free alternatives are demanded by politics. One of the two most promising lead-free replacement materials is the ferroelectric bismuth sodium titanate (Bi0.5Na0.5)TiO3 (BNT). Like PZT, it crystallizes in the perovskite structure. Since the dielectric and piezoelectric properties of pure BNT ceramics are insufficient for application, BNT is often modified by the addition of dopants. These influence a great variety of material properties to different degrees, e.g. the sintering behavior, the dielectric and piezoelectric properties and their respective temperature stabilities. Doping of BNT aims to decrease the sintering temperature in order to avoid Bi vaporization, to increase the depolarization temperature and to enhance the piezoelectric coefficient. The effects of numerous dopants on the resulting performance of BNT were studied extensively in the literature. However, so far little attention has been payed to the way in which dopants interact with the piezomaterial. Nevertheless, it is the understanding of these relationships that would make targeted modifications and improvements of BNT possible. The primary goal of this study was to investigate and explain the effects of a model dopant -cobalt- on the phase formation, sintering behavior and microstructure of BNT as well as on the resulting dielectric and piezoelectric properties. In this regard, a core issue was to determine the preferred lattice site of Co in BNT. BNT was synthesized from oxide powders using the classic solid-state route and sintered at temperatures ranging from 1000 °C to 1150 °C. Cobalt was added in concentrations between 0.1 mol% and 2.6 mol% Co prior to the calcination as Co3O4. About one third of the total cobalt amount was incorporated into the BNT lattice on the perovskite B-site, that is, it substituted for Ti. The cobalt in BNT appeared to be in equilibrium with the secondary phase Co2TiO4, which invariably formed at cobalt concentrations greater than 0.1 mol% Co. For charge balancing reasons, oxygen vacancies were created in the lattice of cobalt-doped BNT. These markedly enhanced the diffusivity. As a result, the sintering temperature of doped BNT decreased with increasing cobalt concentrations, and high final densities were achieved. However, in highly doped BNT sample swelling occurred at elevated temperatures of the sintering cycle. This phenomenon was attributed to evaporating oxygen caused by the valence transition of Co3+ to Co2+. Up to 950 °C, BNT was found to densify via solid state sintering mechanisms. Above this temperature, a small amount of liquid phase was present, which probably formed from decomposing BNT because of a slight Ti-deficiency due to doping. Increased Bi vaporization from the melt above 1000 °C appeared to have stabilized sodium cobalt titanate, an additional secondary phase. The rotation of the iso-lines in the kinetic field diagram of doped BNT was interpreted such that the activation energy for grain growth was higher than the activation energy for densification. Possible reasons are the solute-drag effect and the pinning of domain walls by secondary phase particles. Both the depolarization temperature and the piezoelectric coefficient d33 decreased with increasing cobalt concentrations. The dielectric properties deteriorated as well. This was attributed to the high electrical conductivity of the doped samples, which prevented full poling.
- Polyelectrolyte Complexes and their Therapeutic Potential (2014)
- This thesis describes the preparation of polyelectrolyte nanostructures, the characterization of interpolyelectrolyte complexes (IPECs) made from these structures and their use in a therapeutic context. The therapeutic use of such IPECs connects the two major topics of this work: First, the delivery of genes into eukaryotic cells in vitro by means of new star-shaped polycations was explored. Second, the structure of ionic multicompartment micelles (MCMs) when complexed with polyions was studied and the performance of these nanostructures as delivery agents of anti-cancer drugs both in vitro and in vivo was tested. To better understand structure-property relationships of polycations relevant for gene delivery, a library of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) homopolymers was synthesized. Star-shaped polymers with a different number of arms and molecular weights were created by using sugar-based or inorganic nanoparticles as core molecules with varying number of initiation sites. The cytotoxicity as well as transfection performance of polyplexes from these polymers and plasmid DNA was determined for different PDMAEMA-nitrogen/DNA phosphate ratios in CHO-K1 cells. A decrease of the cytotoxicity of polymers with a given molecular weight was observed with increasing degree of branching, i.e., with increased arm-number. Star-shaped PDMAEMA with roughly 20 arms (Si-PDMAEMA) showed exceptionally high transfection efficiency. The superior transfection behavior of this specific polymer was demonstrated in non-dividing or differentiated (C2C12 and human T lymphocytes) cell lines. Additionally, polymeric micelles were produced from a polybutadiene-block-PDMAEMA diblock copolymer in aqueous solution and subsequently used for gene transfection. Their transfection efficiency was in the same range as that of Si-PDMAEMA, hinting towards a general design principle for highly effective gene vectors. This consists of a star-shaped architecture of PDMAEMA chains emanating from a common center. The second major part of this thesis deals with the structure of ionic MCMs complexed with diverse polycations as well as the drug delivery capabilities of some of these complex micellar structures. MCMs from polybutadiene-block-poly(1-methyl-2-vinyl pyridinium)-block-poly(methacrylic acid) (BVqMAA) triblock terpolymers were used as the basis for further structural modifications. These micelles exhibit a core-shell-corona morphology, where PB forms the core of the micelles, a discontinuous (patchy) shell consisting of an IPEC between P2VPq and PMAA is present and finally a corona of excess PMAA stabilizes the micelles in aqueous solution. At sufficiently high pH a portion of the corona carries negative charges, which were then used to form further IPECs with either cationic homopolymers or double-hydrophilic block copolymers featuring one positively charged block. If polycations other than poly(2-vinyl pyridine) such as quaternized PDMAEMA were used for the complexation, a new and distinguishable IPEC compartment was formed on top of the already existing P2VPq/PMAA IPEC. In the case of MCMs with a short to moderate block length of the corona, i.e., the degree of polymerization (DP) of PMAA was between 345 to 550 units, a layered arrangement of the newly formed IPEC compartment was found. For BVqMAA micelles with a long PMAA corona (DP of PMAA = 1350) complexed with different quaternized homopolymers, a patchy arrangement of the newly formed IPEC compartment instead of a layered one was found. The formation of this new structure is due to an interfacial energy minimization between the new IPEC and the compartmentalized core of the micelles that became possible due to the exceptionally long PMAA corona of the precursor micelles. Finally, MCMs from BVqMAA were tested for their capacity to deliver a hydrophobic anti-cancer drug for photodynamic therapy to lung cancer cells in vitro and in vivo. The influence of the corona composition was studied by forming complexes with a double-hydrophilic diblock copolymer, poly(L-lysine)-block-poly(ethylene glycol) (PLL-b-PEG). A new cylinder-on-sphere morphology was observed in electron microscopy for BVqMAA/PLL-b-PEG complex micelles at high complexation ratios between lysine and MAA units. Highest cytotoxicity and uptake were found for pure BVqMAA micelles, both decreasing with increasing amount of PLL-b-PEG attached to the micelles. In mice, a prolonged blood circulation time in the range of several hours was exclusively observed when fully PEGylated micelles were injected. Those micelles were the only ones showing an enhanced accumulation in a subcutaneous tumor model 24 h after intravenous injection. The amount of drug delivered to the tumor tissue by the micelles suppressed tumor growth for up to 21 days after a single dose injection and photoirradiation step. The potential of complex micelles on the basis of BVqMAA MCMs could thus be proven.
- Group 3 and Group 13 Metal Hydride Compounds (2013)
- The aim of this thesis was to synthesize (and characterize) group 3 and group 13 metal alkyl and hydride complexes. These complexes were supported by aminopyridinato, guanidinato and phenolato ligands. Guanidinato ligand stabilized aluminum alkyl complexes were synthesized through alkane elimination. Aminopyridinato and guanidinato ligand stabilized aluminum hydride complexes were synthesized using H2 elimination. Mononuclear structures featuring tetrahedral coordination of the central aluminum atom were observed for the guanidinato ligand stabilized aluminum dialkyl complexes. The (Al)N-C-N(Al) bond angles in the corresponding complexes were determined using structural data. A decrease in the angle with increasing steric bulk of the ligands backbone was observed. Studies regarding the dependency of the used aminopyridinato and guanidinato ligand on the structure and stability of aluminum hydride complexes were carried out. The prepared aminopyridinato ligand stabilized alane complex adopts a binuclear, double hydride bridged structure. The aluminum atoms are five-coordinated in this compound. This complex is thermally unstable. Intramolecular ligand redistribution reactions were observed even at room temperature resulting in a mononuclear aluminum monohydride complex stabilized by two aminopyridinato ligands. Again, the aluminum atom was five-coordinated in this compound. To obtain thermally stable complexes, guanidinato ligand stabilized aluminum hydride complexes were synthesized. Based on available literature, guanidinato ligands are not likely prone to follow ligand transfer reactions. If the guanidine PipGuH (N,N'-bis(2,6-diisopropylphenyl)piperidine-1-carboximidamide) is reacted with alane, an isostructural (to the aminopyridinato ligand stabilized aluminum hydride complex) binuclear, double hydride bridged complex was observed. Moreover, the reaction of a bulky guanidine ligand with lithiumalanate was studied. Formation of a novel guanidinato ligand stabilized alanate complex (81 % yield) was observed. This is a rare example of a σ-alane lithium complex. Guanidinato or phenolato ligand stabilized lanthanoid dialkyl complexes were synthesized starting from lanthanoid trialkyl complexes. These trialkyls were prepared by salt metathesis reaction of lithium alkyls with lanthanoid trichlorides. Hydrogenolysis with H2 was used to convert the guanidinato ligand stabilized yttrium dialkyl complex into a trinuclear guanidinato ligand stabilized yttrium hexahydride cluster compound. This cluster compound was studied by single crystal X-ray structure analysis and NMR spectroscopy. Highly dynamic behavior of the hydrides and the guanidinato ligands was observed by variable temperature 1H NMR spectroscopy. A heterobimetallic lutetium–tungsten polyhydride cluster compound was prepared by reaction of bis cyclopentadienyl tungsten dihydride with a phenolato ligand stabilized lutetium dialkyl complex. Cluster formation proceeded via C–H bond activation of the Cp ligands that stabilize the transition metal-containing educt followed by alkane elimination. Single crystal structure analysis revealed a cluster composed of three tungsten atoms and two lutetium atoms. Each of the two Lu atoms is double bridged by two µ2-hydrides and two µ3-hydrides to the W atoms. This finding was confirmed by 1H NMR spectroscopy. In addition, the first examples of ternary rare earth–transition metal polyhydride cluster compounds were synthesized starting from a phenolato ligand stabilized lutetium monoalkyl complex featuring a direct Lu–Re bond. Cluster formation proceeded by reaction with bis cyclopentadienyl tungsten dihydride or the analogue molybdenum compound. For both cluster compounds, the average yield was 50 %. Both of the ternary compounds were characterized by single crystal structure analysis and NMR spectroscopy. These studies revealed isostructural clusters featuring two lutetium atoms, either two tungsten or two molybdenum atoms and a rhenium atom. The W and Mo atoms, respectively, are bridged by two µ2-hydrides to the lutetium atoms. Quantum chemical calculations of the electronic structure, based on a simplified model (substituting H for the tert-butyl groups of the phenolato ligand) showed ionic W–H∙∙∙Lu interactions and a covalent, polar Lu–Re bond.
- Mesostructuring of SiCN Materials and Catalysts via Microphase Separation Technique utilizing High-Density Polyethylene Blocks (2013)
- The objective of this thesis is to utilize the hydroxylterminated polyethylene (PE-OH)produced via Ziegler's "Aufbaureaktion" for the synthesis of 1) porous polyethylene templates for the synthesis of structurally inverted porous SiCN (siliconcarbonitride) 2) SiCN mesomaterials using PE-OH as porogen 3) porous SiCN supported gold catalysts. Porous polyethylene template was synthesized from polyethylene-block-polylactide (PEOPL) copolymer by microphase separation technique and selective etching of polylactide block.1H NMR was used to confirm the formation of copolymer. Atomic Force Microscopy (AFM) was used to analyse the microphase separated PEOPL copolymer. The progress of etching polylactide block was monitored by Fourier Transform Infrared Spectroscopy (FTIR).Scanning Electron Microscopy (SEM) was used to analyse the porous polyethylene template. The SiCN mesomaterials were synthesized from PE-OH by linking with commercially available polysilazane (HTT1800). Linked copolymer was microphase separate, cross-linked, and pyrolysed for the synthesis of SiCN mesostructures. Upon tuning the weight (volume) ratio of HTT1800 and PE-OH, various morphologies such as lamellae, fibers, and disordered biconteneous SiCN can be synthesized (Figure 1.1).These morphologies were confirmed by AFM, TEM, SEM and Small Angle X-ray Scattering (SAXS). Die SiCN-Mesomaterialien wurden durch Bindung des PE-OHs an kommerziell erhältlichem Polysilazan (HTT1800) erhalten. Das entstandene Copolymer wurde mirkophasensepariert, vernetzt und pyrolisert. Durch Variation des Gewichts- (Volumen-) Verhältnisses von HTT1800 und PE-OH konnten verschiedene Morphologien wie Lamellen, Fasern und bicontinuierlem SiCN erhalten werden. Diese Morphologien wurden mittels AFM, TEM, REM und Kleinwinkelröntgenstreuung (SAXS) untersucht. Porous SiCN supported goldceramic (Au@SiCN) catalyst was synthesized by copolymer formation, microphase separation, crosslinking, and pyrolysis. The biconteneous SiCN morphology has been chosen as a support for the synthesis of porous catalyst due to high surface area and the pores in the range of mesoscale (2-50 nm). Gold nanoparticles were introuduced by addingtetrameric aminopyridinato gold complex. The synthesized Au@SiCN catalysts were characterized by TEM, powder XRD, and N2 physisorption. The stability of nanoparticles may be due to the nitrogen functionality of Si-C-N network (Figure 1.2). The catalytic performance of the synthesized catalyst was demonstrated in the oxidation of cyclic and linear alkenes with air. The catalyst was highly selective for the epoxide products. Zusammenfassung Ziel dieser Doktorarbeit ist es, Hydroxy-terminiertes Polyethylen (PE-OH), welches über Zieglers "Aufbaureaktion" zugänglich ist, für die Synthese von 1) einem porösen Polyethylentemplat für die Herstellung von porösen SiCN 2) SiCN-Mesomaterien mittels PE-OH als porogen 3) poröse SiCN geträgerte Gold-Katalyatoren. Das poröse Polyethylentemplat wurde durch Mikrophasenseparation mittels einem Polyethylen-block-polylactid (PEOPL)Copolymer und selektivem Herauslösen des Polylactidblocks synthetisiert. Die Bildung des Copolymers wurde mittels 1H-NMR bestätigt. Das mikrophasenseparierte PEOPL-Copolymer wurde mittels Rasterkraftmikroskopie (AFM) analysiert. Das Herauslösen des Polylactid-Blocks wurde mittels Fouriertransformierter Infrarotspektroskopie (FTIR) verfolgt. Das poröse Polyethylentemplat wurde mittels Rasterelektronenmikroskopie (REM) analysiert. Die SiCN-Mesomaterialien wurden durch Bindung des PE-OHs an kommerziell erhältlichem Polysilazan (HTT1800) erhalten. Das entstandene Copolymer wurde mirkophasensepariert, vernetzt und pyrolisert. Durch Variation des Gewichts- (Volumen-) Verhältnisses von HTT1800 und PE-OH konnten verschiedene Morphologien wie Lamellen, Fasern und bicontinuierlem SiCN erhalten werden. Diese Morphologien wurden mittels AFM, TEM, REM und Kleinwinkelröntgenstreuung (SAXS) untersucht. Die porösen SiCN geträgerten Gold-Katalysatoren (Au@SiCN) wurden durch Copolymerbildung, Mikrophasenseparation, Vernetzung und Pyrolyse synthetisiert. Aufgrund der hohen Oberfläche und Poren im Mesobereich (2-50 nm) wurde die bikontinuierliche SiCN Morphologie als Träger für die Synthese von porösen Katalysatoren verwendet. Durch die Zugabe eines tetramerischen Aminopyridinato-Gold-Komplexes konnten Goldnanopartikel in die poröse SiCN-Matrix eingeführt werden. Der synthetisierte Au@SiCN Katalysator wurde mittels TEM, Pulverdiffraktometrie (XRD) und N2-Physisorption (BET) charakterisiert. Die Nanopartikel können dabei durch die Stickstoff-Funktionen des Si-C-N-Netzwerkes stabilisiert werden. Der hergestellte Katalysator wurde in der katalytischen Oxidation von zyklischen und linearen Alkanen mit Luftsauerstoff getestet. Hierbei war der Katalysator sehr selektiv hinsichtlich der Epoxidierung.
- Hybrid Devices: Morphology Control by Self-Assembly (2013)
- This thesis focuses on innovative concepts for hybrid photovoltaic devices. In particular, it aims at the improvement of light harvesting and the control of morphology. Hybrid devices combine the advantage of excellent electronic properties of inorganic semiconductors and the convenient processability of organic materials. However, the creation of suitable morphologies which guarantee a high interface area between donor and acceptor as well as continuous charge percolation pathways still remains a challenge. This thesis addresses the key issues utilizing state-of-the-art synthesis and characterization methods for the development of highly functional dyes as well as well-controlled polymers and blockcopolymers. In the first part, BODIPY (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) dyes were investigated which feature a broad absorption range up to the IR region accompanied by high extinction coefficients. These dyes were tested in solid state dye sensitized solar cells. In addition, triphenylamine based sensitizers were examined which feature beneficial redox potentials and excellent stability but at the expense of the broad absorption. Besides the light harvesting, a second issue concerning solid state dye sensitized solar cells is the lack of control over the morphology of the titania network such as network wall thickness and pore diameter. On basis of polymer brush particles made of a polystyrene core and a polystyrene sulfonate corona, a novel template assisted preparation of a mesoporous TiO2 electrode was established. In contrast to established methods, our template permits the individual control of the TiO2 network density and pore size. With variation of the TiO2 content during the hydrolysis, a fundamental correlation between the TiO2 density, the sensitized interface area and the resulting current generation was discovered. These results contribute to an improved knowledge toward dye sensitized hybrid solar cells. Building up on the knowledge gained from the polymer brush templates, novel amphiphilic semiconducting block copolymers were developed which facilitate the self-assembly of hybrid composites. The semiconductor component is based on well-known triphenylamine derivatives, while the hydrophilic block comprises the polystyrene sulfonate which features unique coordination and catalytic characteristics. The controlled reversible addition−fragmentation chain-transfer (RAFT) process was chosen for polymerization. In order to improve the versatility, the procedure was extended toward a combination of RAFT and "click" chemistry. The resulting amphiphilic semiconductor block copolymers form micelles in polar solvents or water. I utilized the highly charged micelles to attach oppositely charged CdSe nanorods. On the other hand, these block copolymer micelles were assembled on conductive substrates and annealed in saturated DMF vapor leading to microphase separation and a vertical alignment of the microdomains. Altogether, these studies pave the way for a profound basis for the development of morphology controlled hybrid devices. In the final part of this thesis the concept of amphiphilic semiconductor polymers or conjugated polyelectrolyte was developed in order to completely avoid insulating organic blocks. In this regard, a conjugated polythiophene backbone was combined with the sulfonate groups in the side chain. The presented approach significantly improves the control of the polymer synthesis permitting the modulation of the molecular weight, a narrow polymer distribution, a regioregular conformation and well-defined end groups. The highly regioregular conformation induces an unprecedented aggregation phenomenon. Studying the optical properties of the conjugated polyelectrolytes, a distinct correlation between molecular weight and aggregation was observed in aqueous solutions. Further, the electrical properties were studied in detail. A bulk hole transport mobility of 1.3 ± 0.5 x 10^-2 cm^2/Vs was determined which is among the highest values reported so far. In contrast to other conjugated polyelectrolytes impedance spectroscopy revealed a pure electronic transport mechanism without ion reorganization. In conclusion, this thesis comprises innovative concepts to improve light harvesting and gain control over the morphology of hybrid devices. The established synthesis protocols enable the controlled preparation of well-defined functional amphiphilic polymers and block copolymers. The achieved results not only allow new approaches for the optimization of hybrid devices, but also provide the basis for a more comprehensive investigation of physical processes due to the systematic morphology control in such devices.
- Design of Robust Heterogeneous Catalysts for Sustainable Chemistry (2013)
- Robust heterogeneous catalysts based on polymer derived non-oxide ceramics (SiC/SiCN) with integrated late transition metal (Ni, Pd) nanoparticles (NPs) were designed, characterized and tested for their catalytic potential. For the decoration of SiCN support with metal NPs, a molecular approach was applied which makes the use of amido metal complexes for the chemical modification of the preceramic polymer (commercially known as HTT 1800, Clariant Advanced Materials GmbH, Sulzbach, Germany) by the transfer of metal to its nitrogen functions. The modified polymer was transformed to an amorphous SiCN material containing metal NPs by controlled pyrolysis under an inert atmosphere. By following aforementioned approach, Cu@SiCN materials (non-porous) have already been developed in our research group. In present thesis, attempts were made to fabricate porous SiCN/SiC materials with good accessibility of metal (Ni and Pd) NPs. Firstly, the synthesis of palladium containg SiCN materials by the pyrolysis of palladium modified polysilazane was attempted. It was found that during polymer to ceramic transformation, palladium reacts with silicon to form intermetallic palladium silicide particles. The materials were characterized (TGA, FT-IR, NMR, PXRD and TEM) and applied in catalytic hydrogenation reactions. The activity of the catalysts was found low because of the silicidation of metal and non-porous SiCN support. The issues of the low porosity of SiCN ceramics and the formation of metal silicides were addressed in the synthesis of Ni@SiCN materials. Controlled pyroylsis of Ni modified polysilazane at 600°C provided microporous Ni@SiCN materials, whereas at 1100°C the formation of nickel silicides in non-porous SiCN matrix was observed. Ni@SiCN materials were characterized by solid state NMR, FT-IR, PXRD, TGA, N2-physisorption and TEM. Hyperpolarized 129Xe NMR was used to study the effect of nickel loading and annealing time on pore structure. The microporous materials showed good thermal stability and activity in selective hydrogenation of aryl acetylenes but as polymer to ceramic conversion was not complete at 600°C, the materials possessed low hydrothermal stability at higher temperatures due to the hydrolysis of Si-N bonds. In order to replace Si-N bonds with more stable Si-C bonds, a commercial polycarbosilane was used to fabricate SiC materials with integrated Ni NPs by the pyrolysis of nanostructured polycarbosilane-block-polyethylene (PCS-b-PE) polymer. PCS-b-PE was synthesized by the reaction of PCS with PE-OH catalyzed by an amido nickel complex followed by its nanostructuring via microphase separation technique. The length of PE block affected the type of pores generated in SiC material and the synthesis of highly porous materials with micro-, meso- and hierarchical porosity was achieved. Ni@SiC materials were characterized by TGA, PXRD, N2-physisorption and TEM. Hierarchically porous Ni@SiC selectively cleaves aromatic C-O bond of aryl ethers in water and was found a reusable catalyst. Lastly, controlled pyrolysis of palladium modified polysilzane provided nanoporous SiCN materials with very small and highly accessible Pd NPs. This shows the role of SiCN support whose nitrogen atoms have a stabilizing effect on small metal nanoparticles. Moreover, SiCN support ineracts nicely with the NPs leading to the prevention of their leaching. In general, NPs have agglomeration tendencies with increasing metal loading but in the case of Pd@SiCN, size of metal NPs remained small even with a palladium loading of 14 wt%. Pulse titration with hydrogen showed high accessibility of Pd. Pd@SiCN materials showed better activity than commercial Pd/C catalyst in oxidation of alcohols in the absence of air or oxygen with the evolution of hydrogen. M@SiCN/SiC materials may find applications in sustainable production of chemicals and fuels from renewable sources, for instance, from lignocellulosic biomass.
- Bottom-up Self-Assembly across Hierarchies: From Triblock Terpolymers to Patchy Particles to Colloidal (Co-)Polymers (2013)
- In this work the bottom-up self-assembly of compartmentalized particles on multiple hierarchies was investigated. ABC triblock terpolymers were directed as basic build-ing blocks into nano-scale corona-compartmentalized (patchy) particles via selection of kinetic self-assembly pathways. An extremely efficient and versatile step-wise self-assembly process was developed offering unique nano-engineering capabilities over addressable corona patches. Thereby, carefully chosen solvent sequences were of outmost importance. Depending on the volume ratio of the core forming blocks, VA/VB, two species with different geometrical distribution of the patches were identified: for VA/VB > 1, a Janus-like AB distribution, with patches A and C emanating from opposing sides of the B core and for VA/VB < 1 an ABA distribution, with two A patches on opposing sides of the B core protected by an equatorial C corona. The par-ticles were then used as colloidal building blocks (CBBs) that, upon addition of non-solvent for A, underwent next level hierarchical self-assembly. The AB CBBs self-assemble into spherical multicompartment micelles (MCMs) with precise control over aggregation number (VA/VB). In contrast, ABA CBBs grow into extended linear colloidal polymers of up to several micrometres in length via a step-growth polymerization process. The cluster size (AB)x and the worm length [ABA]m are both conveniently controlled by the solvent quality for the corona block (expansion/contraction). This dynamic tuning of the corona volume is a unique key feature of the bottom-up approach to soft patchy nanoparticles from triblock terpolymers. In a consecutive work, the AB and ABA CBBs were mixed in specific ratios prior to self-assembly by addition of non-solvent for A. With both CBBs present, aggregation by mutual interaction of A patches into mixed colloidal co-assemblies was accomplished. Colloidal co-assembly is a hierarchical structuring process crossing multiple hierarchies primarily driven by the minimization of interfacial energies. It critically depends on both the dynamic volumes change of the corona and of the aggregating patches with changing solvent polarity. The extraordinary quality of the superstructures is ascribed to the selection of kinetic pathways for co-assembly and similarly, to the dynamic tailoring of patch volume. Particles with a large C corona, but small attractive A patch are stable over broad a range of solvent compositions. On the contrary, particles with a small C corona, but large attractive A patch start to cluster even with at low contents of non-solvent for A. Hence, the mismatch of onset of self-assembly is a set screw to either form the colloidal "substrate" in the first step and decorate subsequently or vice versa. Both approaches lead to well-defined and predictable mixed colloidal co-assemblies comprising colloidal molecules, multiblock co-assemblies, telechelic oligomers, ternary co-assemblies and two-dimensional networks, all of which are exclusively accessible with the presented approach. The spherical MCM consist of AB CBBs with a B-core with a Janus-like distribution of the A and C blocks as a result of symmetry breaking during cluster formation in non-solvents for A. This phase separation within MCMs represents a novel and versatile route for the template-free synthesis of terpolymer-based, sub 100 nm Janus particles. The synthesis encompasses facile cross-linking of the patches of spherical MCMs to preserve the phase-separated state. This approach yields narrowly dispersed Janus micelles and offers unique options to nano-engineer core diameter, the Janus balance (volume ratio of A and C hemispheres) and the chemistry of the patches. Homogeneous populations of MCMs even at very high concentrations of 100 g/L enable high throughput synthesis of soft Janus micelles making this novel approach technologically relevant. Beyond that, the Janus balance proved decisive for cluster shape and size when the particles were subjected to a selective solvent for either of the hemispheres. The Janus particles (JPs) with tailored Janus balance were finally applied as disper-sants for multi-walled carbon nanotubes (MWNTs). Thereby, the JPs attach to the tube surface with a suitable hydrophobic patch (polystyrene), while facilitating stabilization in the solvent with the other. Depending on the Janus balance, i.e., the size ratio of adsorbing to stabilizing patch, dense multilayer coatings were obtained or helical arrangements with defined JP-JP interparticle spacing. In both cases, the quantity of attached JPs was substantial and unparalleled. Besides the known applications of JPs in emulsion polymerization and as compatibilizers in polymer blends, JPs proved also effective as non-covalent supracolloidal dispersants for MWNTs and may also find application as general dispersant for other insoluble particulate matter.
- Supramolecular Nanofibers - Preparation, Structure-Property Relations, and Applications (2013)
- Conventional polymer nanofibers have gained tremendous interest in the last years in the fields of catalysis as templates, in medicine as tissue engineering, in functional textiles as protective suits, and especially in air filtration as filter media. Generally, nanofibers are prepared by top-down approaches. However, these processes feature several disadvantages. As consequence cost-effective alternative strategies are required. One strategy to this problem is the bottom-up approach – the self-assembly of small molecules. Therefore, this thesis covers different topics with respect to the preparation, structure-property relations, and application of supramolecular nanofibers: To investigate the impact of the molecular structure on the stacking behavior in the self-assembly process, a set of pyrene-containing model compounds was synthesized. Here, the focus was set on the influences of sterical demanding side groups as well as hydrogen bonding motifs on the stacking of the pyrene units. These influences were, besides others, detected by excimer formation in dilute solution, in the aggregated state and in solid films. It was demonstrated that stacking of the pyrene units is the driving force of the self-assembly process in solution in this system. However, hydrogen bonds are required to obtain well-defined supramolecular nanofibers. The influence of the hydrogen bonding motif and the sterical hindrance on the pyrene stacking becomes more and more significant the closer the molecules are forced together. Hence, the columnar stacking is increasingly disturbed in solid films compared to solution. The class of 1,3,5-benzenetrisamides is one of the simplest and most-versatile motifs in supramolecular chemistry. Within this thesis, two different self-assembly processing pathways of benzenetrisamides from solution; in particular self-assembly upon cooling at constant concentration and self-assembly during solvent evaporation at constant temperature were explored. One factor that determines the actual processing pathway is the solubility of the benzenetrisamide molecule. Exclusive self-assembly upon cooling takes place when the benzenetrisamide is almost completely insoluble in the used solvent at room temperature. The prerequisite for self-assembly during solvent evaporation is certain solubility of the BTAs at room temperature. In addition, these self-assembly pathways were compared with respect to control the supramolecular nanofiber morphology in view of homogeneity, fiber diameter, and fiber diameter distribution. Thereby, influences of external parameters such as temperature, solvent, and concentration were investigated in detail. Especially in air filtration industry nanofibers are an important tool because of their beneficial effects due to their high surface-to-volume ratio. In industry, electrospinning is the standard technique to post-modify nonwoven filters with conventional polymer nanofibers on the filter surface. However, this process is limited to the surface of the scaffold. In this thesis, the principle utilization of supramolecular nanofibers in air filtration is demonstrated for the first time. Here, a solution-based immersion process was developed, which allows a successful in-situ formation of supramolecular nanofibers in nonwoven scaffolds. This results in a stable microfiber-nanofiber composite. The main advantage of this process is the effective incorporation of nanofibers in the volume of the nonwoven fabrics. For supramolecular systems, it was claimed that they are too fragile to be competitive with conventional polymers. But the herein prepared supramolecular nanofibers possess enough stability even upon applied airstreams of 3.0 meter per second. This stability is by far superior than it is required at standard vacuum cleaners which possess flow velocities of 0.25-0.40 meter per second at the filter element. First filtration tests revealed promising filtration efficiencies. Building on these promising results a comprehensive study on structure-property relations at the preparation of microfiber-nanofiber composites in view of optimized filtration efficiencies was investigated. Depending on the selected benzenetrisamide, solvent, and concentration of the immersion solution, the filtration efficiency of the filters can be adjusted. By varying the thickness of the filters by means of double- and triple-layer filters, for supramolecular modified filters, excellent filtration efficiencies over 90 percent were obtained for aerosol particles with the size of 0.2 micrometer.
- Direct Force Measurements on the Colloidal Scale: From Modified Electrodes to Particle Manipulation (2013)
- In this thesis the interfacial surface forces and mechanical properties of thin films have been studied by the colloidal probe technique. One central point is the combination of direct force measurements with an electrochemical setup in order to tune interfacial properties of an electrode modified with an organic layer. In particular the adhesion and ion adsorption have been studied, which are ubiquitous phenomena in the colloid science, electrochemistry, and biology. Moreover, a novel technique has been developed to fabricate chemically and mechanically stable colloidal probes for atomic force microscopy (AFM). Additionally, the elastic properties of polyelectrolyte multilayer films were locally resolved under controlled humidity. The adhesive behaviour of colloidal particles on modified electrodes has been studied by direct force measurements with a micrometre-sized silica probe attached to an AFM-cantilever. By controlling the external potential applied to the modified electrode by means of a potentiostat, separate adhesion contributions at the modification layers in electrolyte solution were quantified. In particular, to determine the influence of the terminating functional groups, gold electrodes modified with self-assembled monolayers (SAMs) terminated in non-ionizable groups were used. It has been demonstrated that electrostatic double-layer forces dominate the adhesion of colloidal particles on hydrophobic and hydrophilic interfaces. In contrast to hydrophilic interface, for hydrophobic one forces due to the solvent exclusion play a significant role and leads to an offset in the adhesive force, which otherwise can be compensated by the external potential. However, the electrocapillarity is of minor importance and can be neglected. To quantify the ion adsorption at organic interfaces a novel approach was followed, which is based on direct force measurements with silica colloidal probes on SAM-modified electrodes in electrolyte solutions. By variation of applied potential and concentration of specifically adsorbed ions, given by the solution's pH, the charging behaviour of hydrophilic SAM-OH and hydrophobic SAM-CH3 has been determined. In difference to electrokinetic techniques, direct force measurements allow to probe the full range of the diffuse layer. The analysis of the diffuse layer potential as a function of externally applied potential provides important information. In particular, the shift of the potential of zero charge (pzc) indicates on the specific ion adsorption in the Stern layer as it alters the charging behaviour of the electrode's interface. It has been demonstrated that hydronium and hydroxide ions adsorb on both the hydrophobic and hydrophilic interfaces. However, the presence of the background electrolyte (KCl) does not shift pzc and thus its ions have no specific affinity towards the interfacial adsorption. The adsorption of hydronium and hydroxide ions is stronger on hydrophobic, than on hydrophilic interface. This is in agreement with theoretical studies. The simple three-capacitor model based on a Langmuir-type adsorption isotherm provides semi-quantitative description of observed dependence of the diffuse double layer potential on applied potential. A new technique for colloidal probe preparation was developed. A great challenge for the force measurements with the AFM is to ensure the cleanliness, chemical and mechanical stability of the used probes. The approach is based on high-temperature sintering of micrometer-sized silica particles to AFM cantilever with enhanced contact area. Due to a "neck" formed by nanometer-sized particles the increased mechanical stability of colloidal probes was achieved, which has been quantitatively determined by lateral force spectroscopy. The implementation of sintering procedure for silica colloids allowed the development of the highly stable colloidal probes, whose surface properties could be renewed by heating. Finally, the mechanical properties of polyelectrolyte multilayer films have been determined by nanoindentation as a function of relative humidity. For these series of measurements again a colloidal probe has been used. It has been demonstrated that films containing polyglutamic acid have Young's modulus, which depends on humidity. The change of stiffness with ambient humidity has reversible character.
- Structure-Property Correlation of Electron Transport Materials in Organic Devices (2013)
- This dissertation deals with organic semiconductors as electron acceptor (n-type) materials in bulk heterojunction (BHJ) solar cells. Important features of an electron acceptor are strong visible light absorption, sufficient high electron mobility and appropriate energy levels with respect to the donor. Furthermore, the blend morphology of donor and acceptor is crucial for the device performance. Within this thesis, the synthesis and characterization of novel n-type polymers is reported and various techniques to evaluate the above mentioned parameters for n-type small molecules and polymers are presented. The aim was to investigate the impact of chemical structure on the optical and electronic properties and morphology of these semiconductors. Successful strategies how to control and improve light harvesting, electron mobility, blend morphology and solar cell performance were identified. The fundamental question of charge transport properties of the materials was addressed by fabricating single carrier devices using the SCLC (space-charge limited currents) method. The morphology was primarily investigated by atomic force microscopy (AFM) and X-ray diffraction (XRD). The first part of this thesis focuses on perylene imide based small molecules and polymers. The side groups of a series of N-substituted perylene bisimides (PBI) were found to play a crucial role on crystallinity and charge transport. The nature of the side groups had great impact on the crystalline structure and electron mobility. When hydrophilic oligoethylenglycol (OEG) side groups were present, the perylene molecules aligned in highly ordered hexagonal or lamellar columns and realized high electron mobilities of up to 7∙10E-3 cm2V-1s-1, while the perylene derivative with only hydrophobic alkyl chains only showed 3∙10E-5 cm2V-1s-1. The substituents at the perylene core also had a major impact on the blend morphology of OPV devices when these materials were used in combination with a donor polymer. Here, we were able to tune the extent of phase separation between donor and acceptor via hydrophilic-hydrophobic interactions of donor polymer and acceptor side groups. To improve light harvesting of perylene compounds, the pi-electron system of PBIs was altered and highly soluble, novel perylene side chain polymers (PPDB and PPDI) were synthesized by nitroxide mediated radical polymerization (NMRP). The pendant perylene moieties were perylene diester benzimidazole (PDB) and perylene diester imide (PDI). Compared to polymers bearing PBI side groups, the visible light absorption of PPDB was broadened and red shifted, whereas a narrower and blue shifted absorption was observed for PPDI. Remarkably, also the electronic nature of the two materials was affected by the modification at the perylene core, as PPDB is an n-type semiconductor and PPDI has a more pronounced p-type character. A comparative study of perylene side-chain polymers synthesized by a combination of NMRP and "click" chemistry revealed that the compound with improved optical properties (PPDEB) exhibited worse charge carrier mobility compared to PPBI. Another striking result was found as an amorphous polymer bearing OEG side chains showed a better electron mobility than the corresponding material with alkyl chains, which was liquid crystalline. A very high electron mobility of 1∙10E-2 cm2V-1s-1 was measured. The second part of this dissertation addresses fullerene based acceptor materials, among which Phenyl-C61-butyric acid methyl ester (PCBM) is the state-of-the-art n-type semiconductor used in OPV. For two fullerene derivatives, Bis-Phenyl-C61-butyric acid methyl ester (bis-PCBM) and Bis-o-quino-dimethane C60 (bis-oQDMC), the LUMO energy levels were higher compared to PCBM. As a result, improved open circuit voltages (Voc) in BHJ solar cells were obtained. The efficiency however did not improve, because of reduced short circuit current densities (Jsc). We found that for the bis-PCBM system, Jsc was limited by low electron transport, while for the bis-oQDMC system an unfavorable blend morphology hampered the performance. The problem of low electron mobility could be overcome by reducing the thickness of the active layer and higher Jsc and overall device performance could be achieved. A drawback of fullerene small molecules is that diffusion, aggregation and crystallization of these molecules within BHJ blends can often negatively affect the stability of the blend morphology and reduce the device performance. We discovered that aggregate and crystallite formation in novel fullerene side chain polymers could be successfully suppressed, whilst high electron mobility and better film properties were achieved. Altogether, new insights into structure-property relation of organic electron transport materials are presented in this work. Moreover, the detailed analysis of charge transport helped to understand the performance of solar cells.


text:
- Product Description
- Customer Reviews (11)
Product Description
The HJC CL-33 includes the following features:
- Lightweight, injection-molded, thermoplastic alloy shell
- Pop-up forehead and side vents allow for flow-through ventilation
- Plush, brushed-Nylex interior for a comfortable fit
- Flip-up shield features a tool-less removal/replacement system
- Nylon strap-retention band neatly secures chin strap
Construction: Injection-molded thermoplastic
Shield: tool-less removal/replacement system
Weight: 2.86 lbs/1300 grams (approx)
Standard: DOT-218
Customer Reviews (11)
Average Customer Rating:
Write a review and share your thoughts with others.
Reviewer: Burt (Nashua, New Hampshire) 9.1.2014
Perfect except for one thing
The vents on the front of the helmet keep snapping shut on their own. Be careful when opening the visor when the forehead vents are open 'cuz the visor catches on them if they're open. BUT, with that exception - PERFECT!
Reviewer: Doug (, SD) 7.8.2014
Nice helmet...could use better padding on sides. Looks good and vents are nice. The customer service at Helmet City was excellent, making sure it arrived in time. I was impressed.
Reviewer: Paul (Olalla, WA) 1.16.2014
Not for crashes
I bought the helmet because it was the cheapest with a full, flip up face shield. The helmet is to be worn over a balaclava and wool watch cap and under a poncho with a hood. The purpose is to try to stay warmer and drier when sailing in the cold wind and rain up here in the pacific northwest. The helmet seems quite comfortable and I'll see how well it works next week on our first sailing trip of the new year.


text:
Opera on the Couch: The Flying Dutchman
by Milton Schaefer, Ph.D., Opera on the Couch, Chair
Drs. Eileen Keller and Lee Rather were discussants for the Opera-on-the-Couch discussion of Wagner's The Flying Dutchman immediately following the November 3 performance at the San Francisco Opera. Their presentations led to a lively back and forth, which was moderated by Dr. Steve Goldberg, between the 80 or more participants.


text:
Set approximately 15 minutes away from the main city centre, but still within the city limits, Bangsar is best known as Kuala Lumpur's international village. This suburb of Kuala Lumpur caters to pockets of varying cultural and social echelons. Popular for its urban nightlife, it's not as rowdy as KL but while the city centre sees more of a tourist and local Chinese crowd, Bangsar's the haunt of expats, upscale yuppies, and KL's well-to-do and college students. The area plays host to the Bangsar Shopping Centre and Bangsar Village shopping complex, but worth special mention is the smorgasbord of upscale eateries and frugally-priced friendly neighbourhood warungs or hawker centres. In a nutshell Bangsar's appeal lies in its ability to cater to everyone. No matter the hour of the night you're sure to come across trendy party animals as well as families out for a late night nasi lemak supper.
Another branch of the popular Cititel chain, this Mid Valley venture is particularly well placed especially for those anxious to sample Malaysia's retail therapy offerings. Winner of the 2008/2009 Malaysian Tourism Premier Award for the 'Best in Hotel Services' in the three-star category, Cititel is a glass, steel and chrome building that towers over the Mid Valley quadrant. The hotel has 646 guestrooms and is flanked by the uber popular Mid Valley Megamall and The Gardens shopping complexes. One of our Top 10 Best Kuala Lumpur hotels, the air con, carpeted rooms feature broadband internet access and a mini bar; hotel facilities include a health spa and well-equipped business centre. Nearby public transportation access includes the Mid Valley KTM Komuter station. Read More...
The absolutely stylish The Garden Hotel & Residences has 448 super fashionable and luxurious air con rooms sporting upmarket, contemporary furnishings and fixtures. Each lodging unit boasts broadband internet access, flat-screen TVs and a pillow menu; the five-star hotel's also got 179 fully-furnished serviced residences and hotel facilities include a saltwater infinity pool, three restaurants and two bars. Flanked by the Mid Valley Megamall and The Gardens shopping centre, the hotel's well situated – the Mid Valley KTM Komuter is a short walk away. Read More...
One of our Top 10 Best Kuala Lumpur hotels, Boulevard Hotel is a four-star venture with plenty of windows, marble floors and 395 rooms as well as 66 studio suites. Sporting contemporary minimalist chic furnishings and fixtures, rooms feature broadband internet access. The property features an on-site herbal spa, fully equipped gym, five function rooms and a spacious café that overlooks the infinity pool. Flanked by The Gardens and Mid Valley Megamall, some of the perks of this hotel include access to the mall's bowling alley and 18-screen cinema; the nearest public transportation access is the Mid Valley KTM Komuter. Read More...
Sri Tiara is a three-star, 30-storey tower block with 150 elegantly furnished two- and three-bedroom apartments with balconies, full kitchens and complimentary wireless internet access. Set on a one-hectare hill slope, the hotel's range of facilities includes a fitness centre, a heated outdoor pool, playground, a sauna and tennis court. The Mid Valley KTM Komuter, Bangsar LRT station and Tun Sambathan Monorail stations are a few kilometres away – Mid Valley Megamall is less than a kilometre away. Read More...
Executive 1 Bedroom Apartment
From MYR 427
Help us keep this website up-to-date by sending us your comments and suggestions. If your question is about a hotel please use this link - For TOUR questions and enquiries please use this link
Asia Web Direct Travel Club members have access to our free travel guides, and lots of other travel specials and benefits from the Asia Travel Specialists.
Please enter your details and we'll send your free {place} Travel Guide to you straight away. We will also add you to our free Asia Web Direct Travel Club Newsletter.
Here's the link to download your guide. We've also emailed you the download link.
We will not pass your details on to any other company or individual. We take your privacy seriously!


text:
Some of you might be familiar with Atrum Viator, a doodle comic that I did forever ago but would never really stick to. Well, recently I've been working on a new, cleaner and clearer version. Firebrand.
The pages are also available here on my dA. So far I'm at 21 since early September. I've been having way too much fun! XD
This is not set in Equestria, but it is in the same world. The main difference is that magic is not common. Some few scholarly unicorns have access to minor magics, but they do not generally share this.
Race attributes:
Earthponies - Strength
Unicorns - Intelligent, No magic
Pegasi - Gliders, Fast, Few can actually fly


text:
UPDATE: We've also got a download of the song below.
The video for Summer Camp's new single "Better Off Without You" pairs the British duo's '80s-vintage twee indie-pop with '70s-vintage footage of youth going wild, all in nicely-executed split-screen. Imagine the teensploitation classic Over The Edge, if it had somehow featured an all-K Records score. Kissinger Twins direct. Watch the video below.
- Summer Camp – "Better Off Without You"Download
The song appears on Summer Camp's album Welcome To Condale, out 11/8 on Apricot/Moshi Moshi.
Tags: Kissinger Twins, Summer Camp
Leave a ReplySign in Sign in with Facebook
You must be logged in to post, reply to, or rate a comment.
%s1 / %s2


text:
A behind-the-scenes look at Lord's, the perfect gift for a family of cricket fans!
This experience is available at Greater London:
Browse our sister gifting sites in Europe:
Best price guarantee If you find the same experience cheaper online within 14 days then we'll refund you 150% of the price difference!
UK's best gift experiences With over 4,000 gift ideas we've gone around the whole UK to bring you the best deals on the best gifts.


text:
Classic Vehicle Hire - Self Drive/Chauffeur Driven Trade Directory : Australia
Misty Rose Limousine & Vintage Wedding Cars
Misty Rose of Adelaide offers a professional chauffeur driven experience. A combination of unique, immaculately presented vehicles, industry accredited chauffeurs, and attention to detail.
Mustang Classic Hire
We cater for any occasion including Weddings, Formals, Special Occasions, Sydney Sight Seeing, Promotions, Corporate and Special events, Photo Shoots, Movies and TV work.
Silver Cloud Wedding Cars
We pride ourselves on our collection of Sydney's most prestigious classic cars, all lovingly cared for and maintained. Our fleet consists of a variety of English cars including Rolls Royce, Bentleys and both modern and classic Jaguars.
Snow White Mustangs
3 Classic Mustangs Available / Weddings, Engagements, Anniversaries / Any Occasion / Chauffeur Driven / Exiting, Fun, Memorable
Supercar Rentals
Supercar Rentals specializes in the self drive rental of contemporary Australian performance cars such as Monaro, HSV and FPV vehicles. Experience the best in Australian Motoring. WE RENT EXCITEMENT!!!
Sydney Belle Wedding Cars
At Sydney Belle, we pride ourselves on being the exclusive Sydney based company to offer gorgeous 1940's Black Buick Wedding cars. We are a family business dedicated to affordable quality, service, & reliability you would expect for your wedding day.
Sydney Classic Car Hire
The Swinging Sixties! Sex, Drugs and Rock n Roll and some of the most stylish cars ever designed. Now you have the chance to relive that time.... though, without the drugs please! My personal car collection is now available for self drive hire.
Vintage Journeys
Vintage Journeys is a privately owned family company, offering bridal and special occasion travel in the Melbourne metropolitan area, plus individual sight seeing and winery tours in nearby country areas.


text:
'Archos 80 Titanium Is Just Right At This Price'
'Low price, Decent build quality'
'Good, solid build quality, Good brightness '
'Feels lightweight but well built'
'8in display that's both bright and colourful'
'Reasonable screen, Good build quality, Smooth application performance'
'Excellent Tablet for the Price!'
'Sharp screen is great for the price'
'Stylish design, Rigid chassis, Screen displays brilliant colors'
'Decent tablet for the money'
'Overall satisfactory screen, wide viewing angles '
'Good tablet for the Dollars'
'Cool Idea Killed by ABYSMAL Battery Life'
'Poor gaming interface'
'Good Price'
'Great little tablet'
'Runs 1080p video smoothly'
'Mediocre build quality'
'Low price & dual-core CPU'
'Units affected by screen issues'
'Loved the tablet..Non-functional Wifi'
'Can access Android Market'
'Very small and light power pack'
'Wide range of connectivity and generic support'
'Full-size USB port '
'Do not buy this product'
ReviewGist helps you find the best products to buy by making sense of online reviews.
We are currently aggregating 360,836 reviews
covering over 28,844 products. See what the press says about ReviewGist here.
The Best Cellphone Buying Guide for 2014 is the definitive starting point for your next cellphone purchase.
© 2007-14 ReviewGist.com. All Rights Reserved.


text:
Maria Papagiannidou died last Sunday. Another very public and active denialist has kicked the bucket; sad but predictable. Her face and "story" is all over the internet.
She appeared on TV espousing the lie of living a "healthy" life with HIV/AIDS, while her immune system CD4 cells were being invaded and killed off.
She wrote a book, "Goodbye AIDS! Did it ever exist?". (Yes it does, and it killed you.)
I know she contacted some people I know about starting HAART but she left it a bit late. She and her husband did everything within their considerable powers to rubbish HIV science, question the medicine and scare people away from treatment: for that she's now paid the ultimate price.
I hope that people who read this will draw one lesson: AIDS DENIAL KILLS.
Don't be taken in by the smiling faces and sob stories of people who claim to live a perfectly healthy life free of (HIV) drugs: if you are HIV positive you can't and will die.
Rethinking AIDS will have to do yet another edit to remove this deceased rethinker: she thought her last thought on Sunday. So farewell Maria. Peace be with you.
UPDATE – New post from Denying AIDS blog on the Maria P New post from Denying AIDS blog
UPDATE(2) – This is her denialist website. I guess its needs updating to reflect the the fact she's gone to a better place.
Filed under: AIDS, Celia Farber, Denialists, HIV Tagged: | AIDS, death, Denying AIDS, HIV, Karri Stokely, Maria Papagiannidou, Rethinking AIDS


text:
LEA: Wirral
Telephone Number: 0151 638 5180
Fax Number: 0151 638 5180
Address: GardensideMoretonWirralMerseyside
Post Code: CH46 2RP
Qualified Teacher? Teach at
Holy Spirit Catholic and Church of England Primary School
, register today.
Links below for postcode: CH46 2RP
View a map of area
Click here to update the details of Holy Spirit Catholic and Church of England Primary School
in, Wirral
Teaching jobs in Wirral
SEN Teachers and Teaching Assistants register FREE with Axcis Education Recruitment. At Axcis we are experts in the recruitment of SEN teachers and support staff. We work with schools across the SEN spectrum: ASD, SLD, MLD, PMLD, EBD. Axcis places qualified SEN teachers and experienced SEN support workers from both the UK and overseas into teaching jobs and teaching assistant jobs nationwide. We have teaching and teaching assistant jobs in SEN schools and supporting SEN pupils in mainstream classrooms. Axcis Education is unique in offering training and career development in SEN.
Advertise your schools vacancies
free of charge, Click here
Home | Teachers | Employers | Contact | Register
Resources | LEAs in the UK | Blog | Become a Teacher | Recruitment Consultant Jobs
Schools - Advertise your vacancies free of charge | School Directory
RSS Job Feeds: All Jobs | UK Jobs |
XML Job Feed: All Jobs
Copyright © Axcis Education Recruitment (2001 - 2014) - All rights reserved
Privacy Policy - Data Protection ACT
E-mail: email@example.com
Tel: 0800 107 9900 (Int. +44 20 7580 2956)
Fax: 0800 107 9902 (Int. +44 20 7504 8761)


text:
Mai T. Le '15 told Flyby that "slack lining" is her study break of choice.
"When you're standing on a rope you can't think about anything else," she said.
What are your favorite ways to relax during exams? Let us know in the Comments section below!
Want to keep up with breaking news? Get the latest, straight to your inbox.


text:
Power 98's "STEP OFF 2013:" Pictures Of Step Performances
by WILLY J April 1, 2013 9:44 AM
The Morning Maddhouse (6a-10a) Read More
The Power 98 Step Off was crazy again this year as step groups from around the Charlotte metro area competed to win the top cash prize!
Congrats to YAK for winning 1st place along with Ransom Middle School and KAOS for winning 2nd and 3rd place, respectively.
We also had special performances from G.T. and B. Smyth who rocked the stage with his latest single "Leggo" ft. 2 Chainz!
Click Here to watch all of the Step Off Performances! Click Here to watch B Smyth perform!


text:
Day Tour Amalfi Coast (8 hours)
A HINT OF HISTORY...The Amalfi Coast is a stretch of coastline famous worldwide for its natural beauty, home for many other major touristic sites. Considered World Heritage by UNESCO, it is named after the town of Amalfi, which reppresents not only its geographical nucleus but also in terms of history. The Amalfi Coast is also known for its diversity: each of its countries of the Coast have their own traditions and landmarks. Furthermore you can enjoy some of its amazing typical products, such as limoncello, the lemon liqueur produced in the area, anchovies and canned fish, pottery made and hand painted.
Tour Description:
For pick up from Hotel/Down Town/Train
The order of the itinerary might change caused from the traffic.
Please , don't hesitate to contact us for any further information you might need.
*Included: Tools ,parking ,petrol and taxes.
Required *


text:
Definitions for Assignmentəˈsaɪn mənt
This page provides all possible meanings and translations of the word Assignment
Random House Webster's College Dictionary
as•sign•ment*əˈsaɪn mənt(n.)
something assigned, as a particular task or duty.
a position of responsibility, post of duty, or the like, to which one is appointed.
an act of assigning; appointment.
the transfer of property, as to assignees for the benefit of creditors. the instrument of transfer.
Category: Law
* Syn: See task.
Origin of assignment:
Princeton's WordNet
assignment, duty assignment(noun)
a duty that you are assigned to perform (especially in the armed forces)
"hazardous duty"
the instrument by which a claim or right or interest or property is transferred from one person to another
assignment, assigning(noun)
the act of distributing something to designated places or persons
"the first task is the assignment of an address to each datum"
grant, assignment(noun)
(law) a transfer of property by deed of conveyance
an undertaking that you have been assigned to do (as by an instructor)
appointment, assignment, designation, naming(noun)
the act of putting a person into a non-elective position
"the appointment had to be approved by the whole committee"
Kernerman English Learner's Dictionary
assignment(noun)əˈsaɪn mənt
a piece of work or a job
a written assignment; a dangerous assignment
the act of assigning, or an assigned task
a position to which someone is assigned
a task given to students, homework or coursework
a transfer of something from one person to another, especially property, or a claim or right; the document that effects this transfer
an operation that assigns a value to a variable
Origin: assignement
Webster Dictionary
an allotting or an appointment to a particular person or use; or for a particular time, as of a cause or causes in court
a transfer of title or interest by writing, as of lease, bond, note, or bill of exchange; a transfer of the whole of some particular estate or interest in lands
the writing by which an interest is transferred
the transfer of the property of a bankrupt to certain persons called assignees, in whom it is vested for the benefit of creditors
In computer programming, an assignment statement sets and/or re-sets the value stored in the storage location denoted by a variable name, in other words, it copies the value into the variable. In most imperative programming languages, the assignment statement is a fundamental construct. Today, the most commonly used notation for this basic operation has come to be x = expr followed by x := expr, although there are many other notations in use. In some languages the symbol used is regarded as an operator while others define the assignment as a statement. Assignments typically allow a variable to hold different values at different times during its life-span and scope. However, some languages does not allow that kind of "destructive" re-assignment, as it might imply changes of non-local state. The purpose is to enforce referential transparency, i.e. functions that do not depend on the state of some variable, but produce the same results for a given set of parametric inputs at any point in time. Modern programs in other languages also often use similar strategies, although less strict, and only in certain parts, in order to reduce complexity, normally in conjunction with complementing methodologies such as data structuring, structured programming and object orientation.
British National Corpus
Written Corpus Frequency
Rank popularity for the word 'Assignment' in Written Corpus Frequency: #3553
Nouns Frequency
Rank popularity for the word 'Assignment' in Nouns Frequency: #2041
Translations for Assignment
Kernerman English Multilingual Dictionary
a duty assigned to someone
You must complete this assignment by tomorrow.
- opdragAfrikaans
- مَهَمَّه، واجِبArabic
- назначениеBulgarian
- tarefaPortuguese (BR)
- úkolCzech
- der AuftragGerman
- opgave; lektie; hvervDanish
- εντεταλμένο έργο, αποστολήGreek
- cometido, tareaSpanish
- kohustus,ülesanneEstonian
- تکلیف؛ مأموریتFarsi
- tehtäväFinnish
- tâcheFrench
- מִנוּיHebrew
- सौंपा हुआ कार्यHindi
- zadaćaCroatian
- kinevezésHungarian
- tugasIndonesian
- verkefniIcelandic
- compitoItalian
- 任務, 課題Japanese
- 배정Korean
- užduotisLithuanian
- uzdevumsLatvian
- tugasanMalay
- taakDutch
- oppgave, oppdrag, lekseNorwegian
- zadaniePolish
- تکلیف؛ مأموریتPersian
- ماموریت ، تکلیفPashto
- tarefaPortuguese
- sarcinăRomanian
- поручениеRussian
- úlohaSlovak
- nalogaSlovenian
- zadatakSerbian
- uppdrag, uppgiftSwedish
- การมอบหมายThai
- görev, ödevTurkish
- 任務Chinese (Trad.)
- завданняUkrainian
- تفویض ، مفوضہUrdu
- nhiệm vụVietnamese
- 任务Chinese (Simp.)
Get even more translations for Assignment »
Find a translation for the Assignment definition in other languages:
Select another language:
Discuss these Assignment definitions with the community:
Use the citation below to add this definition to your bibliography:
"Assignment." Definitions.net. STANDS4 LLC, 2014. Web. 19 Dec. 2014. <http://www.definitions.net/definition/Assignment>.


text:
Tea Party Sympathizers Skewer 401(k) Proposal
BOSTON ( TheStreet) -- Tea Party followers seem to have added " 401(k) plans" to their list of cherished liberties.
Low taxes, abundant weaponry and limited government are at the core of the movement. But President Barack Obama better not touch 401(k)'s, according to public comments aimed to help the departments of Labor and the Treasury determine steps to "enhance retirement security for workers in employer-sponsored retirement plans through lifetime annuities or other arrangements that provide a stream of income after retiring."
The stock-market crash and economic recession erased up to half of many Americans' 401(k) plans and IRAs, a devastating blow to new retirees and those about to enter their Golden Years.
Obama's Middle Class Task Force, headed by Vice President Joe Biden, has cited as one of its goals the availability of "annuities and other forms of guaranteed lifetime income, which transform savings into guaranteed future income, reducing the risks that retirees will outlive their savings."Reading through the 500 comments posted online, it's clear that few of those taking the time to weigh in want anything to do with such a proposal. A sample of the responses: 1. "I am appalled and insulted that you would consider yourself in a better position than I to know what is best for me in regard to my own money. I have already decided to skip both my and my wife's 2009 Roth IRA contribution, and I have already ceased contributing to a retirement plan for 2010. Unless, and until, I hear that you are dropping this disastrous plan, I have made my last retirement contribution." 2. "Is your plan seeking to privatize my IRA by turning it over to the custody of a private insurance company? If that is so, then I've got major heartburn over this plan. Do you realize that as an unsecured creditor (which I would be) to a private insurer, my fate would depend solely on the solvency of the insurer? With the recent revelation that the use of
Select the service that is right for you!COMPARE ALL SERVICES
Action Alerts PLUSTry it NOW
Jim Cramer and Stephanie Link actively manage a real portfolio and reveal their money management tactics while giving advanced notice before every trade.
Product Features:
- $2.5+ million portfolio
- Large-cap and dividend focus
- Intraday trade alerts from Cramer
- Weekly roundups
TheStreet Quant RatingsTry it NOW
Only $49.95/yr
Access the tool that DOMINATES the Russell 2000 and the S&P 500.
Product Features:
- Buy, hold, or sell recommendations for over 4,300 stocks
- Unlimited research reports on your favorite stocks
- A custom stock screener
- Upgrade/downgrade alerts
Stocks Under $10Try it NOW
David Peltier, uncovers low dollar stocks with extraordinary upside potential that are flying under Wall Street's radar.
Product Features:
- Model portfolio
- Stocks trading below $10
- Intraday trade alerts
- Weekly roundups
Dividend Stock AdvisorTry it NOW
Jim Cramer's protege, David Peltier, identifies the best of breed dividend stocks that will pay a reliable AND significant income stream.
Product Features:
- Diversified model portfolio of dividend stocks
- Alerts when market news affect the portfolio
- Bi-weekly updates with exact steps to take - BUY, HOLD, SELL
Real Money ProTry it NOW
All of Real Money, plus 15 more of Wall Street's sharpest minds delivering actionable trading ideas, a comprehensive look at the market, and fundamental and technical analysis.
Product Features:
- Real Money + Doug Kass Plus 15 more Wall Street Pros
- Intraday commentary & news
- Ultra-actionable trading ideas
Options ProfitsTry it NOW
Our options trading pros provide daily market commentary and over 100 monthly option trading ideas and strategies to help you become a well-seasoned trader.
Product Features:
- 100+ monthly options trading ideas
- Actionable options commentary & news
- Real-time trading community
- Options TV


text:
Access to risk mitigation is critical for India's 120 million farmer households (80 percent of whom are small and marginal farmers), who are highly dependent on rain-fed cultivation. Crop failures lead to distress and the inability to service debts, creating a potential debt trap. Crop insurance also helps enhance the viability of crop lending and hence is vital for banks. India's crop insurance program is the world's largest (25 million farmers) yet, 85 million farmer households are not covered. The relatively low coverage is explained by issues in product design and a post-disaster government funding mechanism (latter was partly necessitated by the lack of an actuarially sound premium rating methodology without which estimating payouts is not feasible). A post-disaster funding mechanism is sub-optimal for budget management for government, and, for farmers, it delays claims settlement and leads to high exposure to risk.
Through Non-Lending Technical Assistance (NLTA), the Bank helped design an actuarial premium determination methodology and a cost-effective risk financing solution for crop insurance. Actuarial tools were used to demonstrate, amongst other things, the efficiency and political economy gains possible through faster claims settlements. The approach helped the client gain technical knowledge and use technical tools to influence policymaking. The joint regional and anchor staff team worked collaboratively with the client and national and international experts in this highly specialized area. Capacity building included regular visits of a certified actuary. The team also collaborated with a sub-national agriculture sector lending project to pilot ideas on the ground (use of cell phones to report crop yields). The approach has also involved adapting state-of-the-art tools to second-best technical solutions when necessary to reflect ground realities and political economyconsiderations. The work combined both traditional and new generation (weather) insurance as opposed to promoting one over the other.
The NLTA produced the following key outputs and milestones:
- Formulation of a best-practice, country-specific, actuarially sound premium determination methodology (2007-10) and product design to address farmer risk mitigation helped improve the main existing crop insurance program.
- Policy formulation and piloting of an improved crop insurance program in 50 districts (an estimated 400,000 farmers have participated in the first crop season)
- Review of India's crop insurance program (including underwriting and ratemaking (2007)
- Development of commercial weather-based crop insurance products, which led to an increase of the public insurer's weather-based crop insurance portfolio to almost 1 million farmers and a total annual premium volume in excess of US$50 million (2009-10)
- Development of the public insurer's capacity to transition to a market-based approach (2007-11) and increased involvement of private insurance and reinsurance market in crop insurance
- Policy dialogue on the fiscal and welfare implications of the improved program (2007-11)
- Prototype actuarial software and pricing of more than 200 insurance products, and advice on mobile and remote sensing technology to improve data quality and timeliness (2009-11).
Bank Contribution
The main contribution of the World Bank has been through highly specialized technical and operational advice to the client, including through drawing on national and bringing in international best practices and other country experiences. The NLTA has been supported through the Bank budget supplemented by trust funds (total cost around US$1 million).
While the direct client of the NLTA is AICI, the ultimate beneficiaries are India's farmers. The benefits to farmers come from a better insurance product, greater product options, faster claims settlements and more equitable pricing. Better understanding of risks – through the actuarial premium rates – can facilitate more appropriate agriculture policy and agriculture extension services, thereby improving farmer cropping patterns and productivity.
Click to see project locations mapped:
The NLTA involved collaboration with government, the Agriculture Insurance Company of India (AICI) and various technical institutions. Funding from the Swiss Agency for Development and Cooperation Agency, the Financial Sector Reform and Strengthening Initiative (FIRST) and the Global Facility for Disaster Reduction and Recovery (GFDRR) sustained activities.
Toward the Future
With the launch of the improved pilot program in 50 districts, the immediate challenge is to address technical and implementation issues that confront any such new product roll-out. For the client, a key next step is to evaluate how well the pilot program has performed. This will be done at the end of three crop seasons (2012). Based on this, a decision will be taken on the scaling up of the program. Technical support to improve market infrastructure and address the complexities of implementing the scaling up of such a large program will remain a challenge going forward.


text:
Through June 15, the posh Broadmoor resort expects to benefit from Frontier Airlines' new, nonstop service to Colorado Springs, Colo., from Los Angeles, Phoenix, Seattle and Portland.
So, to celebrate the new service, the Forbes Five Five Star, AAA Five Diamond-rated resort is giving Frontier Airlines customers a free upgrade.
The Broadmoor's website shows rates starting at $255 for Friday and Saturday night, although Sunday is sold out.
TWITTER: Follow USA TODAY's Barb DeLollis
How do I get my upgrade?
Upon check-in at the resort, just show a same-day Frontier Airlines boarding pass from one of the four new markets.
There is a catch: The free upgrade's subject to availability and the hotel's website shows many sold-out nights, so perhaps you should call in advance to see how likely the upgrade will be to avoid being disappointed.
The resort's located at the gateway to the Colorado Rocky Mountains. It encompasses 3,000 acres with three championship golf courses, a nationally recognized tennis program, a spa and fitness center, 744 lodging rooms and suites, including new cottage suites and 18 restaurants, cafes and lounges.
The Broadmoor, by the way, has an impressive 4,158 followers on Twitter.
Readers: Have you been? Tell us about your stay.
USA TODAY is now using Facebook Comments on our stories and blog posts to provide an enhanced user experience. To post a comment, log into Facebook and then "Add" your comment. To report spam or abuse, click the "X" in the upper right corner of the comment box. To find out more, read the FAQ and Conversation Guidelines.


text:
Practical Science on Movement and Pain
Practical Science on Movement and Pain
What does the word placebo mean? Does the placebo effect involve actual health benefits or just imagined benefits? Is placebo "mind over body" or "all in your head"? Is it unethical to provide a client with placebo treatments? And what about nocebos? In this article I'll answer these questions and discuss some fascinating research by… Read More
Chronic pain is a complex and confusing problem. Unlike acute pain, which is well correlated with injury, chronic pain is often unrelated to tissue damage. It might be driven by a wide variety of factors like sleep, mood, thoughts, or emotions. And chronic pain is connected with other health problems like obesity, anxiety, depression, or IBS. We can better understand… Read More
Could you break the word record for the marathon after just four years of serious training? Dennis Kimetto recently ran the marathon in 2:02:57, 26 seconds faster than anyone else in history. Here is some footage from his incredible run. Looks pretty much like some guy jogging right? Although he doesn't appear to running that fast, he… Read More
I recently returned from a two-week trip to Spain with family and friends. Before I went, I was telling people about it, and they all said "Wow, Spain, awesome!!" And then their expression would shift a little, and they would ask whether I was taking my two young kids. I would say yes, and then they would… Read More
You have probably heard the claim that bad posture causes back pain, or that you should work on your posture to get rid of low back pain. You can find this claim all over the internet – from physical therapists, chiropractors and personal trainers. If you do a Google search for "posture and pain," you… Read More
I recently did two interviews that are now available for your listening pleasure. Here is a link to an interview podcast I did with Erin Goldman of Awakened Heart Yoga. Erin asked many great questions about the connection between movement and emotion, and the value of play in movement health. By the way, Erin also… Read More
Do you experience tension, discomfort, and a pervasive feeling of overall yuckiness while sitting in your chair staring at the computer hour after hour? Let's face it. You probably do. And you probably know that the best solution to this problem is to get out of your chair as often as possible and get moving. Your body… Read More
I have a favor to ask my readers.* I am working on a new set of posts that I think will really drive some traffic to the site. Market research shows people just love to read about certain subjects, and I have put together some great new blog post titles addressing those subjects. But I… Read More
Here's a few quick updates. New Formats for A Guide to Better Movement My book is now available on Kindle and Nook. Are there are any other formats or markets you would like to see? Audio? iTunes? Anyone interested in videos of the lessons in the book? Podcasts I recently did a podcast with Justin Goodhart… Read More
This blog is focused on the central nervous system – how it affects the way we move and feel, and what we can do to change its function in that regard. But that doesn't imply that the structure of the body is unimportant, or that good movement is "all in your head." The structure and health… Read More