ATP and AMP formation from ADP in the presence of cyclodextrin

A new nonenzymatic formation of ATP from ADP was observed in the presence of cyclodextrin in a phosphate buffer of pH 7.00 at 37.0°C under at mospheric conditions. Time conversion curves were obtained in the presence of -cyclodextrin and heptakis-(2,6-dimethyl)--cyclodextrin. The effect of adding -cyclodextrin, MgCl₂, phosphate buffer and creatine was examined kinetically as well as the effect of cyclohexanol as an inhibtor.     

Leaving group effects in gas-phase substitutions and eliminations

Using a methodology recently developed for studying the product distributions of gas-phase S(N)2 and E2 reactions, the effect of the leaving group on the reaction rate and branching ratio was investigated. Using a dianion as the nucleophile, reactions with a series of alkyl bromides, iodides, and trifluoroacetates were examined. The alkyl groups in the study are ethyl, n-propyl, n-butyl, isobutyl, isopropyl, sec-butyl, and tert-butyl. The data indicate that leaving group abilities are directly related to the exothermicities of the reaction processes in both the gas phase and the condensed phase. Gas-phase data give a reactivity order of iodide > trifluoroacetate > bromide for S(N)2 and E2 reactions. Previous condensed phase data indicate a reactivity order of iodide > bromide > trifluoroacetate for substitution reactions; however, the basicities of bromide and trifluoroacetate are reversed in the condensed phase so this reactivity pattern does reflect the relative reaction exothermicities. Aside from this variation, the gas-phase data parallel condensed phase data indicating that the substituent effects are rooted in the nature of the alkyl substrate rather than in differences in solvation. The experimental data are supported by calculations at the MP2/6-311+G(d,p)//MP2/6-31+(d) level.     

Oxidation of Two α-Hydroxy Acids by Vanadium(V)

Summary. The pathways for the oxidation of tartaric acid and citric acid by vanadium(V) in perchloric acid medium have been studied at 303K by following the formation of vanadium(IV) spectrophotometrically at 760nm. The oxidation reaction displays fractional order dependence with respect to both the -hydroxy acids concentrations as well as fractional (tartaric acid) and first order (citric acid) dependencies with respect to the perchloric acid concentration. It does not matter at all whether the ionic strength was varied or was maintained constant. The reaction rate remains essentially constant with increasing ionic strength in the tartaric acid oxidation, but decreases slightly in the citric acid case. A decrease of the dielectric constant of the reaction medium results in a rate decrease in the tartaric acid oxidation and in a rate enhancement in the citric acid reaction. The activation parameters were obtained from studies of the reactions at different temperatures (293 to 313K). Based on the experimentally determined rate laws oxidation mechanisms and theoretical rate laws were proposed.Received April 8, 2003; accepted May 10, 2003 Published online September 18, 2003     

Adsorption and Recovery of Ionic Surfactants by β-Cyclodextrin Polymer

The adsorption and recovery of ionic surfactants, such as dodecylbenzenesulfonic acid (DBS) and benzalkonium chloride (BKC), from an aqueous solution were studied using the β-cyclodextrin polymer (β-CDP). BKC always demonstrated a higher adsorption efficiency than DBS in batch tests, isotherms, and column tests. The adsorption characteristics of the surfactants seemed to be caused by inclusion into β-CD, and they were easily determined using the Langmuir adsorption isotherm. Furthermore, the surfactants adsorbed by β-CDP were easily released by shaking it with a mixture of water and methanol. Recovery efficiency was dependent on the mixture ratio of the solvent, and regenerated β-CDP was reusable as an adsorbent.     

The synthesis of oligosaccharide-branched cyclodextrins and their interaction with concanavalin A

New oligosaccharide-branched -cyclodextrins having a various oligosaccharides in a primary hydroxyl group of -cyclodextrin(CD) were synthesized and examined for the interaction with the immobilized concanavalin A(ConA) compared with 6-O-glucosyl and maltosyl CD. Oligosaccharides were converted to lactones at the reducing end, which was connected with 6-monoamino--CD forming an amide bond. For the analysis of the interaction between ConA immobilized on an aminosilane-hydrogel surface and various oligosaccharide CDs, a biosensor of the FISONS IAsys apparatus based on a resonant mirror detector (RMD) was used. As a result, it interacted with immobilized ConA and both maltosyl--CD(3) and maltosyl--CD(6), and glucosylglucono-amide--CD(7) with the association constants, K_a of 134, 833 and 8730 M^–1, respectively.     

Reaction of ethyl 3-ethoxymethylene-2,4-dioxovalerate and ethyl ethoxymethyleneoxaloacetate with 3-aminopyrazole analogs. Synthesis and chemistry of 3,6,7-trisubstituted pyrazolo[1,5-a]pyrimidine derivatives

The chemical reactivity of a series of 3-substituted-6-acetyl-7-carbethoxypyrazolo[l,5-a]pyrimidines ( 6a,b,c ) and 3-substituted-6,7-dicarbethoxypyrazolo[1,5-a]pyrimidines ( 7a,b,c ), prepared by the condensations of the 3-aminopyrazole analogs ( 3a,b,c ) with ethyl 3-ethoxymethylene-2,4-dioxovalerate ( 1 ) or ethyl 3-ethoxymethyleneoxaloacetate ( 2 ), was investigated. Catalytic hydrogenation of 6 or 7 afforded 4,7-dihydro derivatives ( 8 or 9 ). Treatment of 6a,b with acetic acid and water underwent ring transformation into 6H-pyrazolo[1,5-a][1,3]diazepin-6-ones ( 17a,b ). By treatment with phenylhydrazine compounds of type 6 underwent cyclization to yield 2H-dipyrazolo[1,5-a:4′,3′-e]pyrimidines ( 18a,b,c ). Compounds 6 or 7 were treated with an excess of diazomethane at room temperature to give 5-methyl-6H-cyclopropa[5a,6a]pyrazolo-[1,5-a]pyrimidines ( 24 and 25 ) in excellent yields. However, when this reaction was carried out under ice cooling, only compounds of type 23 were isolated. Reaction of 6a with ethyl diazoacetate is also described.     

Synthesis of GDP-5-thiosugars and their use as glycosyl donor substrates for glycosyltransferases

Two thiopyranoside analogues of GDP-sugars, GDP-5-thio-d-mannose (14) and GDP-5-thio-l-fucose (15), were synthesized. The syntheses included the phosphorylations of tetra-O-acetyl-5-thio-d-mannosyl bromide (4) and tri-O-benzoyl-l-fucosyl bromide (6) with silver dibenzyl phosphate, deprotection of the phosphate groups, and condensation of the deprotected phosphates with GMP-imidazolidate (13) in the presence of MgCl(2). These GDP-sugar analogues were found to be donor substrates for alpha(1,2)mannosyltransferase and alpha(1,3)fucosyltransferase, affording a 5-thiomannose-containing disaccharide (18) and a 5-thiofucose-containing trisaccharide (21), respectively. The conformation of the disaccharide analogue 18 was similar to that of its native counterpart by ROESY. These findings for GDP-5-thiosugars together with previous demonstrations of enzymatic transfer from UDP-5-thiosugars will allow the production of panels of oligosaccharide analogues with hydrolase-resistant properties.     

In situ chemical aminoacylation with amino acid thioesters linked to a peptide nucleic acid

tRNA-specific chemical aminoacylation was achieved with nonnatural amino acids. A nonnatural amino acid was activated as a thioester derivative, and the latter was linked through a spacer to the N-terminal of a 9-mer peptide nucleic acid that is complementary to the 3'-terminal region of yeast phenylalanine tRNA. Efficient aminoacylation was observed when the amino acid thioester-spacer-PNA conjugate was mixed with the tRNA. The PNA-assisted aminoacylation was also successful in an Escherichia coli in vitro protein synthesizing system that contained an orthogonalized tRNA. The in situ aminoacylation/in vitro translation gave a mutant protein in which the nonnatural amino acid was incorporated into the position directed by a CGGG 4-base codon/anticodon pair.     

Hydrogenation of 1,3-butadiene over magnesium oxide prepared by the decomposition of magnesium oxalate

In order to find the cause of the high activity for hydrogenation of 1,3-butadiene over a magnesium oxide catalyst prepared by thermal decomposition of magnesium oxalate, ESR and poisoning techniques were used. The cause of the high activity was attributed to large surface area and electron donating properties, which might be related to the surface basicity.

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Thermal analysis in numerical thermodynamic modeling of solid fuel conversion

Detailed kinetic models dominate in combustion modeling. However, their application is often complicated by insufficient knowledge of a mechanism and reaction rates for heterophase interactions especially as applied to gasification. The novel approach using thermodynamic model of extreme intermediate states (MEIS) could make up an efficient alternative. MEIS is strictly deterministic and simple in structure. Along with the search for the final equilibrium, it allows partial equilibria to be found and various macroscopic phenomena to be taken into account, e.g., transport phenomena and kinetic rates. The core problem in MEIS construction is formulation of macrokinetic constrains whose form depends on the problem statement and accessible information on the process. Thermal analysis has been deployed to infer proper constraints for modeling of wooden biomass gasification. The advantage of the method consists in much higher availability of the initial information compared with detailed kinetics. Model results are in good agreement with experiment.