Abstract
Stereoselective catalytic intermolecular C-H amination of complex molecules is reported. Site-selective functionalizations occur with very good yields up to 91% and excellent d.e.s up to 99%. However, the precise nature of the nitrene C-H insertion remains a matter of debate despite several physical...
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PMID: 20931128
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Abstract
Synthetic strategies are described to synthesize the calix[4]arene diamine 4 of partial cone (paco) conformation, which on condensation with 9-anthracene carbaldehyde forms the chemosensor 5 in paco conformation. The chemosensor 5 undergoes fluorescence enhancement in the presence of Ni(2+) ions.
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PMID: 20890542
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Abstract
An efficient method for highly diastereoselective synthesis of quaternary α-trifluoromethyl α-amino acids was developed via indium mediated allylation of (R)-phenylglycinol methyl ether based imines of trifluoropyruvate in good yields with high diastereoselectivities at room temperature; to illust...
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PMID: 20856962
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Abstract
Emergency department physicians, along with hospitalists and interventional cardiologists, provide first-line care for patients experiencing symptoms potentially associated with acute coronary syndromes (ACS). Because these health care providers encounter and manage patients with varying degrees of...
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PMID: 21068524
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Abstract
Tricarbonylchloro-rhenium(i) (1-4) and catecholato-platinum(ii) complexes (6, 7) of diimine ligands bearing phenol and O-protected phenol substituents have been prepared and fully characterised including single crystal structure analyses of 1, 4 and 7. The redox behaviour of the catecholato platinum...
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PMID: 20820607
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Abstract
The long-lived room temperature (RT) intra-ligand phosphorescence ((3)IL) of dbbpy Pt(II) bis(acetylide) (dbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine) complexes Pt-1 (λ(em) = 629 nm, τ = 118 μs, quantum yield φ = 17.5%) and Pt-3 (λ(em) = 658 nm, τ = 73.6 μs, φ = 2.1%) (dbbpy = 4,4'-di-tert-bu...
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PMID: 20835478
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Abstract
Streptomyces sp. GF3587 and 3546 were found to be imine-reducing strains with high R- and S-selectivity by screening using 2-methyl-1-pyrroline (2-MPN). Their whole-cell catalysts produced 91 mM R-2-methylpyrrolidine (R-2-MP) with 99.2%e.e. and 27.5 mM S-2-MP (92.3%e.e.) from 2-MPN at 91-92% convers...
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PMID: 20820664
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Abstract
The current syntheses of imines from benzylamines are often performed in organic solvents or under harsh reaction conditions. Clean oxidation of primary benzylamines to imines has been successfully achieved using H(2)O(2) in water at room temperature catalyzed by V(2)O(5). Among the 10 imine product...
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PMID: 20714661
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Abstract
Chiral N-phosphonylimines were found to react with lithium phosphites to provide various substituted chiral α-amino phosphonates in excellent yields (94-97%) and diastereoselectivities (93:7-99:1). The types of bases utilized for generating the nucleophile are crucial for the effectiveness of asymm...
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PMID: 20887612
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Abstract
I phosphorylation via activation of PKA and CaMK II, which are mediated by cyclic AMP levels and Ca(2+) influx.
Copyright (c) 2010 Elsevier B.V. All rights reserved....
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PMID: 20080157
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Abstract
We studied hypoxia-induced dynamic changes in the balance between PKA and PKA-counteracting phosphatases in the microfluidic environment in single cells using picosecond fluorescence spectroscopy and intramolecular fluorescence resonance energy transfer (FRET)-based sensors of PKA activity. First, w...
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PMID: 20453101
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Abstract
The conjugation between nanotubes, coated with different doses of polyethylene imine (PEI) and hepatitis A virus (HAV) was investigated by scanning electron microscopy, Z-potential, thermogravimetric and differential thermal analysis, transmission electron microscopy, energy dispersive x-ray diffrac...
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PMID: 20404402
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Abstract
We examined the difference between the intermolecular Heck-type reactions of imines and of olefins. It was found that in the intermolecular Heck-type coupling of imines, the apparent activation barrier of migratory insertion was as high as +35 kcal mol(-1), which should be the main obstacle of the r...
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PMID: 20437448
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Abstract
The enantioselective reductive cyclization of gamma-chloro N-(tert-butanesulfinyl)ketimines towards the short and efficient synthesis of (S)- and (R)-2-arylpyrrolidines (ee >99%) is described for the first time by treatment with LiBEt(3)H and subsequent acid deprotection.
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PMID: 20358047
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Abstract
A simple, safe and efficient system that can specifically transfect peripheral sensorial neurons can bring new answers to address peripheral neuropathies. A multi-component non-viral gene delivery vector targeted to peripheral nervous system cells was developed, using poly(ethylene imine) (PEI) as s...
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PMID: 20093157
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Abstract
Reaction screening of nucleophilic reaction partners for addition to N-diphenylphosphinylimines employing lanthanum(III) triflate as a catalyst and trifluoroacetic anhydride (TFAA) as an activator is reported. A number of tandem processes leading to novel chemotypes including aza-Prins/intramolecula...
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PMID: 20394364
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Abstract
Intermolecular radical amination reactions of various primary, secondary, and tertiary alkyl radicals by using trimethylstannylated benzophenone imine A as a novel radical acceptor to provide imines of type B are described. These imines are readily reduced with NaBH(4) to the corresponding secondary...
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PMID: 20361746
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Abstract
New chiral beta-(sulfonylamino)sulfinylimidates are synthesized in high overall yield and excellent diastereomeric excess via highly anti-selective Mannich-type reactions of chiral N-tert-butanesulfinyl imidates with N-tosyl aldimines. Deprotection of the beta-(sulfonylamino)sulfinylimidates gave ac...
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PMID: 20361742
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Abstract
The Rh(I)-catalyzed addition of alkenyl and aryl MIDA boronates to N-tert-butanesulfinyl aromatic and aliphatic imines proceeds in good yields (up to 99%) and with very high selectivity (98:2 to >99:1). In comparison to trifluoroborates, higher yields and selectivities are observed for the addition...
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PMID: 20387846
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Abstract
A fascinating mechanistic study of ynamido-palladium-pi-allyl complexes is described that features isolation of a unique silyl ketenimine via aza-Claisen rearrangement, which can be accompanied by an unusual thermal N-to-C 1,3-Ts shift in the formation of tertiary nitriles and a novel cyclopentenimi...
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PMID: 20337418
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Abstract
This paper describes a system for the detection of nitroaromatic explosives consisting of a portable detector based on a specific fluorescent material. The developed sensor was able to perform an ultra trace detection of explosives, such as trinitrotoluene (TNT) or its derivate 2,4-dinitrotoluene (D...
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PMID: 20188960
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Abstract
We reoptimized the catalyst preparation method, and a catalyst derived from Sm(5)O(O-iPr)(13) showed broader substrate generality as well as higher reactivity and stereoselectivity compared to Sm(O-iPr)(3). The optimal system with Sm(5)O(O-iPr)(13) was applicable to various aromatic, heteroaromatic,...
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PMID: 20218689
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Abstract
The reactivity of the trigonal bipyramidal iron(I) complex [SiP(iPr)(3)]Fe(N(2)) ([SiP(iPr)(3)] = (2-iPr(2)PC(6)H(4))(3)Si(-)) toward organoazides has been examined. 1-Adamantylazide was found to coordinate the iron center to form stable [SiP(iPr)(3)]Fe(eta(1)-N(3)Ad). Aryl azides instead afforded u...
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PMID: 20199026
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Abstract
We report the electrical transport characteristics of conjugated oligonaphthalenefluoreneimine (ONI) wires having systematically varied lengths up to 10 nm. Using aryl imine addition chemistry, ONI wires were built from gold substrates by extending the conjugation length through imine linkages betwe...
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PMID: 20218660
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Abstract
The addition of various Grignard reagents to P-t-butyl-P-phenyl-N-phosphinoyl benzaldimine provides a stereoselective method for the synthesis of chiral phosphinoylamines.
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PMID: 20221518
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Abstract
NO is an important mediator of microvascular patency and blood flow. The purpose of this study was to examine the role of enhanced eNOS activity in attenuating sepsis-induced neutrophil-endothelial cell interactions. Microslides coated with human umbilical vein endothelial cells were stimulated with...
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PMID: 19536045
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Abstract
1,4-Butanediol is able to deliver two equivalents of H(2) in hydrogen-transfer reactions to ketones, imines, and alkenes. Unlike simple alcohols, which establish equilibrium in the reduction of ketones, 1,4-butanediol acts essentially irreversibly owing to the formation of butyrolact...
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PMID: 20112336
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Abstract
Following four foliar applications of Nativo 75 WG (trifloxystrobin 25% + tebuconazole 50%) on grapes @ 175 and 350 g/ha, resulting in active applications of trifloxystrobin @ 43.75 and 87.5 g a.i./ha and that of tebuconazole @ 87.5 and 175 g a.i./ha, the average initial deposits of trifloxystrobin...
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PMID: 20039018
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Abstract
We describe a strategy for inducing enantioselectivity in reactions of protio-iminium ions, wherein a chiral catalyst interacts with the highly reactive intermediate through a network of noncovalent interactions. This interaction leads to an attenuation of the reactivity of the iminium ion and allow...
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PMID: 20167783
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Abstract
Highly enantio- and diastereoselective organocatalytic Mannich reactions of glycine Schiff bases with N-Boc-protected imines are described. Imines were generated in situ from bench-stable alpha-amido sulfones. Catalysis mediated by a cinchona alkaloid thiourea provided optically acti...
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PMID: 20085291
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Abstract
Enantiomerically enriched sulfonamides were synthesized by the radical addition of an acetal to enantiomerically pure N-sulfinyl imines using dimethylzinc-air and boron trifluoride diethyl etherate. Higher levels of stereocontrol were observed by using a mesitylenesulfinyl group. Furthermore, an ami...
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PMID: 20118594
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Abstract
We report that some of the synthetic inhibitors designed for Src kinase target have both antioxidant and kinase inhibition properties....
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PMID: 20653236
PDF is available here.
Abstract
Asymmetric addition under mild conditions of dialkyl phosphites on aldimines derived from cinnamaldehyde catalyzed by the inexpensive chiral organocatalyst (R)-3,3'-[4-fluorophenyl](2)-1,1'-binaphthol phosphate has been found effective to give new alpha-amino-phosphonates 9 in moderate yields (30-65...
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PMID: 20736906
PDF is available here.
Abstract
Our results reveal that the inhibition of iNOS in the hypoxic lung reduced the damage observed before the treatment with 1400W, suggesting that iNOS-derived NO(*) may exert a negative effect on this organ during hypoxia/re-oxygenation. These findings are notable, since they indicate that any therape...
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PMID: 20663293
PDF is available here.
Abstract
A fluorescent and colorimetric probe bearing salicylaldehyde hydrazone functionality has been prepared for cyanide sensing. The detection of cyanide was performed via the nucleophilic attack of cyanide anion on the imine group of the probe with a 1:1 binding stoichiometry, which could be confirmed b...
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PMID: 19836585
PDF is available here.
Abstract
We assert that cervical cancer contain a subpopulation of tumor initiating cells with stem-like properties, thus facilitating the approach to therapeutic strategies aimed at eradicating the tumorigenic subpopulation within cervical cancer....
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PMID: 19787230
PDF is available here.
Abstract
We show that dynamic covalent chemistry is an efficient tool for functionalizing surfaces in such a way that their interfacial properties can be varied controllably in space and time. Modulation of pH is used to tune the fast, selective and reversible attachment of functional amines (with different...
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PMID: 21378957
PDF is available here.
Abstract
The Strecker reaction is one of the most important multicomponent reactions developed, leading to alpha-aminonitriles that are versatile substrates for many synthetic applications. In the present study, this reaction type has been applied to a double dynamic covalent resolution protocol, leading to...
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PMID: 19807186
PDF is available here.
Abstract
These results indicated that the positive HA/PEI/DNA ternary complexes (HA:PEI charge ratio, 7.5%) can target malignant breast cancer cells with high CD44 level and might be a promising candidate vector for gene therapy....
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PMID: 19545193
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Abstract
Highly enantioselective rhodium-catalyzed addition of arylboroxines to N-phosphinoylaldimines was realized by the steric tuning of a diphenylphosphorus moiety to a di(o-tolyl)phosphorus moiety of a chiral amidomonophosphane. The presence of MS 4 A in a 5:1 solvent mixture of dioxane-propanol was ess...
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PMID: 19739616
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Abstract
We herein formulated and characterized an in situ-forming gel consisting of sodium carboxymethylcellulose (CMC) and poly(ethyleneimine) (PEI) and examined its use as an in vivo scaffold for rat bone marrow stem cells (rBMSCs). The changes of zeta potential, size, and viscosity of CMC solutions with...
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PMID: 19366343
PDF is available here.
Abstract
N-Aryl, N-alkyl, N-alkoxy, and N-amino derivatives of 2-[bis(pentafluorophenyl)boryl]benzylideneamine were synthesized by the condensation reactions of 2-[bis(pentafluorophenyl)boryl]benzaldehyde with the corresponding amines. Their structures were investigated by NMR and X-ray crystallographic anal...
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PMID: 19778080
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Abstract
We have explored the highly enantioselective Strecker hydrocyanation of a wide range of aromatic, alpha,beta-unsaturated, heterocyclic, and aliphatic aldimines with good to excellent conversions and ees up to 98% in the presence of catalytic amounts of Yb(OTf)(3)-pybox complexes.
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PMID: 20448986
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Abstract
Recent developments in catalytic C-H amination are discussed in this feature article. The careful design of reagents and catalysts now provides efficient conditions for exquisitely selective intramolecular as well as intermolecular nitrene C-H insertion. The parallel emergence of C-H activation/amin...
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PMID: 20448953
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Abstract
The rhodium-catalyzed oxidative coupling of aromatic imines with alkynes effectively proceeds via regioselective C-H bond cleavage to produce indenone imine and isoquinoline derivatives.
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PMID: 20448973
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Abstract
A general rhodium-catalyzed oxidative coupling reaction between internal alkynes and aryl aldimines is described. This process affords 3,4-disubstituted isoquinolines in good yield and high regioselectivity. Preliminary mechanistic studies suggest that the C-N bond formation arises from the reductiv...
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PMID: 19705909
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Abstract
Highly enantio- and diastereoselective organocatalytic Mannich additions of alpha-isothiocyanato imides to sulfonyl imines are reported. Enantiomerically enriched syn-alpha,beta-diamino acid derivatives can be obtained in excellent yields using catalyst loadings as low as 0.25 mol %.
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PMID: 19642698
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Abstract
We report here a simple approach to chiral catalyst formation: coupling of an available pool of Brønsted acids, namely, amino acid derivatives, with tunable ligands on copper catalysts. This system can be used to generate many different chiral environments simply by changing the amino acid or lig...
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PMID: 19630398
PDF is available here.
Abstract
Phenyl azides with powerful electron-donating substituents are known to deviate from the usual photochemical behavior of other phenyl azides. They do not undergo ring expansion but form basic nitrenes that protonate to form nitrenium ions. The photochemistry of the widely used photoaffinity labeling...
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PMID: 19624129
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Abstract
We replaced the imino moiety of each base with N1-deazaadenosine. This single-atom change resulted in an 8-fold loss in k(obs) for A9 and displacement of the base from the active site; no effects were observed for A10. We propose that the imino moiety of A9 promotes a key water-mediated contact that...
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PMID: 19634899
PDF is available here.
Abstract
This paper describes the synthesis of a series of Pd(IV) complexes of general structure (N~C)(2)Pd(IV)(O(2)CR)(2) (N~C = a rigid cyclometalated ligand; O(2)CR = carboxylate) by reaction of (N~C)(2)Pd(II) with PhI(O(2)CR)(2). The majority of these complexes undergo clean C-O bond-forming reductive el...
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PMID: 19459631
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Abstract
Using pd(cf(3)co(2))2/(S,S)-f-Binaphane as the catalyst, an efficient enantioselective synthesis of sultams was developed via asymmetric hydrogenation of the corresponding cyclic imines with high enantioselectivities. The hydrogenation products can be conveniently transformed to chiral homoallylic a...
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PMID: 19507826
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Abstract
We developed a simple and convenient copper-catalyzed method for the synthesis of quinoline-2-carboxylate derivatives through sequential intermolecular addition of alkynes onto imines and subsequent intramolecular ring closure by arylation. The efficiency of this system allowed the reactions to be c...
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PMID: 19572501
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Abstract
The catalytic enantioselective Mannich reaction promoted by chiral bifunctional organocatalysts is described. The treatment of beta-ketoesters with N-Boc-aldimines under mild reaction conditions afforded the corresponding beta-amino beta-ketoesters with excellent diastereoselectivities (up to 100:0...
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PMID: 19555053
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Abstract
A series of mononuclear and dinuclear zinc compounds, [Na(Et(2)O)](2)[((H)L(iPr))Zn-Zn((H)L(iPr))] x Et(2)O (1), [Zn(2)((H)L(iPr))(3)K(2)(Et(2)O)(2)](n) (2, (H)L(iPr) = [(2,6-(i)Pr(2)C(6)H(3))NCH](2)), [Zn((H)L(Mes))(2)] (4, (H)L(Mes) = [(2,4,6-Me(3)C(6)H(2))NCH](2)), and [ZnL(Mes)(2)Na(2)(THF)(2)]...
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PMID: 20449092
PDF is available here.
Abstract
We previously showed that adducts could be quantified by high-performance liquid chromatography with electrochemical detection following proteolytic hydrolysis, and that the concentration of adducts in serum of overdose patients correlated with toxicity. The following study examined the pharmacokine...
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PMID: 19439490
PDF is available here.
Abstract
We have expressed two recombinant forms of the P. gingivalis PAD in Escherichia coli, a truncated form with a 43-amino acid N-terminal deletion and the full-length form of PAD as predicted from the DNA sequence. Both forms contain a poly-His tag and Xpress epitope at the N-terminus to aid in detecti...
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PMID: 19545534
PDF is available here.
Abstract
We investigated the in-vitro effects of E5555 on platelet function beyond PAR-1 blockade in healthy volunteers and CAD patients treated with aspirin (ASA) with or without clopidogrel. Conventional aggregation induced by 5 microM ADP, 1 microg/ml collagen, 10 microM TRAP, whole blood aggregation with...
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PMID: 19572075
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Abstract
We report here a cellular model for screening NOS inhibitors. Stable transformants were generated by overexpressing rat neuronal NOS in HEK 293T cells. The enzyme was activated by introducing calcium ions into cells, and its activity was assayed by determining the amount of nitrite that was formed i...
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PMID: 19362065
PDF is available here.