Molecular recognition with C-clamp porphyrins: synthesis, structural, and complexation studies

The cholesterolaemic effect of 2 hypercholesterolaemic diets was tested in 12 rat inbred strains. Diet I is a commercial diet supplemented with 2.0% (w/w) cholesterol and 5.0% (w/w) olive oil; diet II is identical to diet I with addition of 0.5% (w/w) sodium cholate. Strains with the highest plasma cholesterol response after diet I (BN and LEW) also had the highest cholesterol response after diet II (hyperresponders, mean response > 3.5 mmol/l). In the strains DA, SHR, BC, WAG, LOU, PVG and BUF the strain mean cholesterol response remained below 1.3 mmol/l after both diets (hyporesponders). Strains F344 and OM had an intermediate cholesterol response after both diets (normoresponders, mean response between 1.3 and 3.5 mmol/l). Only in the strains LOU, PVG and SHR there appeared to be a significant higher cholesterol response after diet II when compared with the cholesterol response after diet I. In the strain WKY this difference was of a borderline significance (P = 0.052) and this strain turned from a normoresponder after diet I into a hyperresponder after diet II. Liver cholesterol levels as measured after feeding diet II for two weeks also appeared to be strain-specific. No correlation was found between the plasma cholesterol response after diet II and the liver cholesterol levels. Changes in plasma phospholipid and triglyceride levels have been measured for both diet I and diet II. For group means a correlation between the cholesterol response and the change in phospholipid levels was found (r = 0.86 for diet I, P < 0.001 and r = 0.76 for diet II, P < 0.01). No such correlation was found for triglyceride levels.     

非平衡体系络合交换分离钆铒的研究

以P204为萃取剂及二乙基三胺五乙酸（DTPA）为水相络合剂,研究了用非平衡溶剂萃取法从氯化稀土溶液中分离钇 铒的水相pH值,适合时间,DTPA浓度等因素对分离钇铒的影响,结果表明,在水相加入DTPA,钇的萃取速度较快,铒的萃取速率较慢,控制两相混合时间,用非平衡溶剂萃取法可有效分离钇铒。     

Anodic synthesis of 8-methylnonanoic acid and 8-methylnon-trans-6-enoic acid. The synthesis of dihydrocapsaicin and capsaicin (author''s transl)]

The author describes a rare case of the torsion of the pregnant fallopian tube with the macerated fetus and simultaneous intrauterine pregnancy. He points out dignostic difficulties in such cases.     

Chemical synthesis of D-ribo-phytosphingosine-1-phosphate, a potential modulator of cellular processes

OBJECTIVE: The nonpenetrating, arcuate-legged clip has proved its ability to provide a high-quality microvascular anastomosis. This study assessed the feasibility of constructing a coronary end-to-side anastomosis on the beating heart with a novel mechanical, sutureless anastomotic device that applies 12 circumferential clips simultaneously. METHODS: In 14 consecutive pigs (70-90 kg), the left internal thoracic artery (diameter, 3 mm) was grafted to the left anterior descending coronary artery (diameter, 3 mm) by means of a one-shot anastomotic stapler prototype. Endothelial denudation, medial necrosis, and intimal hyperplasia were analyzed quantitatively and compared with those seen in conventionally sutured anastomoses (n = 4). RESULTS: In 8 of 14 anastomoses, the one-shot anastomotic stapler successfully applied all 12 clips circumferentially across the everted arteriotomy edges. In the remaining, either 1 (n = 4) or 3 and 4 adjoining malaligned clips had to be replaced manually with a single-clip applicator. Coronary occlusion was limited to approximately 3 minutes. At follow-up, all anastomoses were patent angiographically. At 2 days, in 2 of 7 cases, a local coronary dissection was observed, and there was a considerable loss of endothelial cells and medial damage. At 28 days, however, minimal intimal hyperplasia was seen at the anastomotic lining, although more pronounced when compared with conventionally sutured anastomoses. CONCLUSIONS: The one-shot anastomotic stapler prototype enabled short-occlusive (3 minutes), sutureless end-to-side grafting on the beating porcine heart. In spite of early endothelial and medial damage and 2 local dissections, all anastomoses remained patent with minimal intimal hyperplasia at 4 weeks.     

Retrobiosynthetic NMR studies with 13C-labeled glucose. Formation of gallic acid in plants and fungi

The biosynthesis of gallic acid was studied in cultures of the fungus Phycomyces blakesleeanus and in leaves of the tree Rhus typhina. Fungal cultures were grown with [1-13C]glucose or with a mixture of unlabeled glucose and [U-13C6]glucose. Young leaves of R. typhina were kept in an incubation chamber and were supplied with a solution containing a mixture of unlabeled glucose and [U-13C6]glucose via the leaf stem. Isotope distributions in isolated gallic acid and aromatic amino acids were analyzed by one-dimensional 1H and 13C NMR spectroscopy. A quantitative analysis of the complex isotopomer composition of metabolites was obtained by deconvolution of the 13C13C coupling multiplets using numerical simulation methods. This approach required the accurate analysis of heavy isotope chemical shift effects in a variety of different isotopomers and the analysis of long range 13C13C coupling constants. The resulting isotopomer patterns were interpreted using a retrobiosynthetic approach based on a comparison between the isotopomer patterns of gallic acid and tyrosine. The data show that both in the fungus and in the plant all carbon atoms of gallic acid are biosynthetically equivalent to carbon atoms of shikimate. Notably, the carboxylic group of gallic acid is derived from the carboxylic group of an early intermediate of the shikimate pathway and not from the side chain of phenylalanine or tyrosine. It follows that the committed precursor of gallic acid is an intermediate of the shikimate pathway prior to prephenate or arogenate, most probably 5-dehydroshikimate. A formation of gallic acid via phenylalanine, the lignin precursor, caffeic acid, or 3,4, 5-trihydroxycinnamic acid can be ruled out as major pathways in the fungus and in young leaves of R. typhina. The incorporation of uniformly 13C-labeled glucose followed by quantitative NMR analysis of isotopomer patterns is suggested as a general method for biosynthetic studies. As shown by the plant experiment, this approach is also applicable to systems with low incorporation rates.     

Controlled chemical modification of hyaluronic acid: synthesis, applications, and biodegradation of hydrazide derivatives

Controlled modification of the carboxylic acid moieties of hyaluronic acid with mono- and polyfunctional hydrazides leads to biochemical probes, biopolymers with altered physical and chemical properties, tethered drugs for controlled release, and crosslinked hydrogels as biocompatible scaffoldings for tissue engineering. Methods for polyhydrazide synthesis, for prodrug preparation, for hydrogel crosslinking, and for monitoring biodegradation are described.     

微波消解-硼酸络合-原子吸收光谱法测定钢中全铝

试验了微波消解-硼酸络合-原子吸收光谱法测定钢中全铝的主要条件及效果,提出以硼酸络合消除氢氟酸的影响,避免了高氯酸发烟带来的某些弊端。试样在国产MK-Ⅲ型实验室微波炉上消解,适宜的消解条件为:消解压力1 5MPa,消解时间3min。试验表明,微波消解样品方法与熔融回收残渣铝的传统方法相比具有快速、简便、结果准确等显著优点。     

Reversible induction of ATP synthesis by DNA damage and repair in Escherichia coli. In vivo NMR studies

Early metabolic events in Escherichia coli exposed to nalidixic acid, a topoisomerase II inhibitor and an inducer of the SOS system, were investigated by in vivo NMR spectroscopy, a technique that permits monitoring of bacteria under controlled physiological conditions. The energetics of AB1157 (wild type) and of its isogenic, SOS-defective mutants, recBC, lexA, and DeltarecA, were studied by 31P and 19F NMR before, during, and after exposure to nalidixic acid. The content of the NTP in E. coli embedded in agarose beads and perfused at 36 degreesC was found to be 4.3 +/- 1.1 x 10(-18) mol/cell, yielding a concentration of approximately 2.7 +/- 0.7 mM. Nalidixic acid induced in the wild type and mutants a rapid 2-fold increase in the content of the NTP, predominantly ATP. This induction did not involve synthesis of uracil derivatives or breakdown of RNA and caused cell proliferation to stop. Removal of nalidixic acid after 40 min of treatment rescued the cells and resulted in a decrease of ATP to control levels and resumption of proliferation. However, in DeltarecA cells, which were more sensitive to the activity of the drug, ATP elevation could not be reversed, and ATP content continued to increase faster than in control cells. The results ruled out association between the elevation of ATP and the induction of the SOS system and suggested involvement of a process reminiscent of apoptosis in the stimulation of ATP synthesis. Thus, the presence of the RecA protein was found to be essential for reversing the ATP increase and cell rescue, possibly by its function in repair of DNA damage.     

Poly-2'-deoxy-2'-fluoro-cytidylic acid: enzymatic synthesis, spectroscopic characterization and interaction with poly-inosinic acid

The polymerization of 2'deoxy-2'-fluoro-cytidine-diphosphate (dCflDP) by polynucleotide phosphorylase is barely detectable in the presence of Mg++ under usual experimental conditions for polymerization of nucleoside diphosphates. High concentrations of enzyme have to be used to accomplish the synthesis. Mn++ is a better activator than Mg++ for the reaction. cCflDP inhibits the polymerization of CDP and has a Km=8.8X10-3M, six times higher than CDP.- The polymer, poly (dCfl), ressembles in many respects poly(C), but not poly(dC): the acid selfstructure forms at similar pK's; interaction with poly(I) yields a 1:1 complex the CD spectrum of which is similar to that of poly(I).poly(C). Finally, the Tm's of poly(I).poly(dCfl) are comparable to those of poly(I).poly(C).     

硅、锰系TRIP钢成分及热处理工艺的优化

本文采用正交设计及方差分析法,对获取良好TRIP效应的Si、Mn系低碳低合金钢化学成分及热处理工艺进行了优化.结果表明:化学成分为0.28%C-1.62%Si-1.09%Mn的钢,经等温淬火工艺790℃×4min→400℃×3min处理后,获得最佳综合机械性能,强塑积达322.33MPa·%.     

Inclusion complexation of propofol with 2-hydroxypropyl-beta-cyclodextrin. Physicochemical, nuclear magnetic resonance spectroscopic studies, and anesthetic properties in rat. trapani@ippo.uniba.it

An aqueous formulations of propofol 1 can be prepared by solubilizing it in the presence of 2-hydroxypropyl-beta-cyclodextrin (HP-beta-CD). This is potentially useful for parenteral administration of the drug. The aqueous solubility of 1 linearly increased as a function of HP-beta-CD concentration and showed features of an AL type diagram. Thermodynamic parameters were obtained by using the temperature dependence of the stability constant at temperatures of between 25 and 37 degrees C. The results indicate that complex formation is enthalpically, rather than entropically, driven and that it may involve van der Waals (dispersive) forces, rather than hydrophobic interactions. The structure of the inclusion complex propofol/HP-beta-CD was investigated in D2O, using 1H and 13C NMR spectroscopy. These studies revealed that the whole aromatic ring, as well as part of the isopropyl groups of the guest molecule, is located inside the HP-beta-CD cavity, while the hydroxy group is located at the rim of the wider cavity end. The geometrical features of the inclusion complex 1-HP-beta-CD are confirmed by 1D NOE difference spectra and molecular modeling experiments. The anesthetic activity in rat was investigated, and it was found that there are significant differences in induction time and sleeping time between 1 solubilized in the presence of HP-beta-CD and the formulation currently used (Diprivan), which is a 1% w/v oil/water emulsion.     

Effect of tinidazole, metronidazole and nitrofurazone on nucleic acid synthesis in Clostridium bifermentans

Coplanar lines of different orientations rotating in depth and viewed in parallel projection may appear to rotate in different directions and reverse independently of each other, or they may appear coplanar and all reverse together. The frequency of the latter "grouped" appearance for lines with an orientation range of 30 degrees was a function of the number of lines in a given space. Grouping was greater for lines converging to an implicit vanishing point and for lines with collinear edges regardless of their orientations. Line length, and by inference, interline separation also had effect of the nature of the response.     

Chemical synthesis of the precursor molecule of the Aequorea green fluorescent protein, subsequent folding, and development of fluorescence

The present paper describes the total chemical synthesis of the precursor molecule of the Aequorea green fluorescent protein (GFP). The molecule is made up of 238 amino acid residues in a single polypeptide chain and is nonfluorescent. To carry out the synthesis, a procedure, first described in 1981 for the synthesis of complex peptides, was used. The procedure is based on performing segment condensation reactions in solution while providing maximum protection to the segment. The effectiveness of the procedure has been demonstrated by the synthesis of various biologically active peptides and small proteins, such as human angiogenin, a 123-residue protein analogue of ribonuclease A, human midkine, a 121-residue protein, and pleiotrophin, a 136-residue protein analogue of midkine. The GFP precursor molecule was synthesized from 26 fully protected segments in solution, and the final 238-residue peptide was treated with anhydrous hydrogen fluoride to obtain the precursor molecule of GFP containing two Cys(acetamidomethyl) residues. After removal of the acetamidomethyl groups, the product was dissolved in 0.1 M Tris. HCl buffer (pH 8.0) in the presence of DTT. After several hours at room temperature, the solution began to emit a green fluorescence (lambdamax = 509 nm) under near-UV light. Both fluorescence excitation and fluorescence emission spectra were measured and were found to have the same shape and maxima as those reported for native GFP. The present results demonstrate the utility of the segment condensation procedure in synthesizing large protein molecules such as GFP. The result also provides evidence that the formation of the chromophore in GFP is not dependent on any external cofactor.     

Simple, efficient protocol for enzymatic synthesis of uniformly 13C, 15N-labeled DNA for heteronuclear NMR studies

The use of uniformly 13C,15N-labeled RNA has greatly facilitated structural studies of RNA oligonucleotides by NMR. Application of similar methodologies for the study of DNA has been limited, primarily due to the lack of adequate methods for sample preparation. Methods for both chemical and enzymatic synthesis of DNA oligonucleotides uniformly labeled with 13C and/or 15N have been published, but have not yet been widely used. We have developed a modified procedure for preparing uniformly 13C,15N-labeled DNA based on enzymatic synthesis using Taq DNA polymerase. The highly efficient protocol results in quantitative polymerization of the template and approximately 80% incorporation of the labeled dNTPs. Procedures for avoiding non-templated addition of nucleotides or for their removal are given. The method has been used to synthesize several DNA oligonucleotides, including two complementary 15 base strands, a 32 base DNA oligonucleotide that folds to form an intramolecular triplex and a 12 base oligonucleotide that dimerizes and folds to form a quadruplex. Heteronuclear NMR spectra of the samples illustrate the quality of the labeled DNA obtained by these procedures.     

Parameters of self-reinforcement and depression.

Assessed the levels of 3 components of self-reinforcement (self-expectation, self-evaluation, and self-reward) in 2 groups of 40 hospitalized psychiatric patients (clinically depressed and clinically nondepressed). Tasks included a word association measure, the WAIS Digit Symbol subtest, and a task involving decisions that would benefit the ward. The depressed group showed significantly lower levels on all 3 variables, which were significantly interrelated. Ss in the depressed group were significantly more reinforcing to others on all 3 variables than to themselves, as compared with the nondepressed group. Despite lower levels of self-reinforcement, there were no differences between the 2 groups' objective performances. The overall results suggest qualifications to a self-reinforcement theory of depression. (31 ref) (PsycINFO Database Record (c) 2010 APA, all rights reserved)