Kinetic Analysis of the Hydrolysis of Pentose-1-phosphates through Apparent Nucleoside Phosphorolysis Equilibrium Shifts**

Herein, we report an addition to the toolbox for the monitoring and quantification of the hydrolytic decay of pentose-1-phosphates, which are known to be elusive and difficult to quantify. This communication describes how apparent equilibrium shifts of a nucleoside phosphorolysis reaction can be employed to calculate hydrolytic loss of pentose-1-phosphates based on the measurement of post-hydrolysis equilibrium concentrations of a nucleoside and a nucleobase. To demonstrate this approach, we assessed the stability of the relatively stable ribose-1-phosphate at 98 °C and found half-lives of 1.8–11.7 h depending on the medium pH. This approach can be extended to other sugar phosphates and related reaction systems to quantify the stability of UV-inactive and hard-to-detect reaction products and intermediates.     

Point Mutations of Nicotinic Receptor α1 Subunit Reveal New Molecular Features of G153S Slow-Channel Myasthenia

Slow-channel congenital myasthenic syndromes (SCCMSs) are rare genetic diseases caused by mutations in muscle nicotinic acetylcholine receptor (nAChR) subunits. Most of the known SCCMS-associated mutations localize at the transmembrane region near the ion pore. Only two SCCMS point mutations are at the extracellular domains near the acetylcholine binding site, α1(G153S) being one of them. In this work, a combination of molecular dynamics, targeted mutagenesis, fluorescent Ca²⁺ imaging and patch-clamp electrophysiology has been applied to G153S mutant muscle nAChR to investigate the role of hydrogen bonds formed by Ser 153 with C-loop residues near the acetylcholine-binding site. Introduction of L199T mutation to the C-loop in the vicinity of Ser 153 changed hydrogen bonds distribution, decreased acetylcholine potency (EC₅₀ 2607 vs. 146 nM) of the double mutant and decay kinetics of acetylcholine-evoked cytoplasmic Ca²⁺ rise (τ 14.2 ± 0.3 vs. 34.0 ± 0.4 s). These results shed light on molecular mechanisms of nAChR activation-desensitization and on the involvement of such mechanisms in channelopathy genesis.     

U：CaF2晶体的分凝特性与光谱性质

应用TGT法生长了直径为75mm的U：CaF2晶体，宏观上透明完整.应用公式K0=Cs/Cl计算了U在CaF2晶体中的分凝系数等于0.53.应用溶质分布一般公式Cs=K0C0(1-g)K0-1，计算U的浓度分布与测量值，数值符合说明晶体生长过程接近平衡状态.分析不同条件下生长的U: CaF2晶体的晶胞参数和吸收光谱，结果表明生长气氛决定U的价态及电荷补偿机理：无PbF2存在的条件下，U为+4价，晶体呈绿色；PbF2的加入起到氟化去氧作用，U倾向于以离子半径最接近于Ca2+的U3+存在，晶体呈红色.从晶体生长开始到结束的部位，U3+:CaF2晶体吸收光谱的峰位不变，峰强呈现与U浓度相同的增加趋势.U3+:CaF2晶体外层厚约5mm处呈黄色，含有U3+和U2+的混合价态离子，其原理是石墨坩埚的还原作用通过单质铅，使部分的U3+进一步还原成了U2+. 关键词： 铀 氟化钙晶体 分凝系数 晶胞参数     

Phase modulation in dipolar-coupled A2 spin systems: effect of maximum state mixing in H NMR in vivo

Coupling constants of nuclear spin systems can be determined from phase modulation of multiplet resonances. Strongly coupled systems such as citrate in prostatic tissue exhibit a more complex modulation than AX connectivities, because of substantial mixing of quantum states. An extreme limit is the coupling of n isochronous spins (A_n system). It is observable only for directly connected spins like the methylene protons of creatine and phosphocreatine which experience residual dipolar coupling in intact muscle tissue in vivo. We will demonstrate that phase modulation of this “pseudo-strong” system is quite simple compared to those of AB systems. Theory predicts that the spin-echo experiment yields conditions as in the case of weak interactions, in particular, the phase modulation depends linearly on the line splitting and the echo time.     

Thermal treatment on composite γ-zirconium phosphate-silica

The prepared amorphous γ-ZrP\SiO₂ composite had a complicated composition, since a part of γ-ZrP is converted to α-form during the exfoliation of it. The γ-ZrP\SiO₂ composite have specific surface area of 421 m²g^–1. The acidic P–OH groups of the lamellae species placed on the surface (it is ≈1.0 meq g^–1), do not destroy until the temperature of 1030 K. During the thermal treatment the total mass loss of 7.79% was found. This value corresponds to 0.42 mole of H₂O per molecule unit. The water loss process was found very slow, because of the placing of bilamellar species in the composite.     

Studies on calcium‐containing poly(urethane ether)s

The calcium salt of mono(hydroxyethoxyethyl)phthalate [Ca(HEEP)₂] was synthesized by the reaction of diethylene glycol, phthalic anhydride, and calcium acetate. Calcium‐containing poly(urethane ether)s (PUEs) were synthesized by the reaction of hexamethylene diisocyanate (HMDI) or tolylene 2,4‐diisocyanate (TDI) with a mixture of Ca(HEEP)₂ and poly(ethylene glycol) (PEG₃₀₀ or PEG₄₀₀) with di‐n‐butyltin dilaurate as a catalyst. A series of calcium‐containing PUEs of different compositions were synthesized with Ca(HEEP)₂/PEG₃₀₀ (or PEG₄₀₀)/diisocyanate (HMDI or TDI) molar ratios of 2:2:4, 3:1:4, and 1:3:4 so that the coating properties of the PUEs could be studied. Blank PUEs without calcium‐containing ionic diols were also prepared by the reaction of PEG₃₀₀ or PEG₄₀₀ with HMDI or TDI. The PUEs were well characterized by Fourier transform infrared, ¹H and ¹³C NMR, solid‐state cross‐polarity/magic‐angle‐spinning ¹³C NMR, viscosity, solubility, and X‐ray diffraction studies. The thermal properties of the polymers were also studied with thermogravimetric analysis and differential scanning calorimetry. The PUEs were applied as top coats on acrylic‐coated leather, and their physicomechanical properties were also studied. The coating properties of PUEs, such as the tensile strength, elongation at break, tear strength, water vapor permeability, flexing endurance, cold crack resistance, abrasion resistance, color fastness, and adhesive strength, were better than the standard values. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2865–2878, 2003     

An Electroacoustic Investigation of Concentrated Aqueous Suspensions of Calcium Pyrophosphate

The zeta potential of concentrated suspensions of calcium pyrophosphate were investigated using electroacoustics. The particles were negatively charged over the entire pH range studied. It proved impossible to reduce the pH of the suspension below 1.8, but the iso electric point could be estimated to occur at approximately pH 1. Two commercially available dispersants (one cationic and one anionic) were then added in small increments to the suspension in order to follow the change in zeta potential as the dispersants adsorbed onto the particles. From the shape of the curve it was possible to estimate the optimum adsorbed amount of dispersant required to fully coat the particles. The cationic dispersant adsorbed strongly and the optimum dosage was estimated at 2.5 ml of active polymer/kg of powder. Anionic dispersants are known to adsorb onto negatively charged ceramic oxide particles, but the anionic dispersant used in this study did not adsorb onto the negatively charged calcium pyrophosphate particles.     

若干具有[(PO4)2Mo5O15]簇骼的化合物的光谱研究

本文对所合成的具有 [(PO4 ) 2 Mo5O1 5]簇骼的 3种新颖的有机 磷钼酸盐簇合物(NH3CH2 CH2 NH3) 2 5[(PO4 ) (HPO4 )Mo5O1 5]·7 5H2 O (Ⅰ ) ,(H3NCH2 CH2 NH3) 3·[(PO4 ) 2 Mo5O1 5]·3H2 O (Ⅱ )和(H3NCH2 CH2 NH3) 2 ·[Cu(en) ][(PO4 ) 2 Mo5O1 5]·5H2 O (Ⅲ )用FTIR ,NIR Raman ,紫外 可见漫反射光谱 (UV VisDRS)和荧光光谱等研究手段 ,对其进行光谱研究 ,探讨其结构和性能的关系。在这些化合物中 ,化合物Ⅰ和Ⅱ具有孤立的 [(PO4 ) 2 Mo5O1 5]簇骼基元 ,而化合物Ⅲ的 [(PO4 ) 2 Mo5O1 5]簇骼基元是由 [Cuen]基团桥联成链 ;磷钼酸盐的特征振动频率和这些化合物的结构相关 ;UV VisDRS显示 ,在 2 0 0和 2 6 0nm左右有两个杂多化合物的特征吸收谱带 ;化合物的稳态荧光光谱中 ,观察到以 2 4 0nm激发 ,在大约 4 0 0nm附近出现的由金属氧簇Oμ→Mo跃迁激发所引起的较强的发射峰 ,在化合物 (Ⅲ )中 ,还观察到通过 [Cuen]的荷移跃迁的以 5 70nm激发所产生的 6 0 4nm的发射峰。     

Ca(NO3)2•4H2O-catalysed Biginelli Reaction: One-pot Synthesis of 1,2,3,4-Tetrahydropyrimidin-2-ones/pyrimidine-2-thiones under Solvent-free Conditions

The synthesis of 1,2,3,4-dihydropyrimidinone/thione derivatives was achieved in good to excellent yields using calcium(II) nitrate as catalyst to promote the Biginelli three-component condensation reaction from a diversity of aromatic aldehydes, β-keto compounds and urea or thiourea. The reaction was carried out under solvent-free conditions.     

Structures and syntheses of layered and framework amine-bearing uranyl phosphate and uranyl arsenates

Two hydrated uranyl arsenates and a uranyl phosphate were synthesized by hydrothermal methods in the presence of amine structure-directing agents and their structures determined: (N₂C₆H₁₄)[(UO₂)(AsO₄)]₂(H₂O)₃, DabcoUAs, {NH(C₂H₅)₃}[(UO₂)₂(AsO₄)(AsO₃OH)], TriethUAs, and (N₂C₄H₁₂)(UO₂)[(UO₂)(PO₄)]₄(H₂O)₂, PiperUP. Intensity data were collected at room temperature using MoKα X-radiation and a CCD-based area detector. The crystal structures were refined by full-matrix least-squares techniques on the basis of F² to agreement indices (DabcoUAs, TriethUAs, PiperUP) wR₂=5.6%, 8.3%, 7.2% for all data, and R₁=2.9%, 3.3%, 4.0%, calculated for 1777, 5822, 9119 unique observed reflections (|F_o|?4σ_F), respectively. DabcoUAs is monoclinic, space group C2/m, Z=2, a=18.581(1), b=7.1897(4), c=7.1909(4) Å, β=102.886(1)°, V=936.43(9) Å³, D_calc=3.50 g/cm³. TriethUAs is monoclinic, space group P2₁/n, Z=4, a=9.6359(4), b=18.4678(7), c=10.0708(4) Å, β=92.282(1)°, V=1790.7(1) Å³, D_calc=3.41 g/cm³. PiperUP is monoclinic, space group Pn, Z=2, a=9.3278(4), b=15.5529(7), c=9.6474(5) Å, β=93.266(1)°, V=1397.3(1) Å³, D_calc=4.41 g/cm³. The structure of DabcoUAs contains the autunite-type sheet formed by the sharing of vertices between uranyl square bipyramids and arsenate tetrahedra. The triethylenediammonium cations are located in the interlayer along with two H₂O groups and are disordered. Both TriethUAs and PiperUP contain sheets formed of uranyl pentagonal bipyramids and tetrahedra (arsenate and phosphate, respectively) with the uranophane sheet-anion topology. In TriethUAs, triethlyammonium cations are located in the interlayer. In PiperUP, the sheets are connected by a uranyl pentagonal bipyramid that shares corners with phosphate tetrahedra of adjacent sheets, resulting in a framework with piperazinium cations and H₂O groups in the cavities of the structure.