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Stephen Paulus Sheet Music: 2 items found
The Dale Warland Christmas Editions, Vol. I
Arranged by Dale Warland, Jeffrey Van, and Stephen Paulus. For Choral (SATB). Festival Choral. 40 pages. Hal Leonard #43550. Published by Hal Leonard (HL.41923044)
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The Dale Warland Christmas Editions - Vol.II - SATB
Composed by Jeffrey Van. Arranged by Dale Warland, Stephen Paulus, John Rutter, Cary John Franklin, and Elizabeth Poston. For Choral (SATB). Festival Choral. Vocal Standards. Difficulty: medium. Vocal score (6 copies needed for performance). Vocal score. 64 pages. Published by Hal Leonard (HL.41923054)
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Stephen Paulus


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Poll: What should be done to improve Sacramento's bicycling scene?
Sunday's Conversation tackled in The Sacramento Bee's Opinion section focused on how bicycling fits into Sacramento's traffic scene.• On a mission to get bikes off sidewalks
• A solution for bikes and pedestrians
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The Sacramento Bee is pleased to provide this opportunity to share information, experiences and observations about what's in the news. Some of the comments may be reprinted elsewhere on the site or in the newspaper. We encourage lively, open debate on the issues of the day, and ask that you refrain from profanity, hate speech, personal comments and remarks that are off point. Thank you for taking the time to offer your thoughts.

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Oregon plant breeder Carol Deppe, author of The Tao of Vegetable Gardening, holds a PhD in biology from Harvard University and specializes in developing public-domain crops for organic growing conditions, sustainable agriculture, and human survival for the next thousand years. Carol is author of The Resilient Gardener: Food Production and Self-Reliance in Uncertain Times (Chelsea Green, 2010), Breed Your Own Vegetable Varieties, 2nd ed. (Chelsea Green, 2000), Tao Te Ching: A Window to the Tao through the Words of Lao Tzu (Fertile Valley Publishing, 2010), and Taoist Stories (Fertile Valley Publishing, 2014). Visit www.caroldeppe.com for articles and further adventures.
Carol Deppe will lead several workshops at the Mother Earth News Fair in Albany, Oregon from June 6-7th. Workshop topics will include the eat-all greens garden, the do-it-yourself seed bank, gardening and farming with climate change, and growing your own cornbread, polenta and other corn-based baked goods.
Carol Deppe will speak at the NW Permaculture Convergence on August 28-30 at the River Road Park District Recreation Center in Eugene. Carol's books will be available for sale and signing at the event.
The Tao of Vegetable Gardening, explores the practical methods as well as the deeper essence of gardening. Organized into chapters that echo fundamental Taoist concepts: Balance, Flexibility, Honoring the Essential Nature, Effortless Effort, Non-Doing, and even Non-Knowing, The Tao of Vegetable Gardening illustrates the key principles and practices that home gardeners need to know to successfully plant and grow the most popular vegetables.
If you're a dedicated gardener you probably know about hot-water-bath canning and pickling, but there are many other ways to preserve the bounty of your harvest so it will last the whole year. This set combines a classic book on food preservation with a new book on gardening that includes some innovative preservation methods.
Scientist/gardener Carol Deppe combines her passion for gardening with newly emerging scientific information from many fieldsresilience science, climatology, climate change, ecology, anthropology, paleontology, sustainable agriculture, nutrition, health, and medicine. In The Resilient Gardener, Deppe extends these principles with detailed information about growing and using five keystone crops that are especially important for anyone seeking greater self-reliance: potatoes, corn, beans, squash, and eggs.
In the age of biotech companies, genetic patents, and multinational seed companies, Deppe makes learning to save and breed your own seed and varieties easy and desirable for the gardener or farmer.
Sign up for our e-newsletter today and get 25% off your next purchase in our bookstore. Please note that discount codes do not combine with other offers or books already on sale.


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C-suite InsiderInsight Article | Mar 31, 2015 |For this installment of C-suite Insider, we spoke with Bob Geneczko just days after his retirement from PPL. But, we'll let him tell his own story.
Low Income Population Subsidizes OthersView from the Top | Mar 29, 2015 |The U.S. Hispanic Chamber of Commerce held its national convention in Salt Lake City this fall. As the largest gathering of Hispanic business leaders in the country, it got me thinking about our community's economic and cultural strength and how to ensure Hispanics remain an economic force in America.
Analysts in the utility industry have much work to do these days. With the deluge of data that has accompanied the smart grid evolution, analysts are leveraging the billions of rows of data and working to transform it into actionable insight. Analytics that utilizes data from the smart meters, coupled with data from a smart distribution system, has empowered---and will continue to empower---utilities to answer operational questions and solve problems with greater speed and accuracy.
Alex PischalnikovInsight Article | Mar 24, 2015 |The utilities industry is undergoing a major revolution---digital technologies and the Internet of Things (IoT) are enabling a smarter grid and a renewed focus on the customer. While wearable devices are a fairly new entry into this technology ecosystem, they offer utilities promising opportunities to make operations more efficient and to increase customer satisfaction.
A Changing Energy Landscape Creates OpportunityView from the Top | Mar 22, 2015 |Today's utility business environment is more volatile, more uncertain and more complex than in the past. How do we navigate and plot a strategic course forward in this moving and evolving market?
By failing to take advantage of the deals on the market and by staying loyal to their old supplier, around 13.5 million households are missing out on a slice of a potential £2.7 billion in savings, and while millions of these would reduce their energy bills by more than £200, many would save even more.
Featured from EnergyBiz Magazine
DATA ANALYTICS FOR UTILITIES is no longer a future-tense topic for the industry. It is no longer a question of can your utility benefit from analytics tools, but how well is your utility implementing its analytics program. Today's analytic leader must demonstrate an expertise in understanding data and advanced analytics while using cutting-edge tools to drive business decision-making. The tools
Fitch Ratings has upgraded the long-term Issuer Default Rating (IDR) of Ameren Illinois Company (AIC) by one notch to 'BBB+' from 'BBB'. In addition, Fitch has affirmed the long-term IDRs of Ameren Corp. (AEE) and Union Electric Company (UE) at 'BBB+'.


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Some place where we can talk, get to know one another, and be cool!
Would like a nice meet and greet lunch so we can get to know a little more about each other.
My first date idea is something simple like out to lunch or dinner so we could get all the neves out n talk get to know each other.
Fish and chips on the beach, movies, dinner in restaurant
Lunch then drinks pub or club or walking our dogs
Go for some lunch or dinner and then have fun playing some games
Would like to meet for lunch or dinner to get to know each other
l think coffee to start if things go ok then maybe a movie and then arrange another coffee date and work things from there slowly
Ilove to meet a woman. And have a drink and talk
Depending on the season and weather would ultimately decided our fate date for a first day.
Lunch or dinner Chicago Italian man likes all types of places let me know.
Grab a small bite and go for a walk.. Hang out at a park or some where to sightsee..
Meet to see if there is an attraction, if so then start to build relationship.
Going out to eat walk in the park a good movie and looking in to my girl eyes and talking to her about her day in life taking time for her
So that I can care take them out for a meal and drink and a walkand show I am the right person that I will not let you down
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Dual Boot Windows Versus Running In Virtual Machine
Msg#: 4652782 posted
6:43 pm on Mar 10, 2014
(gmt 0)
Anyone have opinions on dual boot versus running windows in a virtual machine under Linux Mint 13?
I have Mint 13 installed right now. My copy of windows 7 is supposed to be arriving later today.
My first thought is to run as a dual boot with win 7 and mint.
I am concerned that running under virtual machine might make it slower or increase complexity / increase chances of incompatibility.
My life is already complex enough as it is...
Dell Optiplex 780
Intel(R) Core(TM)2 Duo CPU E8400 @ 3.00GHz
4 gigs ram
Intel® Q45 Express Chipset w/ICH10DO
Thanks in advance.
wa desert rat
Msg#: 4652782 posted
2:31 am on Mar 20, 2014
(gmt 0)
And finally, the old saw that Windows is targeted because there are so many of them is only partly right. They are targeted because it is ridiculously easy to exploit them AND there are a lot of them
The only known operating system that could be owned by simply mousing over a single pixel on a web site. Good grief!
Msg#: 4652782 posted
8:31 am on Mar 20, 2014
(gmt 0)
Android does dispel some myths about Linux not getting viruses, there are plenty of instances of exploits out there.
Are the bits of Android that are exploited parts it shares with conventional Linux? What proportion are social engineering attacks? Without answers to those questions it proves nothing.
Also, how come Windows servers have a worse track record than *nix servers? There are fewer of them.
Msg#: 4652782 posted
9:42 pm on Mar 20, 2014
(gmt 0)
> And then there are the botnets of infected Windows boxes
And linux boxes, as I noted. There are a lot of linux servers being used as botnets. And Android, which is NOT always infected by users installing junk apps. Some apps appear to be doing a useful job but have hidden expolit functions. The fault, of course, lies with the appstore having such lax rules. I wonder who administers it? :)
Whether or not the IP of a virus implanter is static does not matter, except in so far as your mail servers implement DSL range blocks. And Windows would only fall for such attacks if the adminstrator/user were careless or stupid. My local windows machines are virus-free and I've had only one expolit on my online web server and that was through an exploitable FTP srver, still not fully explained but I believe was via a password stolen from one of my clients.
It all comes down to the implementation and implementer/maintainer. If they know what they are doing Windows is almost as safe as linux: the difference is. With linux you do not have to work quite so hard at protecting it.
Sorry, guys. We seem to have strayed from the original topic.
I'm about to find out about Hyper-V "VPS" on a Windows box. I've rented the windows 2012 server and expect access in a day or so. I will, during the next week, try installing postscript. I'm also hoping to use linux FTP services to give users (and me!) safer access to their web sites: we'll have to see about that one. :)
wa desert rat
Msg#: 4652782 posted
11:45 pm on Mar 20, 2014
(gmt 0)
And Android, which is NOT always infected by users installing junk apps. Some apps appear to be doing a useful job but have hidden expolit functions. The fault, of course, lies with the appstore having such lax rules. I wonder who administers it? :)
Android, which is based on Linux but developed by Google, has been highly altered to make it easy to work with on a phone or tablet. Even so, your first sentence is contradicted by your second sentence. I'm not sure what you're driving at.
And Windows is exploitable because of a decision made when they designed Win98. Gates thought that the Internet was a fad and that his market would be businesses using file sharing (SMB) and home users playing games. To that end he ignored tcp/ip (added later by stealing it from BSD Unix - it even had the copyright for years) and tying the graphics closely to the core of the OS (ring zero). Changing that now would require a major change in the APIs but it is at the heart of why Windows OSes are all exploitable; and mostly in the same ways.
Linux can be cracked but it is much mroe difficult to exploit and turn it into a botnet. Even the few "botnets" based on Linux are Java-based (an exploit through Java). That fix, btw, has been out for some time.
The conventional wisdom that Linux is just as insecure as Windows has been pushed by Microsoft and its allies because if the business world ever discovered that the insane amounts of money they spend to keep their MS networks safe could have been avoided, I suspect they'd revolt.
Msg#: 4652782 posted
11:57 pm on Mar 20, 2014
(gmt 0)
As to "linux does not get viruses" - that is not stricly true.
There has been no successful exploit of Linux since 2002 so, no, Linux does not get viruses. And, even then, that virus was squashed the same day.
Viruses are targetted at linux, though less often, and can be installed on the machine by an inattentive or dumb "user".
Which is the biggest difference with Windows where such things get installed by smart users. It's that inability to be installed on their own that is Linux/Unix/BSD's biggest protection.
As well as this, there was a bulletin today concerning linux web servers which are vulnerable because they haven't upgraded PHP (for example).
Please don't blame Linux servers for PHP and the admin's fault. Linux had nothing to do with that problem.
Some (probably not all) has been designed and installed by NSA aided no doubt by GCHQ.
Let's also not get into the latest fad "threat".
Msg#: 4652782 posted
2:14 pm on Mar 21, 2014
(gmt 0)
The same could be said about most environments, in many cases users open an email attachment or knowingly install software that has a hidden payload.
Has there been even a single Linux exploit that requires only opening an email?
Linux software is almost always installed from a repository and signed. There is little temptation even for naive users to download stuff of the internet and install it because it is difficult to do that, whereas installing from a repo (the Linux equivalent of an app store) is the easier.
In fact, that style of software installation is probably the best single thing about Linux and open source BSD. Windows and Mac now have app stores that are sort of similar, but they STILL do not have dependency management.
Msg#: 4652782 posted
2:15 pm on Mar 21, 2014
(gmt 0)
@dstiles, you are right we have wondered off the thread topic. Perhaps a moderator can cut some of this to a separate thread?
Msg#: 4652782 posted
9:37 pm on Mar 21, 2014
(gmt 0)
drhowarddrfine - and today there is evidence of unpatched linux being infected. Admittedly some are over 7 years old. Again, I accept this is user problems.
graeme_p - As we've noted, usually it requires someone to accept the payload. I have several linux apps that I had to install outside of the repository but I do tread with care. :)
Again, I accept that linux viruses come into the hens' teeth and rocking-horse droppings category.
On topic: I got control of the windows 2012 box today and am gradually working through various security settings, setting up disk paritions etc. Hopefully installing linux into a partition over the weekend.
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Polymer 45 (2004) 5013–5020 www.elsevier.com/locate/polymer Block copolymer grafted-silica particles: a core/double shell hybrid inorganic/organic material G. Laruelle, J. Parvole, J. Francois, L. Billon* ` ´ ´ ´ ´ Laboratoire de Physico-Chimie des Polymeres, UMR 5067 CNRS, Universite de Pau et Pays de l'Adour Helioparc Pau-Pyrenees, 2 Av. P. Angot, 64053 Pau Cedex 09, France Received 19 December 2003; received in revised form 7 May 2004; accepted 13 May 2004 Available online 2 June 2004 Abstract Hybrid inorganic/organic materials consisting of a poly(n-butyl acrylate)-b-poly(styrene) diblock copolymer anchored to silica particles were synthesized via 'grafting from' technique using a controlled/living free radical polymerization named stable free radical polymerization. XPS and FTIR analysis were used to control the effectiveness of the chemical modification of the silica particles. Thermal characterizations were performed by thermal gravimetric analysis (TGA) and by differential scattering calorimetry (DSC). The TGA permitted the determination of the quantity of grafted polymer and thus the grafting density; DSC was used to study the influence of the silica and blocks of the copolymer on their thermal behaviors. The glass transition temperature of the grafted copolymers was compared to these of free polymers or copolymers homologues. q 2004 Elsevier Ltd. All rights reserved. Keywords: Block copolymers; Stable free radical polymerization; Inorganic/organic materials 1. Introduction used. However these polymerizations require specific experimental conditions thus making their application The synthesis of dense film of polymer chains covalently difficult, while recent advances in controlled/'living' free bound to surfaces is an important field of research for its radical polymerization (suppression of terminations and ability to control and tune the properties of surfaces [1 – 3]. chain transfer reactions), a less constraining technique, have The first approach used, named 'grafting to' [1], consists in made it viable for the synthesis of well defined and narrow the condensation of functionalized polymers with reactive polydispersity polymers. Atom transfer radical polymeriz- groups of a solid substrate. This method does not give ation (ATRP) [9 –11] and stable free radical polymerization highly dense polymer brushes because chemi-sorption of the (SFRP) [12 –15] belong to the controlled/'living' radical first fraction of chains hinders the diffusion of the following polymerization. These polymerizations are based on the chains to the surface for further attachments [2]. Another reversible activation and deactivation of growing radicals. A approach, named 'grafting from', has been considered to very low concentration of propagating radicals is produced obtain better densities. In this technique, a mono-layer of suppressing termination reactions and giving polymers with initiator molecules is covalently attached to a solid surface narrow polydispersity. Another advantage with these two [4 – 6]. After activation the chains grow from the interface techniques is that the chains formed are end-capped by a then the only limit to propagation is the diffusion of dormant function that can be further thermo-activated to monomers to the active species. prepare block copolymers [15b]. Matyjaszewski et al. have used the ATRP technique to generate PS-b-PBzA from the To have a good control of the polymer mono-layer polysilsesquioxane nanoparticles, spending a lot of space thickness and polymer structure, living polymerization, for for the characterization of the particles and their nanoscale example anionic [7] or cationic [8] polymerizations, can be morphology on surfaces [9b]. Moreover, Hawker et al. have * Corresponding author. Tel.: þ 33-5-59-40-76-09; fax: þ33-5-59-40-76- described that tethering alkoxyamine initiators to a solid 23. support (as silicon wafer) can form PS brushes and that E-mail address: email@example.com (L. Billon). well-defined PS-b-PMMA block copolymer brushes can be 0032-3861/$ - see front matter q 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.polymer.2004.05.030 5014 G. Laruelle et al. / Polymer 45 (2004) 5013–5020 prepared [2]. But in the two previous studies [2,9b], the Refractive index detector and a 996 Waters Photodiode block copolymers were formed by sequences with high or array detector. A calibration curve established with low ambient glass transition temperatures and there is no polydispersity polystyrene standards was used for the characterization on the thermal properties of the grafted determination of the polyacrylate molecular weights. macromolecular chains. Thermal Gravimetric Analysis (TGA) was performed on In this paper, we present the preparation of polymer a TA Instruments TGA 2950 at a scan rate of 10 8C min21 brushes on silica particles via 'grafting from' approach. The under air. DSC was carried out using a DSC Q 100 polymer chosen was poly(n-butyl acrylate) (PBA) and was apparatus from TA Instruments at a scan rate of 20 8C/min prepared by stable free radical polymerization. In a second for both heating and cooling. The reported glass transition step, we have activated the chain end functions of PBA end temperatures were determined from the second heating run thus we have made a copolymer with polystyrene (PS), and were taken as the middle point of the DH=dt step in the verifying the control of chain terminal functionality DSC spectra. obtained during the stable free radical polymerization of butyl acrylate. The aim of this study was to generate hybrid 2.3. Mono-layer self assembly and polymerizations inorganic/organic particles by nitroxide-mediated polymer- ization (NMP), in order to elaborate a core-shell nano- The elaboration and the synthesis of the polyfunctional composite with a hard core of silica coated by a double shell coupling agent are based on a molecular engineering of a rubbery inner shell (PBA T g < 2 50 8C) and a glassy involving a multi-step reaction. Indeed, this coupling thermoplastic outer shell (PS T g < 100 8C). agent has to be constituted in its molecular structure of three functional groups. 2. Experimental part 2.4. Allyl 2-bromopropionate 2.1. Materials To a solution of 6.15 g (106 mmol) of 2-propen-1-ol in 400 ml of dichloromethane was added 14.8 ml of triethyl- Fumed Silica particles with an average elemental amine (110 mmol) and the solution was cooled to 0 8C in diameter of 13 nm and a specific surface area of an ice bath. Using an addition funnel, 16.4 ml (157 mmol) 255 m2 g21 (Aldrich) were dried overnight at 120 8C of 2-bromopropionyl bromide were added dropwise and the under vacuum before used. Toluene was distilled under temperature was kept on to 0 8C. Upon complete addition, nitrogen atmosphere from over molten sodium. MONAMS the mixture was brought to room temperature and allowed to alkoxyamine and SG1 counter-radical have been used as stir overnight. The product was washed with 3 £ 100 ml of received from ATOFINA. All other solvents and chemical H2O, dried over anhydrous MgSO4 and the solvent was products were purchased and used without further evaporated. The remaining pale yellow oil was distilled purification. under reduced pressure (60 mtorr) at 60 –70 8C, and 15.38 g (75%) of the product was collected. 2.2. Characterizations and measurements 2.5. Allyl alkoxyamine synthesis X-ray photoelectron spectroscopy analyses were per- formed with a Surface Science Instrument (SSI) spectro- To a round bottom flask containing 1.5 g (7.8 mmol) of meter at room temperature, using a monochromatic and allyl 2-bromopropionate, 2.6 g (7 mmol) of N-tert-butyl-N- focused (spot diameter of 600 mm, 100 W) Al Ka radiation (1-diethylphosphono-2, 2-dimethyl) propyl nitroxide at (1486.6 eV) under a residual pressure of 5 £ 1028 Pa. The 80% of purity (also referred to as DEPN or SG1), hemispherical analyzer worked under constant pass energy 0.5625 g (3.9 mmol) CuBr, 0.495 g (7.8 mmol) Cu and mode, 50 eV for high resolution spectra and 150 eV for 0.675 g (3.9 mmol) de PMDETA was added 15 ml of quantitative analysis. The binding energy scale was freshly distilled toluene. The mixture was stirred for 4 h at calibrated from the carbon contamination using the C1S room temperature in order to complete an Atom Transfer line (284.6 eV) (a mean atomic percentage of 8% was Radical Addition (ATRA). The green solution was filtered determined). under celite in order to eliminate the copper. After filtration, The Fourier transform infrared (FTIR) spectra were the yellow solution was washed with 2 £ 25 ml of 40% recorded using a Bruker IFS 66/S spectrometer at a aqueous solution of ammonium formate and 25 ml of resolution of 4 cm21 in absorption mode. 100 to 1000 aqueous solution saturated with sodium hydrogenocar- scans were accumulated. bonate. The remaining yellow oil was distilled under Size Exclusion Chromatography (SEC) characterization reduced pressure and 0.894 g (30%) of a orange oil was was performed using a 2690 Waters Alliance System with collected. This solution in toluene was directly used for the THF as eluent. It was equipped with four Styragel columns immobilization of the alkoxyamine initiator to silica HR 0.5, 2, 4 and 6 working in series at 40 8C, a 2410 Waters particle. G. Laruelle et al. / Polymer 45 (2004) 5013–5020 5015 2.6. Immobilization of the allyl alkoxyamine initiator to 3. Results and discussion silica 3.1. Synthesis of hybrid particles The surface modification reaction has been realized using glass apparatus flamed under vacuum. To a round bottom The silica used to synthesize the polymer brushes was flask, 1.04 mmol of allyl alkoxyamine previously synthe- previously grafted by an alkoxyamine initiator, called sized and 0.9 g of silica were introduced with 5 ml of freshly coupling agent, derivated from DEPN [14] and composed distilled toluene (Silica was dried overnight at 180 8C under ¨ by three functions as described by Ruhe [5,6] and us [16] vacuum). Under N2 atmosphere, 0.5 ml of triethylamine was (Fig. 1) (a grafting function, an initiating function and a added dropwise and the mixture was stirred overnight at cleavable function). The synthesis of this coupling agent room temperature. The particles were washed free of any and these nano-particles are described in the experimental part of a previous article [17]. From these modified adsorbed initiator with five cycles of centrifugation and re- particles, we initiated the bulk polymerization of n-butyl suspension in methanol and dichloromethane, and then acrylate. Free alkoxyamine initiator (MONAMS [15]) and a volatile products were removed under vacuum. slight excess of counter radical nitroxide (DEPN) ([DEPN]/ [MONAMS] ¼ 0.05) were added to the solution. The 2.7. Polymerizations additional initiator permits the polymerization of free chains, which can be later compared with the de-grafted chains thanks to the cleavable function of the coupling Under inert atmosphere, 1 g of modified silica particles agent, while the nitroxide permits a better control on the was suspended in a mixture of 20 ml of n-butyl acrylate, free polymerization of the grafted and free chains. The first alkoxyamine MONAMS ([n-BA]/[MONAMS] ¼ 390) and monomer used was n-butyl acrylate, three PBA samples of SG1 ([SG1]/ [MONAMS] ¼ 0.05) using the schlenk different molecular weights were prepared by varying the process. This mixture was thoroughly degassed for 30 min polymerization time but keeping the same ratio [BA]/ and heated to 120 8C for 1 – 8 h. The nano-composites were [MONAMS]. The experimental conditions are resumed in washed and centrifuged in toluene (five cycles) to remove Table 1. The macromolecular dimensions (M n, M w, Ip) non-attached polymer. The removal of adsorbed polymer on of the free PBA (untethered) were determined by SEC these hybrid inorganic/organic silica-particles was moni- (Table 1). At this point, the PBA chains were not degrafted tored by FTIR up to no significant variation of the because we wanted to synthesize block copolymer with absorbance of the characteristic peak of carbonyl function styrene. The polydispersity decreases with the polymeriz- (acrylic polymer). ation time and the values obtained for the three PBA are comprised between 1.4 and 1.2 significant of a controlled free radical polymerization. 2.8. Copolymerizations The grafted PBA chains obtained by NMP are terminated by an alkoxyamine function thus permitting an initiation of Under inert atmosphere, 1 g of poly(n-butyl acrylate) a new NMP. We decided to re-initiate NMP from the PBA modified silica particles was suspended in a mixture grafted silica in presence of styrene in order to obtain a core- of styrene, free alkoxyamine MONAMS ([St]/ shell hybrid-composite with a hard core of silica and by a [MONAMS] ¼ 200) and SG1 ([SG1]/[MONAMS] ¼ 0.05) double shell of a soft material and a hard material (Fig. 2). using the schlenk process. This mixture was thoroughly We used the three different PBA grafted silicas and choose degassed for 30 min and heated to 120 8C for 3 h. The to have the same molecular mass of the polystyrene block hybrid-composites were washed and centrifuged in toluene for the three samples. So, the same procedure was used: bulk (five cycles) to remove non-attached polymer. polymerization in the presence of the PBA grafted silica, free initiator (MONAMS) and nitroxide (DEPN). The conditions are resumed in Table 1. The free PS obtained 2.9. Degrafting procedure in the three experiments have a similar molecular weight A total of 500 mg of inorganic/organic silica-particles was suspended in 100 ml of toluene in which 10 ml of MeOH and 50 mg of p-toluene sulfonic acid were added. The mixture was heated to reflux overnight. A study by 1H NMR and SEC do not show any modification of the poly(n- butyl acrylate) structure under this trans-esterification conditions [16]. After freeze-drying of the degrafted Fig. 1. Coupling agent composed of three functions: grafting function (I), polymers, the molecular weights were determined by GPC cleavable function (II) and initiating function for nitroxide-mediated measurements and compared to the free chains. polymerization (III). 5016 G. Laruelle et al. / Polymer 45 (2004) 5013–5020 Table 1 Polymerization conditions of PBA and macromolecular parameters of the free chains as determined by SEC Free PBA chains Free PS chains 21 [BA]/[I]a Time (h) M n (g mol ) Ipb [St]/[I] Time (h) M n (g mol21) Ipb Si 1 390 1 13700 1.38 200 3 11300 1.15 Si 2 390 4 32600 1.25 200 3 11200 1.14 Si 3 390 8 39700 1.21 200 3 10800 1.15 a I: MONAMS b Mw =Mn (10; 800 , Mn , 11; 300Þ: This result will permit the study closely to the polydispersity of each free polymer, of the influence of the PBA block on the PS block and confirming the control of the block copolymer formation conversely. By the presence of the ester function in the by Surface-Initiated Nitroxide Mediated polymerization grafted initiator, the copolymers chains can be cleaved from (Fig. 3), as also described from silicon wafer by Hawker [2]. the silica and characterized by GPC. These characteristics cannot be directly compared with those of the untethered 3.2. Structural characterizations chains generated by the free initiator during the polymeriz- ation. However, if the reaction mechanism is analogous in The modified silicas have been characterized by FTIR bulk and at the surface, the number average molecular (Fig. 4) to determine the effectiveness of the modifications. weight of the grafted copolymers is expected by equal to the Fig. 4 shows the spectra of the three silicas, normalized with same of those of the two homopolymers obtained succes- the peaks of Si-O. Above, the top spectrum corresponds to sively in bulk (PBA then PS). In the particular of the Si3 the silica modified by an alkoxyamine initiator which was sample, this assumption is well verified (Table 1 and Fig. 3). used for the polymerization of butyl acrylate BA. The Indeed, if we compare the number average molar mass of intermediate spectrum were registered for purified silica the degrafted chains (M n Si3 ¼ 51,200 g mol21; Ip ¼ 1.20) obtained after BA polymerization and the spectrum below with the number average molar mass of both free PBA and corresponds to the purified silica obtained after copolymer- free PS synthesized during the same experiments ization of Styrene in order to synthesize PBA-b-PS. On the (M n ¼ 10,800 þ 39,700 ¼ 50,500 g mol21) we observe a right part of the spectrum (b), the peak at 1725 cm21 similar result knowing that the calibration curve was corresponds to the stretching vibration of the carbonyl established with PS standards. Moreover, the polydispersity groups of the poly(butyl acrylate), that well confirms the value of the cleaved block copolymer PBA-b-PS is very presence of poly(butyl acrylate) on the silica particles. On Fig. 2. Schematization of the preparation of a core/soft-hard double shell. G. Laruelle et al. / Polymer 45 (2004) 5013–5020 5017 Fig. 3. Size Exclusion Chromatograms of degrafted PBA-b-PS (a), free PBA (b) and free PS (c). the spectrum (c), this peak is less marked but still present to the presence of silicon (152 eV, Si(2s); 103 eV, Si(2p)) and at 3000 – 3100 cm21 (left part) the new peaks and oxygen atoms (533 eV, O(1s)). After the immobiliz- characteristic of CH aromatic vibrations can be observed. ation of the coupling agent (b), three new signals appear due This indicates the presence of the poly(butyl acrylate)-b- to the phosphorus (133.8 eV, P(2p)), the carbon (285 eV, polystryrene copolymer at the silica' surface. These C(1s)) and nitrogen atoms (400.7 eV, N(1s)) of the grafted qualitative characterizations show the formation of hybrid alkoxyamine compound characteristic of the presence of the composites, first a poly(butyl acrylate) brush on silica and in SG1 nitroxide. Further more, comparison of the XPS spectra a second step after re-initiation, the synthesis of a poly(butyl of the coupling agent mono-layer (b) and the graft PBA (c) acrylate)-b-polystyrene copolymer brushes on silica. shows a strong enhancement of the carbon signal at 285 eV In order to confirm the effective formation of polymer (C(1s)) due to the acrylic part. Additionally, in the (c) brushes, already seen by FTIR, a study by XPS was made. spectra the signals of Si(2p) are attenuated and the C(1s)/ Fig. 5 presents the results of XPS measurements. The O(1s) signals ratio is clearly enhanced demonstrating the spectrum of the bare substrate (Fig. 5(a)) shows signals due presence of organic polymer on the surface of the hybrid Fig. 4. FTIR spectra of initiator grafted silica (a), PBA grafted silica (b) and PBA-b-PS grafted silica (c). 5018 G. Laruelle et al. / Polymer 45 (2004) 5013–5020 Fig. 5. Surface analysis by XPS of silica particles (a), initiator grafted silica (b), PBA grafted silica (c) and silica (d). inorganic/organic particle. Moreover, it was very interesting performed by themogravimetric analysis. An analysis of the to note that the phosphorus and nitrogen atoms of SG1 pure silica used in this work shows no thermal degradation, nitroxide are still remaining at the end chain of macro- no weight loss was encountered in the temperature range molecules after polymerization. The presence of the used (30 – 650 8C). On the thermograms of polymer-grafted nitroxide SG1 gives us the opportunity to elaborate some silicas (Fig. 6), we can see a significant weight loss due to block copolymers at the surface of the silica-particles with the degradation of the grafted organic compound. The antagonist properties such as copolymer PBA-b-PS. The weight loss is more important for the copolymer-grafted XPS spectra of the silica particles obtained after re-initiation silica than for the PBA-grafted silica proving that the in-situ of the SG1 end-capped PBA in presence of styrene is shown copolymerization is effective. The thermal behavior differ- Fig. 5. Indeed the C(1s)/O(1s) and C(1s)/Si(2p) signals ratio ence between the bare silica and grafted silicas permits the increase from 0.23/0.15 to 0.62/0.36, respectively, for estimation of the grafting densities for the initiator, the PBA grafted PBA/PBA-PS silica particles. and the copolymer PBA-b-PS. Indeed, if we make the approximation that at 650 8C all the organic material is 3.3. Grafting density degraded and that only the inorganic material remains we can calculate the grafting density (Table 2). For grafted A thermal study of the different grafted silicas was polymers the density decreases when M n increases (the G. Laruelle et al. / Polymer 45 (2004) 5013–5020 5019 Fig. 6. Thermograms of PBA (a), PBA-b-PS (b) grafted-silicas (Si3) and (c) pure silica. Fig. 7. DSC thermograms of PBA (Mn ¼ 130; 000 g mol21) (a), PBA-b-PS grafted-silica (b), PS ðMn ¼ 10; 000 g mol21) (c) and tri-block copolymer PBA-b-PS-b-PBA (d). density rises from 0.026 PBA chains by nm2 to 0.008 PBA chains by nm2 when M n increases from 14,000 g mol21 to temperature relative to the PBA block (elastomer phase) and 40,000 g mol21). The grafting density for a grafted PBA another relative to the PS block (thermoplastic phase), and the corresponding copolymer PBA-b-PS is nearly characteristic of a phase separation. For the PBA blocks the similar, showing that the re-initiation of the end-capped T g obtained is around 2 20 8C and this of the glassy state SG1 for the copolymerization has a good efficiency. block PS is closed to 80 8C. To compare, we have performed However all these values are far from the grafting density a DSC on homopolymers PBA of different molar mass and of the coupling agent (0.52 molecule nm22) so only small for PBA grafted on silica. For free PBA, T g was comprised amounts of the grafted coupling agent initiate the in situ between 2 53 8C for M n¼ 25; 000g mol21 and 2 47 8C for polymerization due the crowding effect of grafted chains or M n¼ 130; 000g mol21 ; respectively. In case of PBA to a degrafting process at high temperature as we will grafted-silica, T g was equal to 2 35 8C. The PS block and describe in a forthcoming paper. the silica have an important influence on the T g of the PBA. Indeed the T g of the PS is very high in comparison with PBA 3.4. Thermal properties of polymer grafted silica particles so when the glass transition of the PBA occurs, the two extremities of the copolymer chain are fixed, one by the A second thermal study was made by DSC in order to rigidity of the PS the other by the presence of the silica estimate the influence of the silica on the grafted polymers particle. Then the motion of the PBA block is hindered and and the influence of one block on the other for grafted block more energy is needed to pass from a glassy state to a copolymers (Fig. 7 and Table 3). Indeed, in a DSC study, caoutchoutic state thereby increasing the temperature of the Patterson et al. have demonstrated the effects of tethering glass transition of the PBA. The silica has no significant and chain immobilization on the glass transition tempera- direct influence on the PS block because the presence of the ture of PS (thermoplastic polymer). The measured T g of PBA between those two parts. On the other hand the PBA annealed bulk films of hybrid nanoparticles was elevated has an influence on T g of the PS. For the PS block, T g varies with respect to the value of pure bulk PS because of the from 83 8C to 85 8C while for a PS with the same M n chain grafting or immobilization and to the chain extension (10 000 g mol21) T g is 97 8C. This time, the effect is the [9c], phenomena briefly reported by Carrot et al. on PS opposite than the one described before for PBA. When the grafted silica particles also synthesized by ATRP [18]. glass transition of the PS occurs, the PBA block is flexible In our case, DSC spectra of copolymer PS-b-PBA grafted and in movement leading the PS block to be more flexible on the silica (Fig. 7(b)) shows two T g; one under room than if it where alone so the PS block need less energy to Table 2 Determination of the PBA and PBA-b-PS grafting densities by TGA PBA grafting density PBA-b-PS grafting density Weight loss (%)a mmol g21 molecule nm22 mmol m22 Weight loss(%)a mmol g21 molecule nm22 mmol m22 Efficiency (%) Si 1 13.3 16.2 0.040 0.064 26.2 13.8 0.033 0.054 83 –85 Si 2 17.7 9.5 0.022 0.038 18.8 6.8 0.016 0.027 71 –73 Si 3 11.1 4.6 0.011 0.018 15.4 3.6 0.008 0.014 73 –78 a Weight loss by TGA. 5020 G. Laruelle et al. / Polymer 45 (2004) 5013–5020 Table 3 grafted to silica particles was shown, leading to a core/ Glass transition temperatures of core/shell PBA and PBA-b-PS grafted double shell hybrid inorganic/organic material (a double particles by DSC shell constituted by a rubbery inner layer and glassy PBA PS thermoplastic outer layer). The materials obtained have different thermal behaviors, function of the ratio PBA/PS. Tonset (8C) T g (8C) Tonset (8C) T g (8C) So, it is possible to tune the surface properties (for instance the adherence, wetability…) of the inorganic material by Si -PBA 247/240 235/230 – – Si -PBA-b-PS 230/225 222/216 74 83/85 choosing the nature (elastomeric, thermoplastic, hydro- Free PBA 260/255 253/247 – – philic…) and the dimension of an adequate grafted polymer. Free PS – – 90 97 Free PBA-b-PS 240 230 76 83 Free PS-b-PBA-b-PS 245 237 74 82 Acknowledgements pass from a glassy state to a caoutchoutic state thereby The authors are pleased to acknowledge O. Guerret from decreasing is glass transition temperature. In order to ATOFINA for supplying SG1 and MONAMS, and estimate the real influence of the silica particle over the PBA C. Guimon for the XPS measurements. block on the T g of the PBA, we have made a tri-block copolymer PS-b-PBA-b-PS, thanks to a di-alkoxyamine [15b], with two blocks of PS with a M n of 15 000 g mol21 and PBA block with a M n of 50 000 g mol21. The T g for the References PS of the tri-block and for the PS of the PBA-b-PS grafted [1] Mansky P, Liu Y, Huang E, Russel TP, Hawker CJ. Science 1997;119: are very similar confirming the weak and important, 1619. respectively influence of the silica and PBA on this block. ¨ [2] Husseman M, Malmstrom EE, McNamara M, Mate M, Mecerreyes D, The major difference between the tri-block and a grafted di- Benoit D, Hedrick JL, Mansky P, Huang E, Russel TP, Hawker CJ. block copolymer is on the T g of the PBA since its T g for the Macromolecules 1999;32:1424. tri-block is lower (2 42 8C) than for the grafted copolymers [3] Halperin A, Tirell M, Lodge TP. Adv Polym Sci 1991;100:31. (2 22 8C to 2 16 8C) meaning that the silica particles have a [4] Ulman A. Chem Rev 1996;96:1533. ¨ [5] Prucker O, Ruhe JJ. 1998; 31: 592. higher impact than the PS block on the thermal behavior of ¨ [6] Prucker O, Ruhe J. Macromolecules 1998;31:602. the PBA, as a tough and hard matter due to their inorganic [7] Jordan R, Ulman A. J Am Chem Soc 1998;120:243. character. [8] Jordan R, Ulman A, Kang JF, Rafailovich MH, Sokolov J. J Am Chem Soc 1999;121:1016. [9] (a) Luokala B, Siclovan T, Kickelbick G, Vallant T, Hoffmann H, Pakula T. Macromolecules 1999;32:8716. (b) Pyun J, Matyjaszewski 4. Conclusion K, Kowalewski T, Savin D, Patterson G, Kickelbick G, Huesing N. J Am Chem Soc 2001;123:9445. (c) Savin D, Pyun J, Patterson G, Formation of hybrid inorganic/organic materials, by in- Kowalewski T, Matyjaszewski K. J Polym Sci Part B 2002;40:2667. situ polymerization thanks to an alkoxyamine type coupling [10] Chen X, Randall D, Perruchot C, Watts J, Patten T, Von Werne T, agent previously grafted to the inorganic material, was Armes S. J Colloid Interface Sci 2003;257:56. [11] Von Werne T, Patten TE. J Am Chem Soc 2001;123:7497. confirmed by both FTIR and XPS. This 'grafting from' [12] Hedrick JL, Mansky P, Huang E, Russell TP, Hawker CJ. approach has given good polymer grafting densities giving Macromolecules 1999;32:1424. us hope to achieve formation of polymer brushes onto silica. [13] (a) Beyou E, Humbert J, Chaumont P. E-Polymers 2003;020. (b) The use of a stable free radical polymerization (also called Bartholome C, Beyou E, Bourgeat-Lami E, Chaumont P, Zydowicz N. nitroxide-mediated polymerization) permits a control of the Macromolecules 2003;36:7946. [14] Benoit D, Grimaldi S, Finet JP, Tordo P, Fontanille M, Gnanou Y. Am dimension and the structure of the grafted polymers. Indeed, Chem Soc, Polym Div 1997;38:651. we have shown that the molar mass and the polydispersity of [15] (a) Robin S, Guerret O, Coututrier JL, Pirri R, Gnanou Y. the grafted polymer were very similar with a free polymer Macromolecules 2002;35:3844–8. (b) Robin S, Gnanou Y. Macromol made in the same conditions. Another advantage of the Symp. 2001;165:43– 53. (c) Gnanou Y, Robin S, Guerret O, Couturier nitroxide-mediated polymerization is the ability to poly- JL. Polym Prepr 2000;41:1352. [16] Parvole J, Billon L, Montfort JP. Polym Int 2002;51:1111. merize a large range of monomers (styrenic, acrylic, [17] Parvole J, Laruelle G, Guimon C, Francois J, Billon L. Macromol methacrylic) and to make blocks copolymers. For example Rapid Commun 2003;24:1074. in this article the formation of a diblock poly(n-butyl [18] Carrot G, Diamanti S, Manuszak M, Charleux B, Vairon J-P. Polym acrylate)-b-poly(styrene), with narrow polydispersity, Sci Polym Chem 2001;39:4244.
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I tried to send a message via this forum to Brankic1979 and imediapixel. How long does it normally take for a developer to respond?
depends, usually they are fast, and some others support trough there forums/support sites.
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CAFIFTY Replied to a Post by Damon Lavrinc
delete. » 3/24/15 7:00pm Tuesday 7:00pm
delete. » 3/24/15 7:00pm Tuesday 7:00pm
I remember when the R1 went to a cross plane crank and it was a big deal » 11/17/14 11:29pm 11/17/14 11:29pm
SUBARU BLOCK? Wait no Porsche :( » 2/17/14 11:38pm 2/17/14 11:38pm
i laughed, out loud » 2/13/14 1:51pm 2/13/14 1:51pm
So from somone who take this a little too serious here is what i think one member selection
» 2/10/14 4:56pm 2/10/14 4:56pm
Most OEMs have "torque security features" that will notice any major manipulation from devices like these and will put the controller in a limp home mode state. » 2/10/14 1:20pm 2/10/14 1:20pm
Been using racer for a couple years to practice courses before i race them in real life with my chumpcar teams. The results were really good. I currently between jobs so like a true unemployed asshat i have started to play video games (and get tattoos). Just started doing online races and can't seem to catch a break.… » 2/07/14 2:20pm 2/07/14 2:20pm
Don't do it. If its anything like the galant vr4 its pleauged with unfixable troubles » 2/05/14 3:19pm 2/05/14 3:19pm
Already happened. Took 76hours hours http://www.usatoday.com/story/money/ca... » 2/05/14 2:50pm 2/05/14 2:50pm
Not sure how the oiling system is working with the engine standing up like that... » 2/05/14 2:02pm 2/05/14 2:02pm
masochist » 2/05/14 1:58pm 2/05/14 1:58pm
How the hell do you get your background over two screens. I haven't tried that hard to figure this out but it was never obvious when setting up dual monitors. » 2/05/14 12:59pm 2/05/14 12:59pm
I have calibrated this diagnostic before (p0420 &P0430) for a different OEM. But i am assuming VW also uses the pre and post 02 sensor to measure the oxygen capacity of the catalyst. Which is why the shop replaced the O2 sensor first. And there might be logic to not clearing the codes. The catalyst health monitor is a… » 2/04/14 5:06pm 2/04/14 5:06pm
Angels crest highway: » 2/04/14 1:43pm 2/04/14 1:43pm
For the more serious guys out there: » 2/03/14 6:02pm 2/03/14 6:02pm
WONT EVER HAPPEN. Just hype to drive up their stocks. » 1/30/14 6:44pm 1/30/14 6:44pm


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Chicco Relax and Play
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"Great chair looks good and is comfy…"
Lies nice and flat not like some others also has newborn insert so they can't roll around when they are tiny. Toy rack is just at the right height my little one likes looking at it for ages! Chair is nicely padded too and price is reasonable xRead moreLess
Mumsnetter Smtt776Number of total reviews contributed on Mumsnet5
6 reviews posted
2 Mumsnetters found them helpful
"This worked really well for us. Padded and comfortable, and…"
This worked really well for us. Padded and comfortable, and easy to wash, we used this for our son until he was weaned, and about 6 months old - frankly at that point he didnt want to sit in any seat for any period of time! Again, it was useful that it reclined flat when he was a newborn and also could be used upto bolt upright. We also found it really useful to help with reflux issues. We also liked that it could rock or be fixed. However, we never used the toy bar (although we never missed it) as it was impractical and not very interesting.Read moreLess
"This seat was great when my son was small, and…"
This seat was great when my son was small, and he frequently slept in it during the day rather than going in his cot. It was also good once he wanted to sit up more as the seat is adjustable and we used it for early weaning. However when we tilted the seat up, we had to remove the toy bar otherwise the toys dangled in his face.Read moreLess
Mumsnetter Jambers99
2Number of total reviews contributed on Mumsnet1
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2 reviews posted
"We bought this because DS has reflux - the seat…"
We bought this because DS has reflux - the seat has an adjustable back rest so we use it to sit him up after feeds. It's been great for that reason - and DS can also nap in it (although chair does not go completely flat). I can also see us using it as a chair when we start weaning. However the rocking action is not great, doesn't work on carpet; and the toys that come with it are fairly good, but DS prefers others. I think it's great for comfort, but not so great as entertainment.Read moreLess
Mumsnetter Tumshie1Number of total reviews contributed on Mumsnet1
1 review posted


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18 of 21 people found the following review helpful
The Miami Vice Soul Is Here,
By A Customer
This review is from: Escape From Television (Audio CD)
There would be no Miami Vice without Don Johnson or Philip Michael Thomas. The same and not less can be said about Jan Hammer. When he left the series in the last season (1988-1989), even though his successor Tim Truman did a good job, it was like one of the principal characters left. This album contains the quintessential Miami Vice music, although Jan Hammer did material for a 5 CD set. It would be nice to have a Hammer's Miami Vice collection released one day, a complete one (you can find more Miami Vice music on "Snapshots 1.2", Miami Vice I, II, III).
All the music on this CD may be heard on Miami Vice, but the booklet informs that "Forever Tonight" (previously heard with vocals in the albun "Hammer") and "Before the Storm" are not Miami Vice tracks. These two tracks are, respectively, from "Child's play" and "Love at First Sight" episodes of the fourth season (after the release of this album). The hits "Miami Vice Theme" (unfortunately not the rare remix version unavailable on CD, nor the first four episodes "off-guitar version") and "Crockett's Theme" are together with great icons of the series. "Rico's Blues" (along with "Flashback" from Miami Vice volume I) could be named as "Tubbs' theme". "Theresa" shows Jan's refined production on combination of sounds. This can also be said about most tracks of the album, "Before the storm" and its Rhodes piano, "Forever Tonight" (and its remix) with the synth sounds, "Colombia" with the Andean flutes and percussion blocks (actually Farlight CMI samples) are just some examples. A complaint: some differences between what we hear on the episodes and on this album (mixing differences and sometimes more than that). Most of time what is on the CD is better treated than in the episode, but in the episode there was the first impression. But this does not put the style away, not a bit.
One could say that this music is more effective through the episodes action, which is quite non-sense. This music IS the episode action, not the contrary: it was made for that and works like that perfectly well. "The Trial" is the character of criminal judgement of young General Lao Li grandsons, "The Search", in the same way, the mood of Tubbs disappearance or the deadly encouter with druglord Mario Fuente (Frank Zappa). What would be of "Rites of Passage" or "The Prodigal Son" episodes without "Tubbs and Valerie" (one of the most remarkable Miami Vice tunes)? This happens also between "Trust fund Pirates" episode and "Night Talk" (orinally from the "Made for Each Other" episode). And what would be of "One way ticket" without the good vibrated "Rum Cay" and, on the other hand, the extremely dramatic and disturbed "Last Flight"? Possibly those moments would mean much less without those tracks.
Jan Hammer's Vice music was exhaustively imitated during the eighties, and even re-recorded by others. But his music character is unique as some of his timbres are. And for sure the musical character one could hear on this album. We must remember that Hammer is more than just Miami Vice. From Mahavishnu Orchestra to "The First Seven Days", from "Oh, Yeah?" to "Secret Admirer", he passed through lots of musical moments. This CD is one of them, a very important one: the Miami Vice Heart.
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TSBEAUTIFUL13: thank you so much!!!!! i worked hard on it :D
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Hi I'm Nicole i have been alive for 19 years now and i love everything in the cute and cozy categories. and I have my own horse and dog. I love Taylor swift a lot ever since i think i was 7 or 8 because my brother gave me a Burned Cd of some taylor swift Songs and i ended up loving it a lot so that's how i started Loving Taylor Swift!!. my lucky numbers are 13 and 15 .. and i love all of Taylor's Songs and i have all her Cds. so add me as a friend or look at my pictrues!! :) but anyway Stay Fearless and Don't forget to Speak now. but i would really love to meet Taylor One day and take a picture with her and tell her everything like thanks for writing music. I also Love this football player Tim Tebow he is like soo great and sweet. and i love country music and pop music as well. my very 1st Taylor concert was 6/4/11 when she came to Orlando it was the best day of my life i will never forget it :) i also like another country Artist Hunter Hayes I love his songs and he soo cute my favorite song is Wanted. Another Country Artist I Love is Jason Aldean he is so Great my favorite songs is dirt road , my Kinda Party just passin through and Fly Over States. I want to tell you some More things about me i am kinda that Shy girl who Always sits by herself in the corner and is never been really popular. But Since I Joined Taylor connect I don't feel as Shy anymore. oh just in case you are wondering i am a Freshmen in College wow scary lol Anyway Some things about me is i am very caring and i am the kind of friend that you can tell anything to so. ever since i started Loving Taylor Swift i have been trying to be Fearless but its hard sometimes and I try to Speak Now.Taylor is my number 1 Idol and Role model i Always Look up to her.. but I mean sometimes i just love Being in my room Dancing all around the Room to Taylor's Music... Oh and More things about Me are I Love all the twilight Books and Movies!!! I am in Love with Taylor Launter!!!! even though he is 4 years older than me a girl can dream can't she haha lol that it :) I try So hard to Be Just Like Taylor Swift but Sometimes it can be really Hard... I kinda Act just like Taylor I have Blonde wavy hair and My eyes were blue but they are blue green now and I act very weird and crazy like her Like jumping around and Stuff haha lol and I flip my Hair just like Taylor its fun!!. Okay I'm also a HUGE Belieber I love Justin Bieber to death been a Belieber since 2009 So thanks for reading this
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- Shopping Bag ( 0 items )
Published in 1850, this was Cooper's final novel—and America's first courtroom drama. When innocent Mary Monson is accused of murder, she refuses to clear her name, insisting on a jury trial. Cooper, who opposed the trial-by-jury system, mounts his soapbox to rail against the system's susceptibility to corruption, among other flaws.
Published in 1850, this was Cooper's final novel—and America's first courtroom drama. When innocent Mary Monson is accused of murder, she refuses to clear her name, insisting on a jury trial. Cooper, who opposed the trial-by-jury system, mounts his soapbox to rail against the system's susceptibility to corruption, among other flaws.
Posted August 22, 2010
I Also Recommend:
James Fenimore Cooper's last novel (1850), THE WAYS OF THE HOUR, is an old man's sometimes grumpy criticism of America in general and New York State in particular. Opinions are debated freely among young and old, refined and uncouth, idealistic and pragmatic and even the sane and not so sane. Some topics debated:
-- Does the U.S. Constitution's protection of the institution of slavery make slavery a good idea? (Does this remind you of today's press-supported pubic excitement about a mosque at Ground Zero in Manhattan?) *****
-- Does the New York State constitution, revised in 1846, do well or ill in giving a wife complete control over any wealth she has inherited before marriage? *****
-- Does God intend women to be supremely independent of husbands? *****
-- Is the jury system a perversion of justice when jurors increasingly glory in ignoring a judge's instruction as to the law's meaning? *****
-- Is telling the truth the aim of America's "free" press? Or, rather, is making money at any cost the supreme god of journalism? *****
-- Why does the justice system treat convicted criminals more fairly and kindly than it does the innocent -- who may lose fortunes paying lawyers to defend them from malicious renters and jealous neighbors? "It is the innocent who have most reason to dread the law" (Ch.29). *****
All this political and sociological debate is scattered throughout a crime narrative which is reasonably straightforward but also immersed in late Gothic conventions of mysterious ancestry and wealth, a weakened mind, love, courtship and marriage of one aging couple and two young ones. *****
At its narrative core THE WAYS OF THE HOUR (a phrase meaning much the same as "the signs of the time") is a murder mystery and courtroom drama. Two charred bodies are found in a somewhat isolated New York cottage less than 20 miles from downtown New York City. There are witnesses who saw the cottage in flame and a beautiful young woman boarder being assisted to escape by two men who later disappeared. There is flimsy circumstantial evidence, especially a notched foreign gold coin belonging to the dead (or at least disappeared) landlady. This being found in boarder Mary Monson's purse, she stands trial for arson and double murder. Established star of the New York City bar, 60-ish bachelor Thomas Dunscomb is strangely drawn to the mysterious, beautiful obviously wealthy young defendant and represents her in court. *****
Crime scene investigation was in its infancy in the 1840s. But sloppy police investigation does not seem to matter, once public opinion, fanned by the yellow dog press of New York, becomes convinced of the guilt of Mary Monson. There is jury tampering. The accused lives luxuriously in prison, where she plays on a harp like an angel or King David. The lead defense lawyer discovers toward trial's end that Mary is the granddaughter of his one and only love who had jilted him for a richer man. Mary is permitted to cross examine the principal witness against her, regarding Mary's post-crime possession of the notched gold coin known to belong to the disappeared landlady. Mary then proves as good a lawyer as Portia in THE MERCHANT OF VENICE and better even than Perry Mason in applying pressure to a witness. This is a rich, rich novel, deserving more than one reading. -OOO-
Posted November 20, 2011
No text was provided for this review.


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Renaissance Austin Hotel
This pet-friendly Austin hotel is adjacent to the Arboretum at Great Hills Mall and is also located 1.5 mi (2.5 km) from The Domain.
Hotel Features.
Renaissance Austin Hotel has a seasonal outdoor pool, indoor pool, spa tub, sauna, and 24-hour fitness facility. Business amenities include a 24-hour business center, business and secretarial services, complimentary wireless Internet access, 24 meeting rooms, and audio-visual equipment. Renaissance Austin Hotel has a restaurant, cybercafé, and bar/lounge; room service is available. Free parking is available, and babysitting/child care can be arranged for a surcharge.
Amenities featured in guestrooms include hair dryers, coffee/tea makers, and clock radios. Guestrooms have TV with premium cable channels and pay movies. Wireless Internet access is available (surcharge). Business-friendly amenities include multi-line phones, desks, and direct-dial phones. Rollaway beds are available on request, and baby cots/infant beds can be provided for a surcharge.
Very professional staff.
Very friendly staff, lovely hotel- great location that is close to shopping and…
Enter dates to check prices
Hotel Info: 866-539-8117from $159
- Executive Room
- Superior Room, 1 King Bed
- Luxury Suite, 1 King Bed
- Superior Room, 2 Queen Beds
- Signature Suite, 1 King Bed
- Deluxe Room
Recommended hotels
At a glance
Key facts
Hotel size
- This hotel has 492 rooms
- This hotel is arranged over 10 floors
- Check-in time 4 PM-7 PM
- Check-out time is 11 AM
- Express check-in/out
Required at check in
- Credit card or cash deposit required
- Government-issued photo ID required
Travelling with others
- Children (12 years old and younger) stay free when occupying the parent or guardian's room, using existing bedding
- Babysitting/childcare *
- Pets allowed *
- Restrictions apply *
Extra people
- Roll-away beds available, charges may apply*
- Free WiFi in public areas
- WiFi in rooms *
- Free self parking
- Valet parking *
- Accessible parking
In the hotel
- Full breakfast (surcharge)
- 2 restaurants
- Bar/lounge
- Coffee shop/café
- Snack bar/deli
- Room service (during limited hours)
- Indoor pool
- Outdoor seasonal pool
- 24-hour fitness facilities
- Spa tub
- Sauna
- Golfing nearby
- Mountain biking nearby
- Sailing nearby
- Scuba diving nearby
- Windsurfing nearby
- 24-hour business center
- Number of meeting rooms - 24
- Conference space
- Meeting rooms
- Conference space size (feet) - 65000
- Conference space size (meters) - 5850
- 24-hour front desk
- Dry cleaning/laundry service
- Free newspapers in lobby
- Wedding services
- Number of buildings/towers - 1
- Elevator/lift
- ATM/banking
- Safe-deposit box at front desk
- Disabled parking
- Accessibility equipment for the deaf
- Accessible bathroom
- In-room accessibility
- Roll-in shower
In the room
- Climate control
- Air conditioning
- Coffee/tea maker
- Iron/ironing board
- Blackout drapes/curtains
- Premium bedding
- Pillowtop mattress
- Shower/tub combination
- Free toiletries
- Hair dryer
- Pay movies
- Premium TV channels
- Desk
- Free weekday newspaper
- WiFi (surcharge)
- Phone
- Daily housekeeping
Renaissance Austin Hotel's small print
Also known as
- Renaissance Austin
- Austin Renaissance
- Renaissance Austin Hotel
- Renaissance Hotel Austin
- Renaissance Austin Hotel Austin
Pet-friendly rooms can be requested by contacting the property at the number on the booking confirmation.
Optional extras
Valet parking costs USD 16 per day
Breakfast costs between USD 20 and USD 30 per person (approximately)
Pets are allowed for an extra charge of USD 75 per pet, per stay
WiFi is available in guestrooms for USD 15.95 per day (rates may vary)
We have included all charges provided to us by this hotel. However, charges can vary, for example, based on length of stay or the room you book.


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Since venturing into the world of having a daughter, I've realized that having a girl comes with some new territory. She's pretty much the same as the boys. Kind of. I mean, she requires diapers and bottles and baths. Who am I kidding...having a girl is quite a bit different than a boy. One huge difference is that she has already acquired quiet an impressive headband collection in her short 6 … [Read more...]
8 DIY Kitchen Coffee Stations
One thing we've wanted in our kitchen for a while now is a coffee station. We've got a pretty big space for it, it's just a matter of finding the time to work on the project! Here are a few of my favorite designs and ideas that I've found lately. Like a Saturday Shanty 2 Chic One Women's Haven I Should Be Mopping the Floor Driven By Decor Bower Power Blog Magnolia Homes … [Read more...]
12 DIY's To Try | Monday Funday Party
Whew. We have had a time of it trying to get everyone healthy and well in our house this month. I've also been busy preparing for my first kids clothing consignment sale and taking time daily for some preschool homeschool lessons with my three and a half year old. I promise to share some new posts with all of you soon, thank you for bearing with me in the meantime! I'd love for you to check … [Read more...]
Easy Yarn Pom Pom Bouquet
I've been working on trying to make my craft room feel more like "mine". Currently it's a multi-purpose room serving as my craft room/office and our guest bedroom. I think by adding small personal touches to it, it will feel more and more like my personal space and less like the catch all room that it's been since we've lived here! I love this little project because it's the perfect, small way … [Read more...]
Burlap & Floral Grapevine Wreath
I'm back with my second wreath of the season, and so excited to share it with all of you today. It's fairly similar to the tulip grapevine wreath I shared with all of you last week, but there's a reason for that. I've decided that I need to be more consistent with our decor and colors. Too many times I choose colors for holidays that seem to be appropriate for the "season" yet they aren't … [Read more...]


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While five Governors have put in their papers, two have completed their tenure.
The Bharatiya Janata Party-led government which came to power on May 26 had nudged several Governors appointed by the previous Congress-led United Progressive Alliance government to resign in the wake of the change of the government.
While five Governors have put in their papers, two completed their tenure, rendering seven vacancies in the Raj Bhavans.
Top-level government sources maintained that the UPA-era political appointees in Raj Bhavans would have to go.
It is likely that the new gubernatorial appointments may hold for a few more days, sources said.
Though the names of several senior BJP leaders are being speculated upon for gubernatorial appointments and there are vacancies in the Raj Bhavans of U.P., Chhattisgarh, Nagaland, Goa, West Bengal, Karnataka and Tripura, the Narendra Modi government, a day ahead of Parliament's budget session, chose to effect only transfers and hand over additional responsibilities to some of the incumbents.
Keywords: Governors issue, UPA-era Governors, Narendra Modi government


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…kinda like Thug Life…only cuter.
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text:
The UNDP project was initiated in all city corporations.
Mock drills to overcome hazards posed by natural calamities will be carried out in select city schools and corporation divisions shortly.
The initiative comes as part of the Urban Risk Reduction Programme, which is supported by the United Nations Development Programme, in Kochi Corporation. It is estimated that over 10,000 school students and residents of 25 divisions of the corporation will be part of the exercise, said Tinu Rose Francis, city project officer.
Mock drills will be carried out in the schools in December. A similar exercise will be carried out for the city residents to face the challenges before January. The programme attains significance in the wake of possible vulnerabilities of the city to calamities like a dam failure.
The UNDP project, which was initiated in all city corporations in 2010, will conclude next year.
Disaster management experts are also planning to train civic authorities, including the Kochi Mayor, the councillors and officials, in the fundamentals of risk reduction. It had organised such a programme for the civic representatives during the term of the previous council.
School safety programmes covering natural hazards and motor accidents were carried out as part of the programme. Select teachers from the schools were also exposed to various aspects of hazard management. All the schools are supposed to have sufficient first aid facilities as the government had earlier issued directions to schools in this regard. Hence, no separate initiative for ensuring first aid facilities in schools were undertaken, Ms. Francis said.
Keywords: Mock drills, Disaster management


text:
- News
- Local
- Sports
- Business
- Politics
- Opinion
- Lifestyle
- Entertainment
- Obituaries
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The House of Representatives late Thursday voted to bar the National Security Agency from looking for Americans' communications without a warrant within a database of e-mails and phone calls it gathers while targeting foreigners, a technique that critics have labeled a "backdoor search loophole."
The House approved the ban by a 293-123 vote.
The proposal has drawn opposition from security agencies and still has a long way to go before it would become law. But chief sponsors of the provision celebrated the lopsided vote.
"Americans have become increasingly alarmed with the breadth of unwarranted government surveillance," they said in a statement. "By adopting this amendment, Congress can take a sure step toward shutting the back door on mass surveillance."
New York Times


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In Joel test, I have seen a section named, "Can you make a build in one step?". I typically build the code suing Xcode and archive it. Is there a way better than this to do in case of iOS development?
Is there any way to build using a build script? The current way I follow is to use Product -> Archive for generating builds. Is there a better way here to reduce the time?


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Developing Story
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The News & Observer
May 2, 2008
By: Audrey Singer
Many cities, towns, suburbs and rural communities across the country have recently experienced a sudden influx of immigrants. Some places saw their local economies flourish during the high-tech and construction booms of the past decade. Others, facing an economic downturn, are concerned about the costs of providing services to newcomers, especially as their schools see a spike in the enrollment of limited English proficient students.
In short, immigration is bringing change to communities of all kinds and sizes, from the Dallas suburbs to Prince William County, Va., on the metropolitan fringe of Washington, D.C., to rural areas across North Carolina. Heartland states saw surprising increases in immigrants since 2000 — Indiana ranked 10th among all states, close behind Georgia, North Carolina and Arizona. Although most immigrants living in the United States are here legally, about one-third are not. Last year Congress debated immigration reform, but politicians who favored a comprehensive approach and politicians who favored an enforcement-only approach failed to come to terms. Unfortunately, the local problems got lost in the national rhetoric on border enforcement and "amnesty." Yet the groundswell of local pressures guarantees that immigration reform will be one of the biggest domestic issues our next president will face. Many states and localities have stepped into the breach by adopting their own enforcement policies aimed at restricting illegal immigrants. This leads to a patchwork of confusing measures, many of which are socially divisive and costly; some are of questionable legality. Our country's large immigrant population brings many positives. Immigrants keep our workforce numbers up, which means economic growth and more payroll tax contributions to Social Security and Medicare. Immigration assures the United States a young, productive labor force. But there are also challenges and responsibilities. One-third of immigrant workers lack a high school education. Immigration, both legal and illegal, puts stress on community infrastructure, from public schools to municipal providers of law enforcement, fire safety and public health. Although some state treasuries benefit from illegal immigration — Texas, for example, has concluded that illegal immigrants paid $425 million more in state taxes than they consumed in state services — many towns, cities and counties paid more for services to illegal immigrants than they received in taxes. And, so far, the federal government is doing little to help hard-pressed local governments even the score. The United States has more than 37 million immigrants living here, or 12.5 percent of the population. An estimated 11 million to 12 million are without legal status. The current generation of immigrants and their offspring — many of whom are U.S. citizens — will play a central role in our workforce as our native-born population continues to age. Without an adjustment to legal status, however, many may never make the kind of gains needed to secure a place in the labor market, the educational system and in local communities. What's needed is a three-pronged strategy. First, the next president should lead efforts to enact an Earned Legalization program. The program should require a simple registration process that includes a security check, a substantial fee, and a commitment to work and pay taxes while in a temporary legal status. Registrants then would stand in line behind legal immigrants to await permanent status. Achieving this status would depend on work history, tax payments, English language skills and "good moral character." The Earned Legalization program should offer enough promise to illegal immigrants to coax them out of the shadows. But it should be tough enough to weed out those who would do the country harm. Second, the next president should develop an Impact Aid program to compensate state and local governments for their extra costs. Part of this program would be financed through the registration fees paid by illegal immigrants. Third, the next president should announce a New Americans Initiative to help all immigrants integrate into American life. This initiative would allow states to strategically design and run their own New Americans programs through public-private partnerships, seeded initially by Washington. They could pursue new practices or enhance existing programs tailored to their own needs including English language instruction, civics education, welcome centers, and state and local referral services. It's not just immigrant families who need help. So do the communities where they live and the elected officials who govern them. Candidates for high office should stand up for communities with immigrant newcomers who come to America to work and build families, as did the parents and grandparents of today's "mainstream."
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Audrey Singer
Senior Fellow, Metropolitan Policy Program
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March 27, 2015,
Scott Andes and Jonathan Rothwell
March 26, 2015,
Alan Berube
March 25, 2015,
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March 25, 2015,
Bruce Katz and Kelly Kline
March 24, 2015,
Elizabeth Kneebone and Natalie Holmes
March 24, 2015,
Joseph Kane and Robert Puentes
March 23, 2015,
Kenan Fikri and Devashree Saha
March 20, 2015
Metropolitan Policy Program ›
April 5, 2012,
Devashree Saha and Audrey Singer
September 20, 2012,
Audrey Singer
December 7, 2010,
Gary Burtless and Audrey Singer
February 22, 2013,
Audrey Singer
March 15, 2012,
Audrey Singer
February 7, 2013,
Ron Haskins
November 20, 2014,
Ian Hathaway and Robert E. Litan
February 20, 2013,
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October 28, 2010,
Darrell M. West
July 18, 2012,
Neil G. Ruiz
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A dream
MT and Bieber were in it....won't say what they were doing. Naz was in the background eating popcorn. Almost choked on it but Damian gave him a drink.
While that was going on jorf was trying to figure out the mechanics of what MT and Bieber were doing. He thought something was OP.
Mikey raged at jorfs theories of said mechanics and left the dream....again.
My future xwife tried butt in galron took care of it....thanks btw.
Sadly TSI was not in the dream. Maybe tonight?
I had a dream too. I filmed it.
You're welcome.
/grabs Oscar
/shoots the audience
/celebrates at Taco Bell
rofl. crim.
you made me spill my beer!
You guys need a new avenue of gaming
|All times are GMT -7. The time now is 07:20 PM.


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As the title says I'm trying to make a perl daemon which, being long-running I want to be sane on resource usage.
All the examples / documentation I've seen doesn't seem to mention a way to disconnect a session.
The best documentation on the topic I can find in WWW::Mechanize::Firefox::Troubleshooting Where it's suggested the object (and connection?) is kept alive until global destruction.
In short, I've seen no 'disconnect' function, and wonder if I'm missing something.


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NYC Parks Events Calendar
Get up, get out, and do something! Just about any day of the year, you can find something fun, informative, and healthy to enjoy at an area park. Feel free to browse the listings below, or use the search tools to find an event that matches your interests and location.
Viewing 1,181–1,190 out of 3,131 events
from April 1, 2015 to April 25, 2026
Sunday, June 14, 2015
at Orchard Beach Nature Center (in Pelham Bay Park), Bronx
11:00 a.m.
Seining programs, which use nets to catch fish and crustaceans close to shore, are great for kids of all ages.
Category: Nature, Kids, Waterfront, Fishing
Freshwater Fishing
at Parking Lot (in Clove Lakes Park), Staten Island
11:00 a.m.
Catch-and-release fishing is a great way to get outdoors and discover nature just a few blocks from home.
Category: Nature, Kids, Fishing
Waterfront Walks: Guided Tours of Brooklyn Bridge Park
at Pier 1 (in Brooklyn Bridge Park), Brooklyn
11:00 a.m.–12:00 p.m.
Learn about Brooklyn Bridge's unique history, sustainable design, and diverse ecology on these guided tours led by Brooklyn Bridge Park Conservancy docents.
Category: History, Tours, Waterfront
Alley Pond Park Adventure Course: Free Public Sundays
at Alley Pond Park Adventure Center (in Alley Pond Park), Queens
1:00 p.m.–3:30 p.m.
The Alley Pond Park Adventure Course offers free outdoor adventure that fosters trust, communication, and team building.
Category: Education, Games, Kids
QBG Craft Table at The Shops at Skyview Center
at Shops at SkyView Center, Queens
2:00 p.m.–4:00 p.m.
Join us on Level B where we'll be creating a table top planters for Fathers Day!
Category: Arts & Crafts, Kids
Summer on the Hudson: Let's Dance
at Pier I (in Riverside Park South), Manhattan
6:00 p.m.–9:30 p.m.
Learn to dance like a pro at these salsa, cha-cha, and bachata lessons and group social dances led by master teachers from the Piel Canela Dance and Music School.
Category: Education, Dance, Festivals, Fitness, Waterfront
Monday, June 15, 2015
Sit Aerobics
at Hamilton Fish Recreation Center (in Hamilton Fish Park), Manhattan
2:15 p.m.–3:15 p.m.
A seated exercise class that raises the heart rate and improves balance, with minimal impact on joints. For adults and seniors. Recreation center membership is required. Visit the…
Category: Accessible, Fitness, Seniors
New Music Festival
at Bryant Park Lawn (in Bryant Park), Manhattan
5:00 p.m.–9:00 p.m.
Award-winning classical and jazz ensembles perform back to back each week, showcasing works commissioned by Chamber Music America.
Category: Concerts, Free Summer Concerts
Dancing Under the Stars
at Wallenberg Square (in Forest Park), Queens
6:00 p.m.–7:30 p.m.
Enjoy free ballroom dance lessons for people of all levels.
Category: Dance, Fitness, Seniors
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Dr. Michael M. Kirsch, MD
- 34940 Ridge Rd Ste B
Willoughby, OH 44094
- 2 Locations
- (440) 953-1899
Dr. Michael M. Kirsch graduated from the New York University School of Medicine in 1985. He works in Willoughby, OH and 1 other location and specializes in Gastroenterology. Dr. Kirsch is affiliated with Tri-Point Medical Center and West Medical Center.
Gender: Male
Languages Spoken: English
Medical School: New York University School of Medicine; Graduated 1985
*This physician has multiple office locations. See Office Information for details.


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(478): View more from Georgia
Ice cream and condoms, solid grocery store trip
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Ice cream and condoms, solid grocery store trip
Next year, please remind me not to be at a damn Super Bowl party with screaming children whose parents can't control them. I will sell the little suckers to the fucking circus passing through town.
His flight was delayed by two hours though. I just got cock-blocked by clouds :(
I'm not sure how long my penis is exactly, but I will tell you it resembles a bendy straw
You cant use biscuit as a chaser
Specially since he wanted to forget that we even touched, which makes it funnier because I don't think you can take back licking someone's butthole...
I woke up to a stripper (who added me on Facebook) messaging me reminding me to cancel my card if I can't find it
Woke up this morning with Nerf Bullets stuck to everything in my house and nut in my belly button. What exactly happened last night?
But that's fine. Because I am an independent woman who is going to pull some jane Goodall shit and save the world one day......or be a porn star......either way they are going to wish they had fucked me.
I'm sorry but the visual image of you suffocating on vagina is basically hysterical
You just referred to a pillow with a stolen bra strapped to it as "she". Let that sink in for a minute.
I don't remember... but I heard a cop threatened to pepper spay my dick
So our trip to Disney World ended in the three of us stripping at a gay club in orlando.
I asked him why the bed was wet and got.."well there are two options... and its not you."
I thought he was having it in Athens. Alright. Have fun. Please save my dignity and refrain from talking about my boobs and sexual "abilities". If I have any. I just feel like they are going to ask. Repeat after me. And repeat it 5 more times. This is going to be the phrase you're going to rely on tonight: "I can neither deny or confirm such actions."


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Big Bad Booty Daddy
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Comments Thread For: Paris: Peterson Has Khan's Number, He Will Win Again
Undefeated 140lb contender Vernon Paris will look to try to get himself into position for a world title shot as he takes on Zab Super Judah this Saturday night in an IBF eliminator at the Aviator Arena in Brooklyn, NY. The Detroit native was on BoxingScene.coms official audio show The Boxing Lab and spoke about the upcoming bout.
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Even though what Paris has said is true. He should concentrate on trying beat Judah, which is not as easy as it sounds.
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I think Zab time is up and if this kid is as hungry and confident as he speaks inside the ring then I see him beating Zab by KO. Judah just has no temperate and heart against adversity.
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It's going to be another close fight. I'm going with Khan but Peterson will always be a live dog.
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Oooh I hope Zab knocks this kid out! All that smack he talked about Holt losing against Coleman and now against Judah. Left uppercut to end the night for Paris!
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Paris was terrible
How bad is paris?? I mean the kid stunk out Brooklyn. Paris made Judah look like a boxing great. Judah is is okay but Paris was terrible.
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Written on: 29/11/2013 by Austingz (1 review written)
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