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At least 775 records · Page 43Linked to original sources
PubMed2003

A light-activated probe of intracellular protein kinase activity.

The first example of a photoactivated probe of intracellular enzymatic activity is described. The caged derivative of a fluorescent protein kinase C peptide-based sensor was prepared by modifying the free hydroxyl group of a phosphorylatable serine moiety with a photolabile appendage that blocks phosphoryl transfer. We have demonstrated that the caged sensor allows one to (1) sample PKC activity with exquisite temporal precision, (2) control the relative amount of active sensor available for phosphorylation, and (3) examine protein kinase activity at multiple time points.

Acetamides↗
PubMed2005

Catalytic asymmetric synthesis of chiral allylic esters.

Trichloroacetimidate derivatives of prochiral (Z)-2-alken-1-ols react at room temperature with carboxylic acids to give chiral 3-acyloxy-1-alkenes in high enantiopurity in the presence of di-mu-acetatobis[(eta5-(S)-(pR)-2-(2'-(4'-methylethyl)oxazolinyl)cyclopentadienyl,1-C,3'-N)(eta4-tetraphenylcyclobutadiene)cobalt]dipalladium (COP-OAc) or its enantiomer. This reaction has broad scope, proceeds with predictable high stereoinduction, is accomplished at room temperature using high substrate concentrations and low catalyst loadings, and likely proceeds by a novel mechanism.

Acetamides↗
PubMed2002

Method for the gas chromatographic assay with mass selective detection of trichloro compounds in corks and wines applied to elucidate the potential cause of cork taint.

To investigate the role of trichloro compounds as a potential cause of "cork taint" in wine, an assay for trichloroanisole (TCA) and trichlorophenol (TCP) in corks and wine was developed utilizing solid phase extraction on a C(18) cartridge followed by gas chromatography with mass selective detection. Recovery and imprecision for TCA were 86-102 and 1.6-5.8%, respectively, and for TCP 82-103% and 1.7-3.9%, respectively. Limits of detection and quantitation were 0.1 and 2 ng/L, respectively, for TCA, and 0.7 and 4 ng/L, respectively for TCP. A survey of 2400 commercial wines revealed a higher incidence of cork taint in white wine than in red and in wines utilizing composite cork closures; wines from central Europe and Spain had higher overall rates of contamination and those from Canada and Italy the lowest. Significant but modest associations were found between the TCA and TCP contents of the wines and corks, but many wines exhibiting cork taint had low or undetectable concentrations of TCA. Over a 12-month period, experimentally bottled wines exhibited a slow increase in TCA and TCP content while cork closures manifested a decrease; most bottles showing cork taint contained low levels of TCA, and TCP concentrations were well below the sensory threshold. Neither compound was cytotoxic to human cell lines in culture up to final concentrations of 500 ng/mL. It was concluded that these two trichloro compounds are, at most, minor components of cork taint in commercial wines.

Analysis of Variance↗
PubMed2003

Use of trichloroacetimidate linker in solid-phase Peptide synthesis.

A solid-phase method for the preparation of C-terminal amino-alcohol-containing peptides using activated Wang resin is presented. A diverse set of (fluorenylmethoxy)carbonyl (Fmoc) protected amino alcohols was found to load rapidly and efficiently. The synthetic utility of this approach was demonstrated through the direct synthesis of the peptide drug octreotide with excellent yield and purity. These results suggest that the use of trichloroacetimidate activated resins offers an attractive alternative in the preparation of this class of peptides.

Acetamides↗
PubMed2004

Solid-phase synthesis of complex oligosaccharides using a novel capping reagent.

Solid-phase-supported oligosaccharide synthesis of a core N-glycan tetrasaccharide and of a trisaccharide containing the Galili antigen is reported. The synthesis is based on a hydroxymethylbenzyl benzoate spacer-linker system attached to the Merrifield resin, O-Fmoc-protected O-glycosyl trichloroacetimidates as glycosyl donors, and benzoyl isocyanate as a capping reagent for low-reactivity hydroxy groups. In this way, the target molecules could be efficiently obtained with little byproduct formation, and hence final purification was convenient.

Acetamides↗
PubMed2005

From solution phase to "on-column" chemistry: trichloroacetimidate-based glycosylation promoted by perchloric acid-silica.

[reaction: see text] Activation of ester-protected glycosyl trichloroacetimidate donors by perchloric acid immobilized on silica afforded 1,2-trans disaccharides in 60-90% yields. Applying this approach to one-pot sequential glycosylation resulted in efficient syntheses of the N-linked glycan trimannoside and Le(X) and Le(A) trisaccharides in very good yield (76%, 62%, and 59% yields, respectively). Solution phase reactions were also translated to a solid phase format; priming the top of a standard silica chromatography column with perchloric acid immobilized on silica facilitated "on-column" glycosylation with subsequent "in situ" purification of products. Coupling yields from this approach were comparable to those obtained from the corresponding solution-phase disaccharide couplings. A series of glycosylated amino acids were also synthesized in high yield with use of the on-column approach.

Acetamides↗
PubMed2002

Concerning the origin of the high beta-selectivity of glycosidation reactions of 2-deoxy-2-iodo-glucopyranosyl trichloroacetimidates.

[structure: see text] Studies on the glycosidation reactions of conformationally constrained glycosyl imidates 8a and 8b were performed to evaluate the possible involvement of "conformationally inverted" oxonium ion intermediates in glycosidation reactions with 2-deoxy-2-iodo-glucopyranosyl donors. The mechanistic implications of this study are discussed, and intermediates 23 and 24 are invoked to rationalize the observed beta-selectivities.

Carbohydrate Conformation↗
PubMed2003

Automated synthesis of a protected N-linked glycoprotein core pentasaccharide.

[structure: see text] Described is the first automated solid-phase synthesis of the core N-linked pentasaccharide, common to all N-linked glycoproteins via stepwise assembly from mono- and disaccharide building blocks. The challenging beta-mannosidic linkage was incorporated by the inclusion of a disaccharide trichloroacetimidate. This automated synthesis provides rapid access to an oligosaccharide common to an entire class of glycoconjugates.

Acetamides↗
PubMed2004

3-fluoro-6-tert-butyltetrahydropyranosyl trichloroacetamidates. "chiral auxiliary donors" for hydroxyalkyl radicals.

An improved THP-based chiral auxiliary for hydroxyalkyl radicals is reported. The key modifications involve introduction of a fluorine substituent at C-3 to make the acetal center more robust and the use of Schmidt's trichloroacetamidate glycosylation methodology for efficient attachment of the auxiliary to the radical precursor. The resulting chiral hydroxyalkyl radical equivalents add to methyl 2-trifluoroacetoxyacrylate with selectivities ranging from 9:1 (0 degrees C) to 15:1 (-78 degrees C). [structure: see text]

Acetamides↗
PubMed2007

Synthesis of protected chiral vicinal diaminoalcohols by diastereoselective intramolecular benzylic substitution from bistrichloroacetimidates.

An efficient synthesis of chiral dihydrooxazines (2) from 1-aryl-2-amino-propane-1,3-diols (1) via the corresponding bistrichloroacetimidate intermediates has been developed. In this transformation, one trichloroacetimidate acts as a leaving group and the other acts as a nucleophile. The cyclization proceeds through an SN1 mechanism to provide trans-dihydrooxazines with complete diastereoselectivity irrespective of the absolute configuration of the benzylic alcohol. The transformation of 2 into other selectively protected aminodiols is also documented. [reaction: see text].

Amino Alcohols↗
PubMed1999

2-Deoxy-2-iodo- and 2-deoxy-2-bromo-alpha-glucopyranosyl trichloroacetimidates: highly reactive and stereoselective donors for the synthesis of 2-deoxy-beta-glycosides.

[formula: see text] 2-Deoxy-2-iodo- and 2-deoxy-2-bromoglucopyranosyl trichloroacetimidates 8-10 and 22 are extremely useful precursors of 2-deoxy-beta-glycosides. These reactive glycosyl donors undergo highly stereoselective glycosidation reactions at -78 degrees C with a range of glycosyl acceptors using TBS-OTf as the activating agent. beta-Glycosides are obtained with > or = 19:1 selectivity in six of the seven examples reported herein.

Acetamides↗
PubMed1978

Factors influencing lipoprotein lipase activity in choline deficiency.

Subcutaneous injections of the lipotropic agent, ethyl trichloracetate, to rats with established choline deficiency raised their plasma triglycerides by 60% and completely removed the hyperglyceridaemic response of Triton WR 1339. The plasma triglyceride levels of choline-supplemented rats were depressed slightly by ethyl trichloracetate administration, which was effective in abolishing response to Triton WR 1339. Lipoprotein lipase activity of epididymal fat pad was stimulated 60% while plasma lipoprotein was not stimulated by ethyl trichloracetate. The increased peripheral removal of low-density lipoprotein-triglyceride complex, allowing greater use to be made of existing apo-proteins, may explain the lipotropic character of the ester.

Adipose Tissue↗
PubMedDate not supplied

Quantitation of methamphetamine and amphetamine in urine by capillary GC/MS. Part I. Advantages of trichloroacetyl derivatization.

A urine assay for methamphetamine and amphetamine that is compatible with our existing high-volume GC/MS assays for other drugs of abuse has been developed. Trichloroacetic anhydride is used for derivatization and its derivative is substantially less volatile than other commonly used derivatives. The internal standard is the primary amine 2-methylphenethylamine. The procedure utilizes an initial liquid-liquid extraction, a liquid-liquid back extraction for specimen cleanup, and derivatization for removal of excess trichloroacetic anhydride and acid by-product. A GC temperature of about 180 degrees C results in retention times of approximately 2.8, 3.2, and 4.3 min for amphetamine, the internal standard, and methamphetamine, respectively. Five ions are monitored: 91+, 118+, 188+ for amphetamine; 105+, 118+ for 2-methylphenethylamine; and 91+, 118+, 202+ for methamphetamine. Full scan GC/MS data from a variety of other derivatives are examined and used to illustrate the advantages of derivatizing molecules with strongly electronegative atoms near the reaction site. This situation forces fragmentation patterns in which positive charges are located on larger and structurally acceptable identifying mass fragments of the original methamphetamine or amphetamine molecule.

Acetic Anhydrides↗
PubMed1997

Comparative genotoxicity of halogenated acetic acids found in drinking water.

Three short-term assays (SOS chromotest, Ames fluctuation test and newt micronucleus test) were performed to detect the genotoxic activity of organohalides, compounds likely to be found in chlorinated and/or ozonated drinking water: monochloro-, dichloro- and trichloroacetic acids and monobromo-, dibromo- and tribromoacetic acids. With the SOS chromotest, only three of the chemicals studied (dichloroacetic acid, dibromo- and tribromoacetic acids) were found to induce primary DNA damage in Escherichia coli PQ 37. In the Ames fluctuation test, all the compounds except monochloroacetic acid showed mutagenic activity in Salmonella typhimurium strain TA100. In these two in vitro tests, a good correlation between increasing number of substituents and decreasing mutagenicity was observed. Namely, the toxicity of brominated and chlorinated acetic acids decreased when the number of substituents increased. The newt micronucleus test detected a weak clastogenic effect on the peripheral blood erythrocytes of Pleurodeles waltl larvae for trichloroacetic acid only.

Acetates↗
PubMed1994

Dichloroacetic acid and related compounds: induction of prophage in E. coli and mutagenicity and mutation spectra in Salmonella TA100.

We performed three types of studies to evaluate the genotoxicity of the chlorinated organic solvent perchloroethylene (PERC or tetrachloroethylene) and its volatile metabolites, trichloroacetyl chloride (TCAC) and trichloroacetic acid (TCA), as well as the volatile metabolites of trichloroethylene, i.e. dichloroacetyl chloride (DCAC), dichloroacetic acid (DCA), and 2,2,2-trichloroethanol (TCE). In the first set of studies, which involved the evaluation of these chemicals in the Microscreen prophage-induction assay, only DCA (+S9) was genotoxic, producing 6.6-7.2 plaque-forming units/mM. This places DCA among the weakest of the > 100 chemicals that have been identified previously as inducers of prophage in this assay. In the second set of studies, which involved the evaluation of these chemicals in the vapor state in Salmonella TA100 using a Tedlar bag vaporization technique, DCA (+/-S9), DCAC (-S9), and TCAC (+/-S9) were mutagenic, producing 3-5x increases in revertants/plate relative to the background. S9 enhanced the mutagenic potency of DCA but had no effect on the mutagenic potency of TCAC. The potencies ranged from 0.7 to 3.9 rev/p.p.m., resulting in a potency ranking of DCA > DCAC approximately TCAC. The lowest effective concentrations were 50-300 p.p.m., which are similar to those for ethylene oxide and epichlorohydrin in this assay. In the third set of studies, the mutation spectra of DCA, DCAC, and TCAC were determined at the base-substitution allele hisG46 of Salmonella TA100. DCA and DCAC induced primarily G.C-->A.T transitions, whereas TCAC induced primarily G.C-->T.A transversions, which was also the predominant mutation among the background revertants.(ABSTRACT TRUNCATED AT 250 WORDS)

Base Sequence↗
PubMed1997

Haloalkanoate dehalogenase II (DehE) of a Rhizobium sp.--molecular analysis of the gene and formation of carbon monoxide from trihaloacetate by the enzyme.

A 3-kb EcoRI fragment of genomic DNA from a Rhizobium sp. cloned into pUC19 endowed Escherichia coli K-12 with the ability to grow, albeit slowly, with 2-chloropropionic acid as substrate. The construct expressed weakly a gene that encoded a non-stereospecific 2-chloropropionic acid dehalogenase (dehalogenase II; DehE). The dehE gene was not closely linked to the organism's other two dehalogenase genes, dehD and dehL. The derived amino acid sequence of DehE showed little identity with DehD or DehL, but there was significant identity to two other dehalogenases that act non-selectively on 2-chloropropionic acid. The fragment carried a truncated ORF upstream of dehE that was 51% identical to a positively acting regulatory protein, DehR, required for expression of a Pseudomonas putida dehalogenase gene. In its complete form this gene could encode the Rhizobium sp. dehalogenase-regulatory protein. DehE dehalogenated tribromoacetic acid completely, forming stoichiometric amounts of carbon monoxide and carbon dioxide as the other products.

Acetates↗
PubMed2003

Trichloroacetylation of some cyclic enamines.

The pyrrolidine and morpholine enamines of cyclic ketones such as cyclohexanone and cyclopentanone were successfully diacetylated at alpha- and alpha'-positions with trichloroacetyl chloride using zinc catalyst. Morpholine enamines of the cyclic ketones gave acetylated morpholine in good yields besides the corresponding diacetylated cyclic enamines. When the same reactions were performed by using triethylamine without using zinc, monoacetylation products of the same enamines were synthesized.

Amines↗