A comparative study of various computational approaches in calculating the structure of pyridoxal 5'-phosphate (PLP)-dependent beta-lyase protein. The importance of protein environment

Various computational approaches, using molecular mechanics (Amber), semiempirical (AM1), density functional (B3LYP), and various ONIOM methods, have been comparatively investigated for the structure of Escherichia coli NifS CsdB protein. The structure of the entire monomer containing 407 amino acid residues and 579 surrounding water molecules has been optimized. The full geometry optimization in the "active site-only" approach (including only active site atoms) has been found to give the largest root-mean-square (RMS) deviation from the X-ray structure; a much better agreement has been achieved by keeping the atoms leading to the backbones of some amino acids frozen in their positions in the X-ray structure. The best agreement has been attained by including the surrounding protein in the calculations using the two-layer ONIOM (B3LYP:Amber) approach. The results presented in this study conclusively demonstrate the importance of the protein/active-site interaction on the active-site structure of the enzyme. The present theoretical study represents the largest system studied at the ONIOM level to date, containing 7992 atoms, including 84 atoms in the QM region and rest in the MM region.     

Helical poly(3-methyl-4-vinylpyridine)/amino acid complexes: preparation, characterization, and biocompatibility

Helical poly(3-methyl-4-vinylpyridine) (P3M4VP)/amino acid complexes have been prepared via acid-base reaction of the achiral polymer with D and L amino acids: alanine, leucine, valine, serine and phenylalanine. The circular dichroism (CD) spectra of P3M4VP/D- and L-alanine complexes in CH(3)OH/H(2)O show opposing (near mirror image) Cotton effect signals at 278.4, 274.8 and 270.8 nm, indicating the formation of enantiomeric secondary structures. The formation of the enantiomeric structures is supported by observed [alpha](D)(25) values of -3.0 and +3.0 for the P3M4VP/D-alanine and P3M4VP/L-alanine complexes, respectively. The preparation of helical P3M4VP/amino acid complexes has been carried out in CH(3)OH and H(2)O at pH 1.8 and 2.7. The intensities of the Cotton effect signals were good. For example, for the P3M4VP/L-alanine complexes in CH(3)OH/H(2)O and H(2)O (pH 1.8), the second Cotton effect signal around 275-277 nm show [theta;] values of 49 980 and 79 210 deg . cm(2) . dmol(-1), respectively. The formation of the helical secondary structure is rapid. The acid-base reaction between P3M4VP and L-alanine in CH(3)OH/H(2)O, in 10 min, show a CD spectrum with Cotton effect signals at 274 and 272 nm with [theta] values of 27,000 deg . cm(2) . dmol(-1) and -36,000 deg . cm(2) . dmol(-1), respectively. P3M4VP permits ready conformational reorientation on complexation with amino acids, but once the helical P3M4VP/amino acid complexes are formed, it is stable at room temperature. P3M4VP is not compatible with HeLa ovarian cancer cells, but the helical P3M4VP/amino acid complexes are compatible with HeLa cells. The complexes minimally interfere with the adhesion and growth of HeLa cells on complex surfaces. Helical poly(3-methyl-4-vinylpyridine)/D- and L-alanine complexes support the attachment and growth of HeLa cells. The micrographs shows HeLa cells after three days: left panel: on P3M4VP/L-alanine complex; right panel: on P3M4VP/D-alanine complex.     

Spectroscopic Study on Interaction of β-Cyclodextrin with Triprolidine Hydrochloride

The complexation of triprolidine hydrochloride （TRP） and β-cyclodextrin （β-CD） in deuterium oxide was investigated by 400 MHz 1^H NMR spectroscopy. The 800 MHz 2D ROESY data revealed that two 1 ：1 and one 2 ： 1 β-CD-TRP inclusion complexes were formed. Both aromatic moieties （p-tolyl and pyridyl ring） has entered into the β-CD cavity, confirming the existence of two different equilibria for 1 ： 1 inclusion complexes in which p-tolyl ring of the guest is more tightly held by the host cavity. The ROE intermolecular interactions provided the plausible structures of these 1 ： 1 and 2 ： 1 stoichiometric inclusion complexes of β-CD-triprolidine hydrochloride in solu- tion.     

Two-dimensional double-quantum 2H NMR spectroscopy in the solid state under OMAS conditions: correlating 2H chemical shifts with quasistatic line shapes.

Solid-state 2H NMR spectroscopy is a well-established and versatile method to study molecular orientation and dynamics in selectively deuterated samples. Herein, we introduce a 2D 2H double-quantum (DQ) NMR experiment performed under fast magic-angle spinning with a slight offset of the magic angle (OMAS). The experiment combines 2H chemical-shift resolution with DQ-filtered quasistatic 2H line shapes. In this way, it is possible to separate 2H resonances and to independently determine 2H quadrupole couplings at multiple sites. While 2H chemical shifts are resolved in the 2H DQ dimension, the quadrupole parameters can be obtained from characteristic line shapes which are reintroduced in the second dimension by the magic-angle offset. The 2D 2H DQ OMAS experiment is demonstrated on L-histidine which was deuterated at multiple sites by recrystallisation from D2O.     

Feasibility of a liquid-phase microextraction sample clean-up and liquid chromatographic/mass spectrometric screening method for selected anabolic steroid glucuronides in biological samples

Anabolic androgenic steroids (AAS) are metabolized extensively in the human body, resulting mainly in the formation of glucuronide conjugates. Current detection methods for AAS are based on gas chromatographic/mass spectrometric (GC/MS) analysis of the hydrolyzed steroid aglycones. These analyses require laborious sample preparation steps and are therefore time consuming. Our interest was to develop a rapid and straightforward method for intact steroid glucuronides in biological samples, using liquid-phase microextraction (LPME) sample clean-up and concentration method combined with liquid chromatographic/tandem mass spectrometric (LC/MS/MS) analysis. The applicability of LPME was optimized for 13 steroid glucuronides, and compared with conventional liquid-liquid extraction (LLE) and solid-phase extraction (SPE) procedures. An LC/MS/MS method was developed for the quantitative detection of AAS glucuronides, using a deuterium-labeled steroid glucuronide as the internal standard. LPME, owing to its high specificity, was shown to be better suited than conventional LLE and SPE for the clean-up of urinary AAS glucuronides. The LPME/LC/MS/MS method was fast and reliable, offering acceptable reproducibility and linearity with detection limits in the range 2-20 ng ml(-1) for most of the selected AAS glucuronides. The method was successfully applied to in vitro metabolic studies, and also tested with an authentic forensic urine sample. For a urine matrix the method still has some unsolved problems with specificity, which should be overcome before the method can be reliably used for doping analysis, but still offering additional and complementary data for current GC/MS analyses.     

Influence of the exchange‐correlation functional in all‐electron calculations of the vibrational frequencies of corundum (α‐Al2O3)

The equilibrium structural parameters, high‐ and low‐frequency dielectric tensors, Born effective charges, and Γ‐point vibrational frequencies of bulk Al₂O₃ corundum are calculated by using the periodic, ab initio program CRYSTAL, which adopts an all‐electron Gaussian‐type basis set. The effect of basis set and the performance of three different functionals, i.e., LDA, PW91, and B3LYP, are discussed. The mean absolute deviation from the measured frequencies is as small as 7 cm^?1 for both the LDA and B3LYP functionals, indicating that these functionals perform extremely well in this case. The mean absolute deviation increases to 18 cm^?1 when the PW91 functional is used. All three functionals reproduce the equilibrium geometry of corundum to a high level of accuracy, with LDA and B3LYP outperforming PW91 slightly. The comparison of the current all‐electron calculations with previous plane‐wave, pseudo‐potential calculations shows an overall similar performance. The results of isotopic substitution for both Al and O are also presented. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Printed plastic electronics and paperlike displays

Plastic electronic materials and high‐resolution printing methods may be important technologies for new classes of consumer electronic devices that are lightweight, mechanically flexible and bendable, and that can cover large areas at low cost. This article summarizes some of our recent work in this area. It focuses on the materials and patterning techniques that we used to produce plastic active‐matrix backplane circuits for a type of paperlike display. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3327–3334, 2002     

Cycloarsanes (AsCF3)n (n = 4, 5) – Precursors for the Highly Reactive Diarsene F3CAs=AsCF3

Tetrakis(trifluoromethyl) cyclotetraarsane (F₃CAs)₄ ( 2 ) was used to repeat the UV initiated [4+2]‐cycloaddition reaction of the diarsene F₃CAs=AsCF₃ ( 1 ) with cyclohexa‐1,3‐diene (CHD) and to isolate single crystals of the cycloadduct 4 for a X‐ray diffraction analysis. 4 crystallizes in the space group and contains the diarsene group in its E‐configuration. 2 was also applied for [2+2]‐cycloaddition reactions of 1 with tBuC≡P and MeC≡CNⁱPr₂, but in contrast to positive results with (F₃CP)₄ the products were too labile for isolation. However, 2 was successfully used at room temperature as precursor for coordinating 1 as π‐donor ligand to the Pd(PPh₃)₂ complex fragment yielding η²‐bis(trifluoromethyl)diarsene‐bis(triphenylphosphane)‐palladium(0) 5 , which was characterized by X‐ray diffraction of single crystals and by spectroscopic investigations (NMR, IR, MS). Attempts to prove the existence of the diarsene 1 , generated by different methods, by spectroscopic studies very probably failed due to its extreme reactivity, not allowing the necessary concentrations for detection. Quantum chemical calculations of the stability of 1 with respect to dimerization, the stability of the [2+2]‐cycloadduct with 1‐di(isopropyl)aminopropyne and the energy difference between 4 and the 2,3‐dimethyl‐1,3‐butadiene cycloadduct of 1 were performed to understand the considerable differences between 1 and the related diphosphene F₃CP=PCF₃.     

2＇，3＇－O－异亚丙基－5＇－O－［N，N－二（2－氯乙基）磷酰胺基］核苷的合成

２＇，３＇－Ｏ－异亚丙基－５＇－Ｏ－［Ｎ，Ｎ－二（２－氯乙基）磷酰胺基］核苷的合成陈茹玉，迟国臣，陈小茹（南开大学元素有机化学研究所，天津，３０００７１）关键词核苷，亚磷酰化，抗肿瘤活性很多核苷类化合物具有很好的抗肿瘤、抗病毒等生物活性，某些化合物已...     

Electrocatalytic Properties of a Novel Poly‐1‐Naphthylamine‐Modified Electrode Using Ascorbic Acid as Molecule Probe

A glassy carbon electrode was modified with an electropolymerized film of 1‐naphthylamine in aqueous solution. The electrocatalytic properties of this modified electrode (ME) were investigated using ascorbic acid (AA) as probe molecule. The electrochemical behavior of AA in buffer solution was examined by voltammetry and amperometry. The results showed that the ME exhibited good electrocatalytic activity towards the oxidation of AA, as a consequence, it can be used as amperometric sensor of this analyte in a flow injection system with good sensitivity. Calibration curves were linear over the concentration range 0.05–1.50 mM with a phosphate buffer solution pH 3 as the carrier, the detection limit was 1 ppm (S/N=3). The methods were applied to the determination of AA in beverages and pharmaceutical products. A good correlation with a reference method was attained.