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CHEM310 INORGANIC CHEMISTRY Part 3 ORGANOMETALLIC CHEMISTRY 1. Introduction (types and rationale) 2. Molecular orbital (bonding) of CO, arrangement "in space" or ligand types (hapticity) 3. 16 and 18 electron rule (learning to count) 4. Synthesis, steric effects and reactivity - Wilkinsons catalyst (part 1) 5. Characterisation IR nmr etc. 6. Applications (oxidative addition b elimination) What is organometallic chemistry? Chemistry: structures, bonding and properties of molecules. Organometallic compounds: containing direct metal-carbon bonds. Either s or p bonds can occur Main group: (AlMe3)2 Structures s bonds and 3c-2e (or even 4c-2e) bonds Chem 210 Synthesis the first M-C bond Reactivity nucleophilic and basic auxiliaries in organic synthesis source of organic groups for transition metals Strong preference for s-donor groups but Cp is often p-bound (deceptively like with transition metals) Cp2Mg Cp2Fe Electropositive metals: often 3c-2e or 4c-2e hydrides/alkyls (Me3Al)2 (MeLi)4 As a Nucleophile Addition to polar C=X bonds (C=O, C=N, CºN) R + R M O OM Substitution at sp2 carbon (often via addition) OR' R OR' R + - MOR' R M O OM O Substitution at sp3 carbon does occur but is far less easy and often has a multistep mechanism Substitution at other elements: often easy for polar M-X bonds (Si-Cl, B-OMe) Me MeMgBr + B(OMe)3 BrMg B(OMe)2 MeOMgBr + MeB(OMe)2 Me3B OMe As a base More prominent in polar solvents think of free R- acting as base Elimination H R M + RH + MX X mechanism can be more complex than this Metallation H M R M + RH Me2N Me2N chelate effect more important than inductive effect! b-hydrogen transfer Al H Al H O O mainly for Al: for more electropositive elements, deprotonation and nucleophilic attack are faster for less electropositive elements, often no reaction Chemistry: structures, bonding and properties of molecules. Transition metal compounds Some compounds do not contain metal-carbon bond, but they are usually included in the field of organometallic chemistry. They include: • Metal hydride complexes, e.g. • Phosphine complexes, e.g. • N2-complexes, e.g. Exercise. Which of the following compounds is an organometallic compound? 2+ NH3 OCH3 a) b) Cu Ti H3 N NH3 CH3O OCH3 In general, metals in NH3 OCH3 organometallic compounds include: - Cl O c) CH2 d) • main group metals Cl Pt O Pt O CH2 • transition metals Cl O • f-block metals Ph In this course, Li Me P CO transition metals are OC CO our main concern. Me Li O e) Co C Me Li f) OC Co Co CO O C Co CO Li Me OC OC P Ph A brief history of organometallic chemistry 1) Organometallic Chemistry has really been around for millions of years Naturally occurring Cobalimins contain Co—C bonds Vitamin B12 2) Zeise's Salt synthesized in 1827 = K[Pt(C2H4)Cl3] • H2O Confirmed to have H2C=CH2 as a ligand in 1868 Structure not fully known until 1975 3) Ni(CO)4 synthesized in 1890 4) Grignard Reagents (XMgR) synthesized about 1900 Accidentally produced while trying to make other compounds Utility to Organic Synthesis recognized early on 5) Ferrocene synthesized in 1951 Modern Organometallic Chemistry begins with this discovery (Paulson and Miller) 1952 Fischer and Wilkinson Nobel -Prize Winners related to the area: Victor Grignard and Paul Sabatier (1912) Grignard reagent K. Ziegler, G. Natta (1963) Zieglar-Natta catalyst E. O. Fisher, G. Wilkinson (1973) Sandwich compounds K. B. Sharpless, R. Noyori (2001) Hydrogenation and oxidation Yves Chauvin, Robert H. Grubbs, Richard R. Schrock (2005) Metal- catalyzed alkene metathesis Common organometallic ligands M H M C M C C M M M CO M CNR M N2 H H M CS M NO M PR3 M M H X M M M M M M M C M C Why organometallic chemistry ? a). From practical point of view: * OMC are useful for chemical synthesis, especially catalytic processes, e.g. In production of fine chemicals In production of chemicals in large-scale reactions could not be achieved traditionally * Organometallic chemistry is related to material sciences. e.g. Organometallic Polymers PBu3 PBu3 Pt C C C C Pt C C C C n n PBu3 PBu3 Small organometallic compounds: Precursors to films for coating (MOCVD) (h3-C3H5)2Pd -----> Pd film CH3CC-Au-CNMe -----> Au film Luminescent materials * Biological Science. Organometallic chemistry may help us to understand some enzyme-catalyzed reactions. e.g. B12 catalyzed reactions. H R R H b). From academic point of view: * Organometallic compounds display many unexpected behaviors- discover new chemistry- new structures e.g. H H H3N: M M M M M M H SiR3 C C C C M M C M C New reactions, reagents, catalysts, e.g. Ziegler-Natta catalyst, Wilkinson catalyst Reppe reaction, Schwartz's reagent Sharpless epoxidation, Tebbe's reagent Types of bonds possible from Ligands Language: All bonds are coordination or coordinative Remember that all of these bonds are weaker than normal organic bonds (they are dative bonds) Simple ligands e.g. CH3-, Cl-, H2 give s bonds systems are different e.g. CO is a s donor and p acceptor Bridging ligands can occur two metals Metal-metal bonds occur and are called d bonds – they are weak and are a result of d-d orbital overlap 18 Electron Rule (Sidgwick, 1927) • OM chemistry gives rise to many "stable" complexes - how can we tell by a simple method • Every element has a certain number of valence orbitals: 1 { 1s } for H 4 { ns, 3´np } for main group elements 9 { ns, 3´np, 5´(n-1)d } for transition metals s px py pz dxy dxz dyz dx2-y2 dz2 • Therefore, every element wants to be surrounded by 2/8/18 electrons – For main-group metals (8-e), this leads to the standard Lewis structure rules – For transition metals, we get the 18-electron rule • Structures which have this preferred count are called electron-precise • Every orbital wants to be "used", i.e. contribute to binding an electron pair The strength of the preference for electron-precise structures depends on the position of the element in the periodic table • For early transition metals, 18-e is often unattainable for steric reasons - the required number of ligands would not fit • For later transition metals, 16-e is often quite stable (square-planar d8 complexes) • Addition of 2e- from 5th ligand converts complex to 5 CN 18e- , marginally more stable Predicting reactivity 14 e dissociative (C2H4)PdCl2 - C2H4 CO (C2H4)2PdCl2 (C2H4)(CO)PdCl2 ? 16 e CO - C2H4 16 e (C2H4)2(CO)PdCl2 associative 18 e Most likely associative Predicting reactivity 16 e dissociative Cr(CO)5 - CO MeCN 18 e Cr(CO)6 Cr(CO)5(MeCN) 18 e ? MeCN - CO Cr(CO)6(MeCN) associative 20 e (Sterics!) Most likely dissociative N.B. How do you know a fragment forms a covalent or a dative bond? • Chemists are "sloppy" in writing structures. A "line" can mean a covalent bond, a dative bond, recognise/understand the bonding first • Use analogies ("PPh3 is similar to NH3"). • Rewrite the structure properly before you start counting. Cl PPh3 Cl PPh3 Pd = 10 Cl¾ = 1 Pd 1e Pd 2e P® = 2 dative allyl = 3 covalent bond + ¾¾ bond e-count 16 3e "bond" to the allyl fragment "Covalent" count: (ionic method also useful) 1. Number of valence electrons of central atom. • from periodic table 2. Correct for charge, if any • but only if the charge belongs to that atom! 3. Count 1 e for every covalent bond to another atom. 4. Count 2 e for every dative bond from another atom. • no electrons for dative bonds to another atom! 5. Delocalized carbon fragments: usually 1 e per C (hapticity) 6. Three- and four-center bonds need special treatment 7. Add everything N.B. Covalent Model: 18 = (# metal electrons + # ligand electrons) - complex charge The number of metal electrons equals it's row number (i.e., Ti = 4e, Cr = 6 e, Ni = 10 e) Hapto (h) Number (hapticity) For some molecules the molecular formula provides insufficient information with which to classify the metal carbon interactions The hapto number (h) gives the number of carbon (conjugated) atoms bound to the metal It normally, but not necessarily, gives the number of electrons contributed by the ligand We will describe to methods of counting electrons but we will employ only one for the duration of this module The two methods compared: some examples N.B. like oxidation state assignments, electron counting is a formalism and does not necessarily reflect the distribution of electrons in the molecule – useful though Some ligands donate the same number of electrons Number of d-electrons and donation of the other ligands can differ Now we will look at practical examples on the black board Does it look reasonable ? Remember when counting: Odd electron counts are rare In reactions you nearly always go from even to even (or odd to odd), and from n to n-2, n or n+2. Electrons don't just "appear" or "disappear" The optimal count is 2/8/18 e. 16-e also occurs frequently, other counts are much more rare. Exceptions to the 18 Electron Rule ZrCl2(C5H5)2 Zr(4) + [2 x Cl(1)] + [2 x C5H5(5)] =16 TaCl2Me3 Ta(5) + [2+ x Cl(1)] + [3 x M(1)] =10 WMe6 W(6) + [6 x Me(1)] =12 Pt(PPh3)3 Pt(10) + [3 x PPh3(2)] =16 IrCl(CO)(PPh3)2 Ir(9) + Cl(1) + CO(2) + [2 x PPh3(2)] =16 What features do these complexes possess? • Early transition metals (Zr, Ta, W) • Several bulky ligands (PPh3) • Square planar d8 e.g. Pt(II), Ir(I) • σ-donor ligands (Me) Alkyl ligands: Transition metal alkyl complexes important for catalysts e.g. olefin polymerization and hydroformylation thermodynamic Problem is their weak kinetic stability (Thermally fine: M-C bond dissociation energies are typically 40-60 kcal/mol with 20-70 kcal/mol) Simple alkyls are sigma donors, that can be considered to donate one or two electrons to the metal center depending on which electron counting formalism you use Synthesis of Metal Alkyl Complexes 1. Metathetical exchange using a carbon nucleophile (R-). Common reagents are RLi, RMgX (or R2Mg), ZnR2, AlR3, BR3, and PbR4. Much of this alkylation chemistry can be understood with Pearson's "hard- soft" principles 2. Metal-centered nucleophiles (i.e. using R+ as a reagent) Typical examples are a metal anion and alkyl halide (or pseudohalogen). for example: NaFp + RX Fp-R + NaX [Fp = Cp(CO)2Fe] 3. Oxidative Addition. This requires a covalently unsaturated, low- valent complex (16 e- or less). A classic example: 4. Insertion- To form an alkyl, this usually involves an olefin insertion. The simplest generic example is the insertion of ethylene into an M-X bond, i.e. M-X + CH2CH2 M-CH2CH2-X Carbonyl Complexes Bonding of CO Electron donation of the lone pair on carbon s This electron donation makes the metal more electron rich - compensate for this increased electron density, a filled metal d-orbital may interact with the empty p* orbital on the carbonyl ligand p-backbonding or p- backdonation or synergistic bonding Similar for alkenes, acetylenes, phosphines, and dihydrogen. What stabilizes CO complexes is M→C π–bonding The lower the formal charge on the metal ion the more willing it is to donate electrons to the π–orbitals of the CO Thus, metal ions with higher formal charges, e.g. Fe(II) form CO complexes with much greater difficulty than do zero-valent metal ions For example Cr(O) and Ni(O), or negatively charged metal ions such as V(-I) In general to get a feeling for stability examine the charges on the metals Syntheses of metal carbonyls Metal carbonyls can be made in a variety of ways. For Ni and Fe, the homoleptic or binary metal carbonyls can be made by the direct interaction with the metal (Equation 1). In other cases, a reduction of a metal precursor in the presence of CO (or using CO as the reductant) is used (Equations 2-3). Carbon monoxide also reacts with various metal complexes, most typically filling a vacant coordination site (Equation 4) or performing a ligand substitution reactions (Equation 5) Occasionally, CO ligands are derived from the reaction of a coordinated ligand through a deinsertion reaction (Equation 6) Synthesis of carbonyl complexes Direct reaction of the metal – Not practical for all metals due to need for harsh conditions (high P and T) – Ni + 4CO Ni(CO)4 – Fe + 5CO Fe(CO)5 Reductive carbonylation – Useful when very aggressive conditions would be required for direct reaction of metal and CO » Wide variety of reducing agents can be used – CrCl3+ Al + 6CO AlCl3 + Cr(CO)6 – 3Ru(acac)3 + H2 + 12CO Ru3(CO)12 + N.B. From the carbonyl complex we can synthesize other derivatives Main characterization methods: • Xray diffraction Þ (static) structure Þ bonding • NMR Þ structure en dynamic behaviour • EA Þ assessment of purity • (calculations) Useful on occasion: • IR • MS • EPR Not used much: • GC • LC IR spectra and metal-carbon bonds The υCO stretching frequency of the coordinated CO is very informative Recall that the stronger a bond gets, the higher its stretching frequency M=C=O (C=O is a double bond) canonical structure Lower the υCO stretching frequency as compared to the M-C≡O structure (triple bond) Note: υCO for free CO is 2041 cm-1) [Ti(CO)6]2- [V(CO)6]- [Cr(CO)6] [Mn(CO)6]+ [Fe(CO)6]2+ υCO 1748 1858 1984 2094 2204 cm-1 increasing M=C double decreasing M=C double bonding bonding Bridging versus terminal carbonyls Bridging CO groups can be regarded as having a double bond C=O group, as compared to a terminal C≡O, which is more like a triple bond: ~ double bond the C=O group ~ triple bond in a bridging carbonyl is more M like the C=O in M-C≡O C=O a ketone, which typically has M υC=O = 1750 cm-1 terminal carbonyl bridging carbonyl (~ 1850-2125 cm-1) (~1700-1860 cm-1) Bridging CO between 1700 and 2200 cm-1 Bridging versus terminal carbonyls in [Fe2(CO)9] O CO OC C CO Fe OC Fe C C O OC CO O terminal bridging carbonyls carbonyls Summary 1. As the CO bridges more metal centers its stretching frequency drops – same for all p ligands – More back donation 2. As the metal center becomes increasingly electron rich the stretching frequency drops Alkene ligands Dewar-Chatt-Duncanson model The greater the electron density back-donated into the p* orbital on the alkene, the greater the reduction in the C=C bond order Stability of alkene complexes also depends on steric factors as well An empirical ordering of relative stability would be: tetrasubstituted < trisubstituted < trans-disubstituted < cis- disubstituted < monosubstituted < ethylene Alkyne ligands: Similar to alkenes Alkynes tend to be more electropositive-bind more tightly to a transition metal than alkenes -alkynes will often displace alkenes Difference is 2 or 4 electron donor sigma-type fashion (A) as we did for alkenes, including a pi-backbond (B) The orthogonal set can also bind in a pi-type fashion using an orthogonal metal d-orbital (C) The back-donation to the antibonding orbital (D) is a delta-bond-the degree of overlap is quite small - contribution of D to the bonding of alkynes is minimal The net effect p-donation - alkynes are usually non-linear in TM complexes Resonance depict the bonding of an alkyne. I is the metallacyclopropene resonance form Support for this versus a simple two electron donor, II, can be inferred from the C-C bond distance as well the R- C-C-R angles III generally does not contribute to the bonding of alkyne complexes. Ally ligands: Allyl ligands are ambidentate ligands that can bind in both a monohapto and trihapto form The trihapto form can be expressed as a number of difference resonance forms as shown here for an unsubstituted allyl ligand: Important applications Dihydrogen Ligands: Metal is more electropositive than hydrogen Hydrogen acts as a two electron sigma donor to the metal center. The complex is an arrested intermediate in the oxidative addition of dihydrogen How does this affect the oxidation state of the meta? Dihydrogen complexes Bonding is "simple" a 3C-2electron bond. H2 - neutral two electron sigma donor One could also describe a back-donation of electrons from a filled metal orbital to the sigma-* orbital on the dihydrogen Electronic Attributes of Phosphines Like that of carbonyls As electron-withdrawing sigma-donating capacity decreases At the same time, the energy of the p-acceptor (sigma-*) on phosphorous is lowered in energy, providing an increase in backbonding ability. Therefore, range of each capabilities –tuning rough ordering -CO stretching frequency indicator- low CO stretching frequency- greater backbonding to M Experiments such as this permit us to come up with the following empirical ordering: Cone Angle (Tolman) Phosphine Cone Steric hindrance: Ligand Angle A cone angle of 180 degrees - effectively protects (or covers) one half of the coordination sphere of PH3 87o the metal complex PF3 104o P(OMe)3 107o PMe3 118o PMe2Ph 122o PEt3 132o PPh3 145o PCy3 170o P(t-Bu)3 182o P(mesityl)3 212o You would expect a dissociation event to occur first before any other reaction -steric bulk (rate is first order -increasing size) This will also have an effect on activity for catalysts N.B. "flat" can slide past each other For example Wilkinson's catalyst (more later) Has a profound effect on the reactivity! Reaction chemistry of complexes Three general forms: 1. Reactions involving the gain and loss of ligands a. Ligand Dissoc. and Assoc. (Bala) b. Oxidative Addition c. Reductive Elimination d. Nucleophillic displacement 2. Reactions involving modifications of the ligand a. Insertion b. Carbonyl insertion (alkyl migration) c. Hydride elimination (equilibrium) 3. Catalytic processes by the complexes Wilkinson, Monsanto Carbon-carbon bond formation (Heck etc.) a) Ligand dissociation/association (Bala) • Electron count changes by -/+ 2 • No change in oxidation state • Dissociation easiest if ligand stable on its own (CO, olefin, phosphine, Cl-, ...) • Steric factors important M M + Br- Br b) Oxidative Addition Basic reaction: X X LnM + LnM Y Y • Electron count changes by +/- 2 (assuming the reactant was not yet coordinated) • Oxidation state changes by +/- 2 • Mechanism may be complicated The new M-X and M-Y bonds are formed using: • the electron pair of the X-Y bond • one metal-centered lone pair One reaction multiple mechanisms Concerted addition, mostly with non-polar X-Y bonds H2, silanes, alkanes, O2, ... Arene C-H bonds more reactive than alkane C-H bonds (!) X X X LnM + LnM LnM Y Y Y A Intermediate A is a s-complex Reaction may stop here if metal-centered lone pairs are not readily available Final product expected to have cis X,Y groups Stepwise addition, with polar X-Y bonds – HX, R3SnX, acyl and allyl halides, ... – low-valent, electron-rich metal fragment (IrI, Pd(0), ...) X LnM X Y LnM X Y LnM Y B Metal initially acts as nucleophile – Coordinative unsaturation less important Ionic intermediate (B) Final geometry (cis or trans) not easy to predict Radical mechanism is also possible Cis or trans products depends on the mechanism H PEt3 H2 OC Ir H Ir(III) Et3P cis Cl H PEt3 PEt3 HI OC Ir Cl OC Ir I Ir(III) Et3P Et3P Ir(I) Cl cis CH3 PEt3 CH3Br OC Ir Cl Ir(III) Et3P Br trans c) Reductive elimination This is the reverse of oxidative addition - Expect cis elimination Rate depends strongly on types of groups to be eliminated. Usually easy for: • H + alkyl / aryl / acyl – H 1s orbital shape, c.f. insertion • alkyl + acyl – participation of acyl p-system • SiR3 + alkyl etc Often slow for: • alkoxide + alkyl • halide + alkyl – thermodynamic reasons? We will do a number of examples of this reaction Relative rates of reductive elimination L CH3 L CH3 RE Pd + solv Pd LPd(solv) + CH3 CH3 L CH3 solv CH3 -L Complex Rate Constant (s-1) T(oC) Ph3P CH3 Pd 1.04 x 10-3 60 Ph3P CH3 MePh2P CH3 Pd 9.62 x 10-5 60 MePh2P CH3 Ph Ph P CH3 Pd 4.78 x 10-7 80 P CH3 Ph Ph Most crowded is the fastest reaction Special case: Nucleophilic Attack on a Coordinated CO acyl anion Fisher carbene This is Fischer carbene It has a metal carbon double bond Such species can be made for relatively electronegative metal centers N.B. mid to late TMs Fischer carbenes are susceptible to nucleophilic attack at the carbon Fischer carbenes act effectively as σ donors and p acceptors The empty antibonding M=C orbital is primarily on the carbon making it susceptible to attack by nucleophiles Other type is called a Shrock carbene (alkylidene) Characteristic Fischer-type Schrock-type Typical metal (Ox. Middle to late T.M. Early T.M. State) Fe(0), Mo(0) Cr(0) Ti(IV), Ta(V) Substituents At least one highly H or alkyl attached to carbene electronegative carbon heteroatom Typical other Good p acceptors Good s and p ligands donors Electron count 18 10-18 Nucleophilic displacement Ligand displacement can be described as nucleophilic substitutions O.M. complexes with negative charges can behave as nucleophiles in displacement reactions Iron tetracarbonyl (anion) is very useful O R R' R'X O O2 R OH [Fe(CO)4]2- RX [ R Fe(CO)4]- X2 O H+ R X CO R H R O X O R [ R Fe(CO)4]- H+ O H Modifications of the ligand a) Insertion reactions Migratory insertion! The ligands involved must be cis - Electron count changes by -/+ 2 No change in oxidation state If at a metal centre you have a s-bound group (hydride, alkyl, aryl) a ligand containing a p-system (olefin, alkyne, CO) the s-bound group can migrate to the p-system 1. CO, RNC (isonitriles): 1,1-insertion 2. Olefins: 1,2-insertion, b-elimination R R M M M M CO R R 1,1 O 1,2 1,1 Insertion The s-bound group migrates to the p-system if you only see the result, it looks like the p-system has inserted into the M-X bond, hence the name insertion To emphasize that it is actually (mostly) the X group that moves, we use the term migratory insertion (Both possible tutorial) The reverse of insertion is called elimination Insertion reduces the electron count, elimination increases it Neither insertion nor elimination causes a change in oxidation state a- elimination can release the "new" substrate or compound In a 1,1-insertion, metal and X group "move" to the same atom of the inserting substrate. The metal-bound substrate atom increases its valence Me M Me M M Me M S Me CO O SO2 O O CO, isonitriles (RNC) and SO2 often undergo 1,1-insertion 1,2 insertion (olefins) Insertion of an olefin in a metal-alkyl bond produces a new alkyl Thus, the reaction leads to oligomers or polymers of the olefin • polyethene (polythene) • polypropene Standard Cossee mechanism R M M M M R R R Why do olefins polymerise? Driving force: conversion of a p-bond into a s-bond One C=C bond: 150 kcal/mol Two C-C bonds: 2´85 = 170 kcal/mol Energy release: about 20 kcal per mole of monomer (independent of mechanism) Many polymerization mechanisms Radical (ethene, dienes, styrene, acrylates) Cationic (styrene, isobutene) Anionic (styrene, dienes, acrylates) Transition-metal catalyzed (a-olefins, dienes, styrene) b Hydride elimination (usually by b hydrogens) Many transition metal alkyls are unstable (the reverse of insertion) the metal carbon bond is weak compared to a metal hydrogen Bond Alkyl groups with β hydrogen tend to undergo β elimination M -CH2-CH3 M - H + CH2=CH2 Two examples A four-center transition state in which the hydride is transferred to the metal An important prerequisite for beta-hydride elimination is the presence of an open coordination site on the metal complex - no open site is available - displace a ligand metal complex will usually have less than 18 electrons, otherwise a 20 electron olefin-hydride would be the immediate product. To prevent beta-elimination from taking place, one can use alkyls that: Do not contain beta-hydrogens Are oriented so that the beta position can not access the metal center Would give an unstable alkene as the product Catalysis (homogeneous) Reduction of alkenes etc. The size of the substrate has an effect on the rate of reaction Same reaction different catalyst Alternative starting material The Monsanto acetic acid process Methanol - reacted with carbon monoxide in the presence of a catalyst to afford acetic acid Insertion of carbon monoxide into the C-O bond of methanol The catalyst system - iodide and rhodium Iodide promotes the conversion of methanol to methyl iodide, Methyl iodide - the catalytic cycle begins: 1. Oxidative addition of methyl iodide to [Rh(CO)2I2]- 2. Coordination and insertion of CO - intermediate 18-electron acyl complex 3. Can then undergo reductive elimination to yield acetyl iodide and regenerate our catalyst Catvia Process Wacker process (identify the steps) Identify the steps
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Chiri's 2- Virtual Pets!
Notes and Credits (added by acustalow)
Chiri's 2- Virtual Pets! (Download only) sorry guys its glitchy online and may not start
Chiri's 2- Virtual Pets! (Download only) sorry guys its glitchy online and may not start
by Austin "BlackWolf" Custalow
Chiri Garden is an interactive program in which you can create and design a huge array of beautiful scenery and raise virtual pets called "Chiri's." But thats not all, you must buy a turret and defend your Utopia from the Bad Chiri's known as "Boombos." Buy Shops and items from the market to keep your Chiri's happy and healthy. -Acustalow
Download and open in full screen for best gameplay.
Chiri's Now includes Market feature and view mode, plus added scenery.
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VIEWS: 0 PAGES: 21 CATEGORY: Computers: Software POSTED ON: 4/13/2012 Public Domain
BACKGROUND 1. Technical Field The present invention generally relates to distributed networks, and particularly relates to a system and method for deploying and managing intelligent nodes in a distributed network, such as may be used to extend enterprise and IP networkinfrastructure to processing data from sensors, actuators, and other "edge" systems and devices. 2. Background Enterprise networks traditionally work well at linking together different workgroups within organizations and making business applications and data available across those workgroups. However, significant challenges arise when extendingenterprise network connectivity via devices and systems that operate at the network edges and provide physical world data collection and control processing. For example, integrating diverse data from edge devices and systems into enterprise networksoften requires developing customized software code and "middleware" components, to provide for data input/output, formatting, conversion, translation, and communications. The time and expertise needed to develop such software/middleware is prohibitive. Some companies skip the expense altogether and suffer from the attendant inefficiencies arising from having critical assets--sensors, actuators, and other edgesystems and devices--stranded outside of their enterprise networks. Other companies bear the expense and yet get less business value from the effort than they expected, because of limitations, complexity and errors in the custom-developed integrationsoftware. By its very nature, software of that type usually is difficult and expensive to debug and maintain. Worse still, the complex, custom nature of such software clouds upgrade paths, meaning that such software may not be readily extended to newdevices and systems. As a further issue, the convergence of sensors, actuators, and other edge systems and devices into enterprise networks can overwhelm the bandwidth of networks, especially wireless networks. In a
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All hotels in Ludlow, Vermont, United States of America
1 room, 2 adults
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Star Wars Command Endor Attack Set
Where To Buy
Product Description:
Create battles and destroy armies with the Command sets! This Endor Attack set includes a force of 4 Ewok figures and an exclusive Luke Skywalker figure to lead them into battle. Will they prevail against the exclusive Biker Scout Commander and his 4 Biker Scouts? The AT-ST vehicle will destroy opposing warriors as the X-wing Fighter vehicle attacks from above! Take charge and command your own Battle of Endor!
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Early ride on the Zamboni – Wednesday, February 16th
Feb 16, 2011, 10:45 PM EDT
Let's take a look at the results from the five games that ended relatively early on Wednesday.
Is this Devils run a delusional dream that will only serve to ruin the team's chance of getting a lottery pick, or is it the beginning of one of the most unexpected resurgences in ages? The stakes are pretty high for a team that could use more young talent, but also needs to fill the Prudential Center seats. They certainly value this win against the Hurricanes in particular, considering the fact that Carolina holds the eighth spot with 62 points. The Devils are now 12 back and own a five-game winning streak after holding onto a 3-0 lead to beat the Canes.
Ilya Kovalchuk continues to be the top reason for the Devils hot streak, as he scored to earn his sixth goal in his last seven games. Patrik Elias also factored into the win, scoring a goal and an assist while Johan Hedberg earned his 10th win of the season with 25 saves.
This isn't exactly how the Sabres wanted to start their six-game homestand, while the Maple Leafs bolstered their marginal playoff hopes by winning games against Northeast Division teams in back-to-back games. Toronto broke a seven-game losing streak in Buffalo with this win.
Phil Kessel now has three goals in the last two nights while Joey Crabb scored what would be the game-winner shorthanded. James Reimer ended up with the win after taking over for an injured J.S. Giguere.
Los Angeles 4, Columbus 3 (SO)
The Kings kept taking one-goal leads, yet Rick Nash (one goal, two assists) and the Blue Jackets kept scrapping their way back into the game. Jarret Stoll ended up scoring the only shootout goal to win it for Los Angeles, whose 8-0-2 run is their best streak in 31 years.
The Flames could knock them right back out of the top eight if they beat the Dallas Stars tonight, but as of this writing, the Kings are in the West's last playoff spot at the moment.
The Flyers earned a two-goal lead in a 65 second span around the midway point of the first period and eventually built it to 3-0. The Panthers scored two goals in the third to make it interesting, but Danny Briere scored an empty netter to go with his two primary assists to secure the win for Philly.
The Wild still remain ahead of the Blackhawks by one point for 10th place in the West, but Chicago won one for Coach Q and did it the best way you could ask: by earning the victory in regulation.
Both goalies were strong, as Corey Crawford made 33 saves for his 18th win of the season while strong backup Jose Theodore stopped 34 shots in defeat. All four of the game's goals came outside of 5-on-5 play, as Brian Campbell, Troy Brouwer and Matt Cullen notched power-play goals while Jake Dowell iced the contest with an empty-netter.
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Los Angeles-based attorney A. David Youssefyeh has been insulted, had vicious rumors spread about him and even been verbally threatened by many in his Iranian Jewish community here in Southern California over the past three years for speaking in support of his client—many of whom are...
High-tech new water — next steps for sustainable water solutions in California
Israel's special forces operate outside of the box
Kerry heads for Egypt and the Gulf to discuss Iran deal, ISIS
Mossad: All 11 Jews missing after fleeing Iran in the 90s were murdered
Teva buys Allergan for $40.5 billion
Tag: A. David Youssefyeh
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Q&A: Youssefyeh sheds light on Namvar criminal and bankruptcy cases
May 24, 2011 | 7:18 pm
Webcast: Attorney Youssefyeh speaks out year after Namvar scandal
February 18, 2010 | 11:58 pm
I had the unique challenge these past several weeks of researching and writing the cover story for this week's Journal concerning the alleged business fraud scandals that are currently shaking Southern California's Iranian Jewish community to its core. Since late 2008 many in the...


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An entire website full of denim quilt ideas. Quilt Inspiration: Free pattern day ! Denim quilts
I've done the denim rag quilt and it is awesome! Lots of other cool denim quilt tutorials and ideas.
lots of awesome denim quilt tutorials and ideas. Blue jean quilt
TURN OLD JEANS INTO QUILTS - lots of awesome denim quilt tutorials and ideas.
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crochet old jeans...what a great idea
Recycle Jeans, Crochet Bags, Jean Purses, Blue Jeans, Jeans Pur, Denim Bag, Colored Denim, Crocheted Bags, Old Jeans Ideas
@Gina Walters @Beverly Walters crochet old jeans... Can you make me one or two or five?!? I'm thinking we need colored denim like neon pink or green!!!
braided blue jean purse...
Recycled jeans and a few buttons - Upcycled crocheted bag!
cute denim bag
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#Denim tote bag. #jeans #repurpose #reuse #recycle
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Great way to recycle jeans. The bigger the jeans, the bigger the bag.
Recycled Jeans, Grocery Bags, Blue Jeans, Shops Bags, Jeans Bags, Totes Bags, Jeans Pur, Beaches Bags, Old Jeans
jean bags | Shopping bags made from recycled jeans and curtains:
old jeans made into a bag...great as a tote for the beach or reusable shopping bag! Even a bag for gift giving (use toddler/baby jeans for smaller gift bag!) She lined grocery bag w/old curtains
Great way to recycle jeans. The bigger the jeans, the bigger the bag. Hmmm . . . May need to make a beach bag out of my old jeans once I reach my goal weight!
blue jean tote bags. Nice way to reuse old jeans.
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Prayag Consulting Reviews
- Any Location
- Any Job Title
- Any Status
4 Employee ReviewsSort: Popular Rating Date
"Great Learning! Not Employee Friendly "
- Work/Life Balance
- Culture & Values
- Career Opportunities
- Comp & Benefits
- Senior Management
I worked at Prayag ConsultingDoesn't RecommendNeutral OutlookDoesn't RecommendNeutral Outlook
You'll be on job from day one, so you will get a chance to learn things fast. Fixed timings - mostly 9 am to 6 pm
Work : No fixed responsibilities, will be doing so many things you will end up being jack of all trades and king of none. Very few seniors to help you learn and zero trainings in place. Benefits : Zero employee benefits, salary is not at all similar to industry standards. No employee retention strategy. Culture : There is no culture in place, the company is being run as a government organization. Nothing to get motivated - no growth opportunities, no fun and bad leave structure. Leadership : The CEO is nice to work with, but there are some managers who don't know how to manage people and they hardly know how to deal with a project.
Advice to Management
Think of your employees, put a retention strategy in place and introduce employee benefits. Most importantly, come out of your age old principles and look at what is happening around you.
I worked at Prayag Consulting
Brilliant learning environment-every project provides a lot of exposure, very talented bunch of people, fixed timings (mostly till 6/7pm from 9 am)
No retention strategy in place for performing employees, multi-project handling means chaos, monetary performance incentives are missing
Advice to Management
Have retention strategies in place for employees- offer variable pay. Fix job descriptions in reality and paper, and dont change them once employees join. Manage people to grow.
"Always learn in new project "
- Work/Life Balance
- Culture & Values
- Career Opportunities
- Comp & Benefits
- Senior Management
I have been working at Prayag Consulting full-time (More than 8 years)RecommendsPositive OutlookRecommendsPositive Outlook
Good Analyst in the team
Motivation, self improvements, always learn some thing new in different-2 Project
"Not an employee friendly company "
- Work/Life Balance
- Career Opportunities
- Comp & Benefits
- Senior Management
I worked at Prayag ConsultingDoesn't RecommendDoesn't Recommend
Good clients, good starting place for a career in Research, you will be on the job immediately after you join.
Senior Management is hugely employee unfriendly, and they lack people management skills. Appreciation of good work is not part of the company culture, if the company has any culture. There are documents defining various roles - however, none followed - sometimes you will be only editing and formatting PowerPoint slides for 2-3 months and nothing else. And above all, no value for personal life. The environment is more like that of a military training camp for the graduate joinees, rather than that of a professional organisation. Not many senior people have stayed with the company for long.
Advice to Management
The Chairman and CEO are good, but the Second-in-Command fails completely when it comes to managing people or managing projects. Employees complaining about this person is a common place at Prayag. Better hire an experienced person to run the day-to-day operations.
Is this helpful? The community relies on everyone sharing – Add Anonymous Review


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BRAND NEW Stand Up Paddle Boards at DISCOUNTED prices
Through a SPECIAL ebay classifieds test-marketing program, you can buy renowned VESL Stand Up Paddle Boards and accessories BELOW the manufacturer's already low prices.
Summer is here, and now is the time to jump in to the fastest growing sport in the world.
We have Brand New VESL Ultra lite EPS-cored Paddle Boards starting at only $599!!!
Complete VESL Standard Series Stand Up Paddle ...
Jul 23 -
Capistrano Beach - Sporting goods
USA Patriotic Red White Blue Sentinal Flag Collection Party Decor+MORE
USA Patriotic Red White Blue Party + Misc Flag Collection including Valley Forge Sentinel + Vintage items can be used for Arts & Crafts & Party Decorating
July 4 + Memorial Day + Veterans Day + Presidents Day
+ Patriotic Parties + Military Celebrations
3 x 5 FT Valley Forge Sentinel cloth flag with 2 grommets
9Ft triangle 10"flag motif unopened ...
Jul 21 -
Newport Beach - Everything else
Furniture for sale
SOLID Oak wicker rocker chair with wicker seat $60.00
LargeHutch and Buffet 6ft tall/4ft wide/20inches deep $200.00 OBO
Assortment Cigar humidors prices discussed
Large Maple Bookcase 7ft tall/3ft wide/14 inches deep $65.00
A Mini Derby Game very old Antique game
200 year old Cherrywood rocker chair, solid seat is made of cherrywood price to be discussed needs a bit of ...
Jul 21 -
Laguna Woods - Everything else
Pool table, wood, not slate, 8 foot long, leather pockets, NEW
Pool table, wood, not slate, 8 foot long, leather pockets, NEW, Complete with balls, triangle,cues, cue rack.
Jul 6 -
Lakewood - Toys & games
Wood Office Furniture Set
4 book cases - 2 shown. 6' x 31" x 13".
2 filing cabinets - 1 shown. 29"x19"x26".
Desk - 4'x28", 36" h back.
Printer table - 24"x27"x28"
Jul 4 -
Anaheim - Business & industrial
KidKraft Wooden Birthday Cake Set
KidKraft Wooden Birthday Cake Set
Gently used by our daughter and now outgrown.
Includes a serving tray, a serving knife, 5 slices of cake (that each separate to 2) and 5 candles (flames separate from bodies). Assembling the cake improves puzzle-solving skills. Made of composite wood products and solid wood.
Call / text Tony 562-396-4236
Jul 2 -
Cerritos - Toys & games
Cherry Wood Pool Table for sale
Old Antique Cherry Wood Pool Table For Sale
Need space must sell
New pockets, cues, with games. Used Miller Lite Billiard Light
Jul 1 -
Long Beach - Sporting goods
Japanese Geisha Porcelain Fish Bowl planter pot decoration w Stand
If the ad is up, this is still available.
Japanese Geisha Porcelain Fish Bowl with Stand
Price Firm
Dimensions: 21 inches wide x 17 inches tall - 24 inches tall with stand
A classic bowl shape receives thickly-applied details that give a rich texture to Dane Home's Imperial Geisha Fish Bowl. The solid-wood stand receives a deep natural-wood finish and employs concentric circles ...
Jun 19 -
Lake Forest - Everything else
Lena Liu 15" Square Storage Trunk Removable Lid Attached w Brass Latch
Lena Liu 15" Square Storage Trunk Removable Lid Attached w Brass Latches
Chip wood lined. Floral design covered but would also be lovely painted or covered with decorative paper or fabric. You can google FUN ideas
Our home is located near HOAG Hospital
*!* THIS IS NOT A STORE *!* just many items left after closing a vintage decorated creative arts studio / community hospitality center in The ...
Jun 15 -
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Bowers and wilkenson cm9 speaker system in mint condition
My late father upgraded to these just before passing. They have only been used in his a home a handful of times and are mint with no defects or functionality issues.
They sell for 3200.00 a pair. I'm listing the pair for 2300.00 obo.
I am local to Belmont shore/ south long beach. Bellflower blvd exit off the 405. Please text Andy to set up an appointment to hear them. 310-499-6199
Jun 8 -
Long Beach - Musical instruments
stretcher/cot US Army
US Army stretcher/cot. Green canvas cloth, wood handles and metal base on each end. Labeled , US ARMY, ECT CORP DSA 120-68-C-2203. Folds up lengthwise. Measures when opened, 90 inches long to wood handles, 20 inches wide and 5 inches high.
Jun 8 -
Artesia - Sporting goods
Cherry Sleigh Crib/Toddler Bed
Beautiful cherry wood sleigh crib. Has a storage drawer under the bed. Includes a toddler rail that can be switched out with the crib railing when baby gets older. Includes mattress.
Jun 8 -
San Juan Capistrano - Baby & kid stuff
Pottery Barn Desk
wood is in good condition but there are marks on the paint. 4 drawers including file cabinet. text is the best way to contact me. contact me with questions and interest only. Thank you
This ad was posted with the eBay Classifieds mobile app.
Jun 3 -
Dana Point - Everything else
I have multiple office furniture items and some household items for sale. CHEAP.
* Conference table
* Office Credenza
* Filing Cabinets (Wood and Metal)
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* Curio Cabinet
* Dining Room Table (with leaf and 6 chairs)
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* Book Shelves
* Metal Detachable Filing Shelves
Jun 3 -
Anaheim - Business & industrial
200 year old Cherrywood Rocking Chair
A 200 year Cherrywood Rocking Chair
Needs a bit of restoration on the spindles
The seat is of solid Cherrywood. Phone for picture
Jun 2 -
Laguna Woods - Everything else
Old but in good condition Childrens Books
The Tide in the Attic by Aleid Van Rhijn
Castaways in Lilliput by Henry Winterfield
Blue Willow by Doris Gates
Le Timide Petit Lapin By Les Editions Varieities
Rogespierre the scientific Mouse by Pauline Wallace
Mrs Coverlet's Magicians by Mary Nash
A Dog on Barkhan Street by M.S.STOLZ
the Incredible Journey by Sheila Burnford
Secret of the Old Post Box by Dorothy Sterling
The call me Coach ...
moving sale
Moving Sale for serious people only...
- Black Coach
- Wood Table
- Small Fridge
- Plastic Table
- 2 chairs
Jun 2 -
Anaheim - Everything else
Garden Wood Pergola Custom Ready in 3 Days
Great addition for outdoor living in home.
Standard common pergola promotional price :
9' x 9' x 9' = $1200
10' x 10' x 9' = $1300
12' x 12' x 9' = $1500
Can be made in any custom size.
Pick your weather resistant recommended color from:
Natural wood, Cedar, Redwood, Barn Red, Chocolate, Brown, Oak, Golden and Sequoia.
(Or any other color you want.)
Common size ready in 3-5 days including ...
Jun 2 -
Cypress - Everything else
We'll be sending text message alerts for your subscription to


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Clinical Trials
It is not the intention of the Cholangiocarcinoma Foundation to provide specific medical advice. We provide website users with information to help them better understand their health conditions and the current approaches related to prevention, diagnosis, treatment and supportive care. You are urged to always seek the advice of your physician or other qualified healthcare provider.
STUDY NAME: Multicenter, Open-label, Randomized, Controlled Phase III Clinical Study of the Efficacy and Safety of Photodynamic Therapy Using Porfimer Sodium for Injection as Treatment for Unresectable Advanced Perihilar Cholangiocarcinoma
ClinicalTrials.gov Identifier: NCT02082522
A total of 40 centers in North America, Europe and Asia will participate. Please see ClinicalTrials.gov as sites are added.
United States
Arizona, Florida, Minnesota
Mayo Clinic Cancer Center
Contact: Clinical Trials Office
All Mayo Clinic Locations 855-776-0015 (toll-free)
UC Davis Medical Center
Sacramento, California, United States, 95817
Contact: Lisa A Wilson 916-903-9198 firstname.lastname@example.com
Principal Investigator: Shiro Urayama, MD
University of Southern California Keck School of Medicine
Los Angeles, California 90033-1026
Principal Investigator: Jacques Van Dam, MD, Ph.D
Contact: Julie Ann Choudhury, MPH, CHES
Phone: 323-865-3075
Email: email@example.com
Indiana University
Indianapolis, Indiana 46202
Principal Investigator: Lee McHenry, MD
Contact: Sheryl Lynch, RN, CCRC
Phone: 317-944-4228
Email: firstname.lastname@example.com
Oschner Medical Center
Kenner, Louisiana 70065
Principal Investigator: Virendra Joshi, MD
Contact: Casey Eichler, RN
Email: firstname.lastname@example.com
Henry Ford Health System
Detroit, Michigan, 48202
Principal Investigator: Cyrus Piraka, MD
Contact: Joanne Dupuis, RN
Phone: 313-916-8422
North Carolina
Duke University Medical Center
Durham, North Carolina 27710
Principal Investigator: M. Stanley Branch, MD
Phone: 919-681-2941
Email: email@example.com
Southwestern Regional Medical Center, Inc.
Tulsa, Oklahoma 74133
Principal Investigator: Leon Yoder, DO
Contact: Faye Biggs
Phone: 918-286-5448
Email: firstname.lastname@example.com
Thomas Jefferson University
Philadelphia, Pennsylvania 19107
Principal Investigator: David Loren, MD
Contact: Cindi Miller, RN
Phone: 215-955-8108
Email: firstname.lastname@example.com
University of Pittsburgh Medical Center
Pittsburgh, Pennsylvania 15213
Principal Investigator: Adam Slivka, MD
Contact: Kathleen J Bauer, RN
Phone: 412-605-3919
E-Mail: email@example.com
South Carolina
Medical University of South Carolina
Charleston, South Carolina 29425
Principal Investigator: Gregory A. Cote, MD, M.Sc
Contact: Emily DePue
Phone: 843-876-0487
Email: firstname.lastname@example.com
Methodist Dallas Medical Center
Dallas, Texas 75208
Principal Investigator: Paul R Tarnasky, MD
Contact: Nancy L Rosales, CCRP
Phone: 214-947-1284
Email: email@example.com
Virginia Mason Medical Center
Seattle, Washington 98101
Principal Investigator: Seng-Ian Gan, MD
Contact: Sarah Ackermann, CCRC
Phone: 206-341-1295
Email: email@example.com
St. Michael's Hospital
Toronto, Ontario M5B 1W8
Principal Investigator: Paul Kortan, MD
Contact: Maria Cirocco, RN
Phone: 416-864-6060 x2965
Email: firstname.lastname@example.com
Johann-Wolfgang-Goethe Universität Frankfurt
Frankfurt, Hessen 60590
Principal Investigator: Jörg Trojan, Prof Dr med
Contact: Djula Gross
Phone: 49 69 630 15212
Email: firstname.lastname@example.com
Medizinische Hochschule Hannover
Hannover, Niedersachsen 30625
Principal Investigator: Arndt Vogel, Prof Dr med
Contact: Daniela Oehlert
Phone: 49 01 765 326760
Email: firstname.lastname@example.com
Universitaetsklinikum des Saarlandes
Homburg/Saar, Saarland 66421
Principal Investigator: Frank Lammert, Prof Dr med
Contact: Karen Schneider
Phone: 49 68 411 623577
Email: firstname.lastname@example.com
Klinikum Ludwigsburg
Ludwigsburg, Baden Wuerttemberg 71640
Principal Investigator: Karel Caca, Prof Dr med
Contact: Juliane Behn
Phone: 49 71 419 994464
Email: firstname.lastname@example.com
Klinikum Mannheim GmbH
Mannheim, Baden Wuerttemberg 68167
Principal Investigator: Sebastian Belle, Dr med
Contact: Ralf Jesenofsky, Dr rer. nat.
Phone: 49 62 383 5982
Email: email@example.com
Korea, Republic of
Bucheon City
Soonchunhyang University Bucheon Hospital
Bucheon City, Gyeonggi-do 420-767
Principal Investigator: Jong Ho Moon, Prof
Contact: Sun Mi Kim
Phone: 82 32 621 5079
Email: email@example.com
Seoul National University Bundang Hospital
Seongnam-si, Gyeonggi-do 463-707
Principal Investigator: Jin-Hyeok Hwang, Prof
Contact: SooJu Park
Phone: 82 31 787 8216
Email: email@example.com
Konkuk University Medical Center
Seoul, Gwangjin-gu 143-729
Principal Investigator: Young Koog Cheon, Prof
Contact: Hye La Kim
Phone: 82 10 343 67003
Email: firstname.lastname@example.com
Seoul National University Hospital
Seoul 110-744
Principal Investigator: Sang Hyub Lee, MD, PhD
Contact: Ban Seok Lee
Phone: 82 10 747 97170
Email: email@example.com
Severance Hospital, Yonsei University Health System
Seoul, Seodaemun-gu 120-752
Principal Investigator: Seungmin Bang, Prof. MD, PhD
Contact: So Young Jung
Phone: 82 22 227 4156
Email: email@example.com
Michelle Depot, Ph.D.
This research study will evaluate the efficacy and safety of Photodynamic Therapy with porfimer sodium administered with Standard Medical Care (SMC) compared to SMC alone on the overall survival time of patients with non-operable advanced cholangiocarcinoma, a rare cancer of the bile ducts.
Photodynamic therapy (PDT) is a combination of a drug, porfimer sodium (Photofrin), which is activated by a light from a laser that emits no heat. The activation of the drug is done by lighting the abnormal areas using a fiber optic device (very fine fiber like a fishing line that permits light transmission) inserted into a flexible tube with a light called cholangioscope for the bile duct. The light will activate the porfimer sodium concentrated in the abnormal tissue, leading to its destruction.
Enrollment: 200 patients across United States, Canada, South Korea, Germany, and Switzerland
Study Start Date: August 2014
Estimated Study Completion Date: December 2018
- To evaluate the safety and efficacy of photodynamic therapy in advanced nonoperable bile duct cancer.
Required Tests:
- Endoscopic evaluation of the bile duct, CT scan and lab tests.
Potential Side Effects:
- Sensitivity to natural light, temporary inflammation at site of treatment, other typical complications associated with endoscopic evaluation of the bile duct.
INCLUSION CRITERIA – Patients must:
- Males or females aged 18 or older
- Diagnosed with radiologically and biopsy or cytology confirmed inoperable perihilar cholangiocarcinoma Bismuth Tumor Stage III/IV
- Non-menopausal or non-sterile female subjects of childbearing potential must have a negative serum beta-HCG and use a medically acceptable form of birth control
- Able to sign an informed consent
- Diagnostic of cholangiocarcinoma made more than 45 days prior to randomization
- Cholangiocarcinoma with extra-hepatic metastasis or concurrent non-solid malignancy
- Presence or history of other neoplasms (treated during the last five years prior to study entry) other than carcinoma in situ of the cervix or basal carcinoma of the skin
- Previously received photodynamic therapy for cholangiocarcinoma
- Previously undergone surgical resection of the cholangiocarcinoma
- Previously undergone chemotherapy, brachytherapy, or radiotherapy prior to entering the study
- Previously undergone metal stent insertion
- Porphyria or hypersensitivity to porphyrins (constituents of porfimer sodium), gemcitabine, cisplatin or other platinum-containing compounds
- Presence of infection other than the infection of the bile duct (cholangitis)
- Acute or chronic medical or psychological illnesses that prevent endoscopy procedures
- Abnormal blood test results
- Severe impairment of your kidney or liver function
- Very advanced cirrhosis
- Pregnant or intend to become pregnant, breastfeeding or intend to breast-feed during this study
- Participated in another drug study within 90 days before this one
- Unable or unwilling to complete the follow-up evaluations required for the study
STUDY NAME: Study of Low-Dose Radiation Therapy to the Whole Liver in Combination with Gemcitabine and Cisplatin in Intrahepatic Cholangiocarcinoma
ClinicalTrials.gov Identifier: NCT02254681
Virginia Piper Cancer Institute
800 East 28th Street, Suite 602
Minneapolis, MN 55407
Phone: 612-863-7553
Principal Investigator: Srinevas K. Reddy, MD
PI Phone: 612-863-7553
PI E-Mail: firstname.lastname@example.com
Study Coordinator: Laura Rockwell, RN
Study Coordinator Phone: 612-863-9466
Study Coordinator E-mail: firstname.lastname@example.com
In this Phase II study, researchers want to determine whether lower dose radiation therapy improves the response derived from chemotherapy for intrahepatic cholangiocarcinoma by combining chemotherapy treatment with low dose radiation therapy to the entire liver and adjacent lymph nodes. Patients with surgically treatable or untreatable disease, and those with disease confined to or outside the liver are eligible for this study. Patients will have 4 cycles of treatment with each cycle lasting 3 weeks. All patients receive the same treatment. Medical history, physical examination and bloodwork are required.
Enrollment: 45 patients
Study Start Date: 9/25/2014
Estimated Study Completion Date: 01/30/2020
- Determine if the combination of low-dose radiation and chemotherapy results in a better treatment response and longer duration of response compared to that observed with chemotherapy alone
- Determine if the safety of combined low-dose radiation therapy and chemotherapy treatment is substantially different from that of chemotherapy alone
- Determine if low-dose radiotherapy alters the safety of liver surgery for those patients who are candidates for surgery after combined low-dose radiation therapy and chemotherapy treatment
- Have satisfactory heart, lung, and kidney functions to tolerate chemotherapy treatment, and
- Have satisfactory blood test results, and
- Be either fully active or able to walk with assistance
- NOT have had prior chemotherapy, surgery, or radiation for intrahepatic cholangiocarcinoma
- NOT have had prior or current diagnoses of cirrhosis, primary sclerosing cholangitis hepatitis viral infections
- NOT be pregnant or unwilling to use adequate contraception (women)
- Gemcitabine: Flu-like symptoms such as fever, fatigue, muscle aches, headache, cough, and mild nausea/vomiting are common. If a decrease in blood counts occur—the dose of chemotherapy will be adjusted in these cases.
- Cisplatin: Flu-like symptoms such as fever, fatigue, muscle aches, headache, cough, and mild nausea/vomiting are common. A decrease in kidney function may occur—giving fluids and reducing in the dose of chemotherapy usually corrects this problem.
- Radiation: Injury to surrounding structures such as stomach, small intestine, kidney, and spinal cord is possible. However, due to precise direction of the radiation combined with the very low doses used in this study, the likelihood of these side effects are low.
STUDY NAME: PrE0204 - A Multi-Institutional, Single Arm, Two-Stage Phase II Trial of Nab-Paclitaxel and Gemcitabine for First-Line Treatment of Patients with Advanced or Metastatic Cholangiocarcinoma (CCA)
ClinicalTrials.gov Identifier: NCT02181634
A total of 20 US centers will participate. Please see ClinicalTrials.gov as sites are added.
United States, Colorado
Colorado Cancer Research Program
Denver, Colorado, United States, 80222
Contact: Patty Gibson 303-777-2663 email@example.com
United States, Iowa
Siouxland Hematology-Oncology Associates
Sioux City, Iowa, United States, 51101
Contact: Laura Martin 712-252-9329 firstname.lastname@example.com
Contact: Patty Skorey-Solberg 712-252-9358 solbe
United States, Louisiana
Ochsner Medical Center
New Orleans, Louisiana, United States, 70121
Contact: Socea May 504-842-2373 email@example.com
Contact: Shana Lennard 504-842-4498 firstname.lastname@example.com
United States, Massachusetts
University Massachusetts Memorial Medical Center
Worcester, Massachusetts, United States, 01655
Contact: Courtney Coughlin 508-856-2023 firstname.lastname@example.com
Contact: Barbara Butler, RN 508-856-1956 email@example.com
United States, Michigan
University of Michigan Health System
Ann Arbor, Michigan, United States, 48109
Contact: Courtney Wolf 734-936-9238 email@example.com
Contact: Deb Krease 734-764-6847 email@example.com
United States, Minnesota
Metro Minnesota CCOP
St. Louis Park, Minnesota, United States, 55416
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United States, New York
Montefiore Medical Center
Bronx, New York, United States, 10461
Contact: Elaine Keung 718-405-8344 firstname.lastname@example.com
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Knoxville, Tennessee, United States, 37920
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Vanderbilt University/Ingram Cancer Center
Nashville, Tennessee, United States, 37232
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Contact: Marquita Hill 615-875-3260 firstname.lastname@example.com
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Madison, Wisconsin, United States, 53792
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Aurora Cancer Care
Wauwatosa and Green Bay, Wisconsin, United States, 53226
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In this Phase II study, researchers want to evaluate the effectiveness and safety of the combination of nab-paclitaxel and gemcitabine. The effectiveness will be determined by improvement in the length of time during and after treatment, that the cholangiocarcinoma does not get worse. Patients with advanced or metastatic cholangiocarcinoma who are not eligible for curative surgery, transplantation, or ablative therapies will receive nab-paclitaxel and gemcitabine chemotherapy. Patients will receive treatment until the cancer gets worse or spreads. All patients receive the same treatment. Medical history, physical examination, blood work, and a tumor tissue sample are required.
Stage I will enroll 37 patients. If 21 or more patients are progression-free at 6 months, the study will proceed to Stage II and an additional 33 patients will be enrolled.
- Determine the effectiveness of gemcitabine and nab-paclitaxel in patients with advanced cholangiocarcinoma
- Describe the safety and toxicity of the combination of nab-paclitaxel and gemcitabine in patients with advanced cholangiocarcinoma
INCLUSION CRITERIA – Patients must:
- Have a histologically-confirmed diagnosis of cholangiocarcinoma American Joint Committee on Cancer (AJCC) Stage II, III, or IV cholangiocarcinoma (intra-hepatic, extra-hepatic and perihilar) that is not eligible for curative resection, transplantation, or ablative therapies. Tumors of mixed histology are not allowed.
- May have received prior radiation, chemoembolization, radioembolization, or other local ablative therapies, or hepatic resection if completed ≥ 4 weeks prior to registration
- Have satisfactory heart, lung, and kidney functions to tolerate chemotherapy treatment, and
- Have satisfactory blood test results, and
- Be either fully active or able to walk with assistance
EXCLUSION CRITERIA – Patients must:
- NOT have received prior systemic cytotoxic chemotherapy or targeted therapy for this cancer.
- NOT be receiving immunosuppressive medications, including systemic corticosteroids, aside from the following exceptions: used for adrenal replacement, appetite stimulation, acute therapy for asthma or bronchitis (≤ 2 weeks), or anti-nausea/vomiting
- NOT be pregnant or unwilling to use adequate contraception (women)
- MRI or CT scan of the abdomen/pelvic, with contrast
- CT scan of the chest, with contrast
- Basic laboratory work
- Consent to storage of a tumor tissue sample
- Research blood specimens to evaluate for circulating tumor cells
- Gemcitabine: Flu-like symptoms such as fever, fatigue, muscle aches, headache, cough, and mild nausea/vomiting are common. If a decrease in blood counts occur—the dose of chemotherapy will be adjusted.
- Nab-Paclitaxel: Decrease in red blood cells, white blood cells, and platelets, and mild nausea/vomiting are common. A disorder of the nerves which can cause tingling or numbness, with weakness, or decreased sensation or movement may occur.
ClinicalTrials.gov is a registry and results database of publicly and privately supported clinical studies of human participants conducted around the world.
Search for term Cholangiocarcinoma
Search for term Bile Duct Cancer
Video: Participating in a Clinical Trial
This eight minute video features the stories of two clinical research volunteers who provide a personal perspective into the clinical research process. Also in the video are interviews with their family members who offer insight into what it's like when a loved one is undergoing experimental treatment.
Smart Talking about Clinical Studies
This engaging webpage is designed to provide a brief introduction to clinical trials with interactive videos that provide patients with important information about taking part in a clinical trial. You will also find useful information about clinical trials in general and a glossary with definitions of research phrases and terms.
Why They Chose to be Research Volunteers
This video shares the stories of several trial participants including their perspectives and the motivations behind their decision to take part in clinical research.
Clinical Trials 101
In 2010, Dr. Jack Welch from the National Cancer Institute (NCI), joined gave a presentation to the Cholangiocarcinoma Foundation and our community, the purpose of his webinar was to discuss some clinical trial basics and to answer some frequently asked questions.


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While Olivia Munn is esteemed for her comedic chops, highlighted in stints on The Daily Show and Funny or Die, her style is no laughing matter—sleek Michael Kors dresses and decadent Marchesa gowns are all part of her red-carpet record. Now that she has joined HBO's hit drama The Newsroom, as the serious Sloan Sabbith, we are looking forward to seeing more of the actress and her style.
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Wed, 01/09/2010 - 06:04
Armajaro Asset Management has appointed Harry Morley as chief executive officer, having previously been group finance director of Armajaro Holdings since 2008.
Tue, 31/08/2010 - 12:07
Lakeview Investment Manager, an activist fund of hedge funds, has appointed Tony Lissuzzo as portfolio manager of the Lakeview Opportunity Funds.
Mon, 30/08/2010 - 10:26
Law firm Sidley Austin has appointed Alyssa A. Grikscheit as a partner in the Latin America and investment funds, advisers and derivatives practices.
Wed, 25/08/2010 - 12:11
C.M. Capital has appointed finance and investment veteran Bruce W. Madding as president and chief investment officer.
Wed, 25/08/2010 - 06:15
Man has appointed Luke Ellis as head of its multi-manager business.
Fri, 20/08/2010 - 06:20
Merriman Curhan Ford has hired Joe Minton as managing director and head of derivatives to launch an agency options trading desk for institutional investors.
Thu, 19/08/2010 - 16:11
Otkritie, one of the largest financial groups in Russia, has bolstered its research team with the appointment of two senior Russian equity market specialists.
Thu, 19/08/2010 - 14:28
LCH.Clearnet has appointed Michael Davie as chief executive of SwapClear, its interest rate swap clearing service.
Thu, 19/08/2010 - 13:52
Stanley Druckenmiller one of the world's most successful hedge fund managers, decided to stepdown this week, telling investors in a full and frank letter, "For me the disappointment of each interim drawdown over the years has taken a cumulative toll that I cannot continue to sustain."
Thu, 19/08/2010 - 13:46
Wed, 29 Jul 2015 00:00:00 GMT
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Glaxo signs deal with Chroma 'worth £1bn'
Wednesday 24 June 2009
Glaxosmithkline, Europe's biggest pharmaceutical company, continued its policy of doing small scale partnership deals and eschewing so-called mega mergers yesterday by penning an exploratory agreement with biotechnology group Chroma.
The deal, which could eventually be worth as much as $1bn, gives GSK access to a technology that Oxford-based Chroma claims helps molecules suppress identifiable cells more efficiently, and with fewer side effects. The deal is centred on compounds developed to treat inflammatory diseases, such as rheumatoid arthritis.
Ian Nicholson, the chief executive of privately-owned Chroma refused to say how much GSK had paid up-front, but the pharma giant has decided to enter the agreement even before the technology has passed "proof-of-concept" assessments, only after which can it be tested on patients. Under the deal GSK will pay Chroma so-called milestones as the technology clears certain regulatory hurdles, and will get the licence to market the drugs, paying Chroma a royalty on any sales.
"We are delighted to collaborate with GSK to advance novel targeted therapies using our technology. This collaboration provides strong validation of our technology platform and will enable Chroma to progress a broad pipeline of novel agents against a range of serious diseases," said Mr Nicholson.
GSK, which also participated in Chroma's £15m equity raising yesterday, has signed several early stage deals in recent months. "This agreement marks GSK's continued efforts to access the best science and technology platforms worldwide. We believe Chroma's platform has tremendous potential, and look forward to working with Chroma to accelerate the discovery and development of innovative new medicines for patients," said Shelagh Wilson, a vice president at the company.
Mr Nicholson also revealed that Chroma is considering a public listing.
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'Gene drive': Scientists sound alarm over supercharged GM organisms which could spread in the wild and cause environmental disasters
Dutch King Willem-Alexander declares the end of the welfare state
Tom Cruise: Reporters banned from asking actor about Scientology
Yvette Cooper: Our choice is years of Tory rule under Jeremy Corbyn – or a return to a Labour government
Is Britain really full up? Are migrants taking our jobs? Leading academic answers the most common anti-immigration claims
Calais Migrant Crisis: Deputy Mayor of Calais labels Cameron's use of 'swarm' as 'racist' and 'ignorant'
Chris Leslie: Jeremy Corbyn's anti-austerity agenda will harm the poor, says Labour shadow Chancellor
While we fixate on Calais, the Home Office is quietly deporting dozens of migrants on 'ghost flights'
Calais crisis: The seven claims made about the migrants - and the reality
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text:
Written on: 27/07/2004 by Sekhemet (21 reviews written)
Good Points
Nice little notebook, was quite cheap.
Bad Points
I've found nothing wrong with Mine.
General Comments
My Toshiba satellite Pro has been everything I hoped it would be. I didn't want a top of the range lap top, just something I could use to write word documents, surf the internet and play CDs. Mine has got 40GB of Hard Drive as well so I can download until my heart is content. While you will find many more powerful and slimmer and more stylish laptops out there, the Pro A40 never claims to do this, and hence why it is so much cheaper. You want a cheap laptop, get one of these babies!
As rated by our community of reviewers
" Quality is superb " Read More
Written by Underhill_Maddy
" SONY VAIO Laptop SFV153B1YM " Read More
Written by bashy100
" Free coupons for laptops " Read More
Written by stellaruby
" Toshiba Satellite C55-B5298 at searchub.com " Read More
" AMAZING! " Read More
Written by timstallion59


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Expat Guide Berlin for Working and Living in Berlin
InterNations worldwide » Germany expats » Berlin expats » Berlin Guide
Sean Henderson
Living in Berlin, from Canada
"The good thing about InterNations is that I got to know the expat community in Berlin as well as internationally minded locals."
Anna Maria Osario
Living in Berlin, from Argentina
"Through InterNations I met so many other Argentinean expats in Berlin, which made the transition period really easy for me."
InterNations - a trusted Network & Guide for Expats in Berlin
- Build up valuable contacts with like-minded Berlin expats
- Find reliable information and trustworthy tips about the expat life in Berlin
- Join top-class InterNations events to meet fellow expatriates in town
Make the most of living and working in Berlin
Expat living in Berlin raises plenty of questions, for instance: ʺWhat are the requirements from German authorities to get a residence permit?", ʺAre inland flights or national trains the cheaper option to travel from Munich to Berlin?ʺ, or "Who can recommend telecommunication providers in town?"
Finding all this expat information about living and working in Berlin takes a lot of time. Our Berlin expat guide is there to make your relocation to Berlin as easy as possible. Starting with restaurants and nightlife to information about local infrastructure, the guide covers all the different aspects of expat life in Berlin.
InterNations provides you with more info than just for Berlin. We also tell you all about moving to Barcelona or living in London, to name but a few expat hotspots.
Berlin Expat Locations
Restaurants & Nightlife
Restaurante Serrano | Fusion Ibero-Andina
Restaurants & Nightlife
American Church in Berlin
Expat Institutions & Clubs
The Grand
Restaurants & Nightlife
Integrative Psychology and Psychotherapy Practice Jan Wichter
Expat Health Care
Inlingua Berlin
International Schools & Education
Europa- Union Berlin e.V.
Culture & Sights
Restaurants & Nightlife
Information on the Expat Life in Berlin
Are you looking specifically for tax consultants in town or the American consulates in Germany? In addition to our expat guide, the expat directory for Berlin provides you with listings of all expatriate-relevant locations and relocation services in Berlin. Furthermore, you might want to also consider our Berlin expats forum to receive first hand information from your fellow expats.
Simply become a member of InterNations Berlin and you'll be warmly received with a friendly Grüß Gott among our expats living and working in Berlin.
Interested in expat life around the world, though? We have additional information on dozens of countries and cities, from moving to Dubai to live in Paris!
City Guides for Communities in Germany
Click on the map to find communities worldwide:


text:
A strong piece of Christian witness: the manager and employees of a Chick-fil-A in Alabama handed out several hundred free sandwiches to drivers stranded on the road in a snow storm. Those of us in the north are looking at the couple of inches of snow that paralyzed the south and wondering, "What the heck [Read More...]
Chick-fil-A Does A Good Thing
When Archaeology and Epidemiology Meet
The past is always present. A group of scientists has managed to extract DNA from the teeth of two people who died during the Justinian Plague in the 6th century, and tests have confirmed that the same pathogen was at the root of the Black Plague of the 14th century, with mutations that are still [Read More...]
Reliquary of St. John of God
Beautiful. Part of the collection released for use from Wellcome Images, which has a huge collection of medical and scientific images. St. John was a health care worker who founded the Brothers Hospitallers. The reliquary contains a piece of his walking stick. [Read more...]
Tetrobot [App o the Mornin']
Tetrobot and Co. ( [Read more...]
Leo XIII on the Role of "Amateurs" in Defending the Faith
Every now and then I come across a complaint, like this one urging the Register to fire Mark Shea, about lay Catholics who speak and write about the faith. The idea that this role should be left to the "professionals" is rooted in either clericalism or elitism. It has no roots whatsoever in the life [Read More...]
iPieta [App o the Mornin']
iPieta (iOS/Android: $3) is huge app, both in scope and size. At 181 MB, it demands a hefty chunk of real-estate. (By comparison, Cut the Rope only takes up 22 MB.) But it earns its space by placing a staggering library of documents and prayers at your fingertips. The documents are divided into four sections: Bible, [Read More...]
Axe in Face [App o the Mornin']
This is older game–from way back in 2011–but still a lot of fun. If you want to get me to buy your game, just go ahead and name it Axe in Face (iOS: $1). Works every time. If you want to be doubly sure I'll buy it, make sure your main character looks like a [Read More...]
Technology Turned Against Kiev Protestors
Kiev is exploding in protests as Ukraine's president attempts to move the country away from EU membership and closer into the Russian orbit. On Tuesday, anyone in the vicinity of the protests received the following message on their phones: "Dear subscriber, you are registered as a participant in a mass disturbance." Registered. Got that? We [Read More...]


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The Seasons of Syracuse
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text: Closed Captioning ON OFF apply | reset x Text Display Background Enhancements font Times New Roman Arial Comic Sans size T T T T color share link May 19th, 2014 1.8 million pounds of ground beef recalled The Department of Agriculture is announcing a recall of ground beef products from the Wolverine Packing Company. Officials say the beef may be contaminated with E. coli bacteria. More video Sponsored Content Now Playing Volkswagen overtakes Toyota in worldwide sales Sponsored Content Now Playing Bible school van crashes into train, kills 1, injures 10 Sponsored Content Now Playing Nike FuelBand owners to get partial refunds Sponsored Content Now Playing Hailstorm damage forces American Airlines plane to turn back TRENDING Now Playing DIY your summer with YouTube star Eva Gutowski Now Playing Rock on! What famous band was first called Smile? Now Playing Netflix says Olsen twins 'teetering' on joining 'Fuller House' Now Playing Mary J. Blige, Queen Latifah cast in NBC's live musical 'The Wiz' LIFESTYLE Now Playing Just peachy: Sweet skillet peach crisp Now Playing Mother knows best: Perfect products for summer Now Playing Elvis Duran introduces his artist of the month: Grace Now Playing Cyndi Lauper: 'Kinky Boots' are made for walking worldwide Most Watched Now Playing Sponsored Content Mothers of teens missing at sea have faith in their skills: 'They're out there' Now Playing Sponsored Content Hope to It: Helping homeless women start over Now Playing Sponsored Content Madeleine McCann detectives contact Australia about remains Now Playing Sponsored Content Jen Welter becomes first female coach in the NFL Now Playing Sponsored Content Still no sign of 2 Florida teens who are missing at sea Now Playing Sponsored Content Mike Huckabee: Jews support my Holocaust comments Now Playing Sponsored Content Trump's attorney sparks outrage, saying: 'You can't rape your spouse'


text:
Registration takes less than 1 minute.
Retailer diverted cargo, formed chassis fleet, and used untapped drayage to combat West Coast congestion.
Singapore investment company Temasek is seeking buyers for Neptune Orient Lines, parent of ocean carrier APL, according to reports from the Wall Street Journal.
A deal for the Chicago-based transportation management service provider would be worth at least $1.8 billion, according to initial reports from Bloomberg Business.
The second quarter financial results of ocean carriers NYK, MOL and "K" Line reflected a weak Asia-Europe market and strong supply pressure.
The U.S. Senate also passed a long-term highway bill that will be debated by the House after the summer break.
The European Commission will now conduct an in-depth analysis under the EU's merger regulations before coming to a decision on FedEx's $4.8 billion offer to buy TNT.


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IRVING, Texas -- The Dallas defensive players frequently profess their love for Wade Phillips. They hardly know the new head coach.
"I didn't really deal a whole lot with him," nose tackle Jay Ratliff said. "Whoever the head coach is, we just need to give them our all and none the less. That's all I know to do."
Interim coach Jason Garrett doesn't seem concerned with establishing a relationship with the defense. He has more important things on his mind, like trying to prepare the Cowboys to actually perform respectably Sunday afternoon against the Giants.
There won't be a getting-to-know-you period with Garrett. He doesn't have time for that.
"Honestly, we're just going to get going," Garrett said. "We're going to get going to work. It's going to happen early on Wednesday morning and they are going to understand the New York Giants are going to present a great challenge for us on Sunday afternoon."
Dez: 'No pressure' after inking $70 million deal
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Rolando McClain to open camp on PUP
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Defense barely knows Jason Garrett