高频单线圈双调谐NMR单晶探头的研制

本文报道了一种测角单晶NMR探头。该探头采用单线圃双调谐电路,工作频率在90MHz-110 MHz连续可调,可进行交叉极化大功率去耦实验。文中提出了一种简单而有效的测角装置,可使单晶绕三个互相垂直轴转动实现单晶的NMR测量。作为典型的应用例子,本文利用该探头实现了单晶DGO(2NH₂CH₂COOH·H₂C₂O₄)屏蔽张量的测量。     

Viscometric study of gelatin in dilute aqueous solutions

The viscosities of aqueous solutions of gelatin at different temperatures were carefully measured in a common glass‐capillary Ubbelohde viscometer at dilute to extremely dilute concentrations. The adsorption effect that occurred in the viscosity measurements was theoretically analyzed and discussed. A theory based on Langmuir isotherms could adequately describe the existing data. Some structural information was obtained by the use of an iterative fitting procedure to treat the reduced viscosity data, which disclosed that individual gelatin chains underwent a coil‐to‐helix transition as the solution cooled from 40 to 15 °C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1804–1812, 2006     

Hierarchical Structure‐Within‐Structure Morphologies in A2‐star‐(B‐alt‐C) Molecules

We employ dissipative particle dynamics (DPD) to examine the self‐assembly behavior of A₂‐star‐(B‐alt‐C) molecules. We successfully observe various types of hierarchical structure‐within‐structures, such as A‐formed spheres in the matrix formed by B and C alternating layers, hexagonally packed A‐formed cylinders in the matrix with B and C segregated layers, B and C alternating layers‐within‐lamellae, coaxial B and C alternating domains within hexagonally packed BC‐formed cylinders in the A‐matrix, and co‐centric BC‐alternating domains within BC‐formed spheres in the A‐matrix, by increasing the A composition. Generally speaking, the small length‐scale B and C segregated domains are in parallel to the large length‐scale structures. This hierarchical periodicity along the same axis as well as the various characteristic structures, that the A₂‐star‐(B‐alt‐C) copolymers display, are quite different from those in A‐block‐(B‐graft‐C) coil‐comb copolymers. Moreover, it is interesting to find that when the copolymer chain length increases, though the hierarchical structure type is maintained, the number of small length‐scale lamellae that can form within the large length‐scale structure increases. These hierarchical structures under various compositions are reported theoretically for the first time in the copolymer systems consisting of the alternating blocks, and are in good agreement with the most recent experimental work by Matsushita and co‐workers (Macromolecules 2007 , 40, 4023).     

Nafion化学修饰圆盘预富集-石墨炉 原子吸收联用法对牛血超氧化物歧化酶中铜、锌分布状态的研究

本文研究了Nafion化学修饰钨丝圆盘预富集-石墨炉原子吸收(GFAAS)方法测定牛血超氧化物歧化酶(SOD)中游离态Cu～(2+)及Zn～(2+)的方法,并用GFAAS法直接测定SOD中铜、锌的总量,证实了牛血SOD中金属辅基铜、锌原子个数比为1:1,初步探讨了一定浓度的牛血SOD中Cu～(2+)、Zn～(2+)的表观离解平衡常数。为提高SOD的活性和稳定性的研究,提供了一种有效的方法。     

Selective formation of AAB- and ABC-type heterotrimeric alpha-helical coiled coils

The alpha-helical coiled coils have a representative amino acid sequence of (abcdefg)(n) heptad repeats. We previously reported that two peptides named IZ-2A and IZ-2W formed an (IZ-2A)(2)/IZ-2W heterotrimer with an Ala-Ala-Trp interaction in the hydrophobic core. In this paper, we describe the selective formation of AAB- and ABC-type heterotrimers. To increase the selectivity of the AAB-type heterotrimeric formation, Lys residues at the f position were mutated to either an Ala or a Gln residue to form IZ-2A(fA) or IZ-2W(fQ). Separately, both IZ-2A(fA) and IZ-2W(fQ) have a random structure at pH 7 and 20 degrees C. However, together IZ-2A(fA) and IZ-2W(fQ) form a 2:1 complex with a thermal transition midpoint (Tm) of 48 degrees C. This procedure was applied to prepare the ABC-type heterotrimer, in which two sets of Ala-Ala-Trp interactions were designed in the hydrophobic core. Interhelical interaction between the e and g positions and the alpha-helical propensity of the amino acid at the f position were also considered in the design. The resultant three peptides selectively formed the ABC-type heterotrimer with a Tm of 51 degrees C. Other peptide combinations had random coil properties.     

Effect of the Coil Angle in an Inductively Coupled Plasma Torch: A Novel Two-Dimensional Model

A two-dimensional model has been developed for the calculation of the electromagnetic (EM) fields generated by spiral coil currents, in order to obtain a better representation of the actual configuration used in a typical inductively coupled plasma (ICP) torch. In order to obtain the EM fields in a two-dimensional model, the change of EM field in tangential direction is neglected and the coil is assumed to be a concentric cylinder. In order to justify our assumption, the EM, flow and temperature fields resulting from five-ring coil and concentric cylinder coil are compared and the results are almost the same except for the EM field in the vicinity of the coil. In the case of the spiral coil, the coil current is inclined with respect to the horizontal plane. Therefore current in the cylinder coil is assumed to have the same inclined angle, which is split into tangential and axial components. The axial electric field and hence an axial current in plasma is induced by the axial component of the spiral coil current. Charge density is accumulated in the plasma, since the axial current cannot form a loop. In order to obtain the EM field and the charge distribution in the plasma generated by the spiral coil, the equations of axial vector potential and electrostatic potential have been derived. Due to the swirling Lorentz force (J_z×B_r) an axisymmetrical swirling fluid model is used to simulate the plasma flow in an axisymetrical configuration. With an inclined angle of the coil current being 3.7° and the frequency being 3 MHz, computational results show that the swirling Lorentz force causes plasma swirling with a maximum speed of 3.41 m/s near the plasma center when the injected sheath gas and central gas are not swirling. In these conditions, the real and imaginary parts of the maximum electrostatic potential are 0.95 V and 1.66 V, respectively. When the electrostatic field is neglected, the swirling velocity of the plasma is 3.95 m/s.     

A strategy for synthesis of polymer-protective bimetallic colloids

A strategy for the synthesis of polymer-protective bimetallic sols is proposed which has the advantage of the strong protective effect of the polymer agent on one of the composites to stabilize the bimetallic colloidal particles. This strategy is certified to be useful to the predication of the formation of stable bimetallic colloids protected by polymer and to the control of the particle size to a certain extent. A series of new PVP-protective bimetallic colloidal dispersions containing noble metal element (Pt, Rh, Pd), light transition metal element (Co, Fe), and boron are obtained from the corresponding salts by the methods of reduction by stage and coreduction, using the NaBH4 as reductant. The TEM, XRD and EPMA measurements indicate the formation of bimetallic colloids. An interesting kind of coil aggregation is observed in the systems of PVP-Pt-Co and PVP-Rh-Co prepared by the method of reduction by stage.     

Chemical modifiers in arsenic determination in biological materials by tungsten coil electrothermal atomic absorption spectrometry

Palladium, iridium, and rhodium are evaluated as possible chemical modifiers in the determination of As in digest solutions of biological materials (human hair and clam) by tungsten coil electrothermal atomic absorption spectrophotometry (TCA-AAS). The modifier in solution was applied onto the coil and thermally pre-reduced; the pre-reduction conditions, the amount of modifier, and the thermal program were optimized. Palladium was not satisfactory, whereas Ir and Rh were effective modifiers and rendered better relative sensitivity for As by a factor of 1.4 and 1.9, respectively compared to the case without modifier. Upon optimization of thermal conditions for As in pre-reduced Ir (2.0 µg) and Rh (2.0 µg) modifiers and in the digest solutions of the study matrices, Rh (2.0 µg) was more effective modifier and was selected as such. The mean within-day repeatability was 2.8% in consecutive measurements (25–100 µg L^–1) (3 cycles, each of n=6) and confirmed good short-term stability of the absorbance measurements. The mean reproducibility was 4.4% (n=20 in a 3-day period) and the detection limit (3 _blank/slope) was 29 pg (n=15). The useful coil lifetime in Rh modifier was extended to 300–400 firings. Validation was by determination of As in the certified reference material (CRM) of Oyster tissue solution with a percentage relative error (E _rel%) of 2% and percentage relative standard deviation (RSD%) of 3% (n=4), and by analytical recovery of As spiked in CRM of human hair [94±8% (n=4)]. The methodology is simple, fast (sample readout frequency 21 h^–1), reliable, of low cost, and was applied to the determination of As in hair samples of exposed and unexposed workers.     

Radiation formation of polymeric nanogels

An alternative method of synthesis of polymeric nanogels is proposed, based not on polymerization, but on intramolecular crosslinking of polymer chains, initiated by pulse irradiation in dilute aqueous solutions. Kinetic data show that for many water-soluble polymers irradiation under these conditions result in intramolecular crosslinking. Preliminary product studies on poly(vinyl alcohol) indicate that in fact internally crosslinked macromolecules can be obtained by this technique.     

Determination of Cr(VI) by portable tungsten coil electrothermal atomic absorption spectrometer after surfactant-assisted dispersive liquid-liquid microextraction

As a new developed instrument, a portable tungsten coil electrothermal atomic absorption spectrometer (W-coil ET-AAS) was first coupled with surfactant assisted dispersive liquid–liquid microextraction (SA-DLLME) to improve its analytical performance and expand its applications in this work. SA-DLLME was very simple, rapid and the extraction efficiency was considerably improved by the effect of surfactant, which was suitable to be coupled with the portable instrument in field analysis. After SA-DLLME, concentrated chromium in organic phase was directly determined on W-coil atomiser. The influence factors relevant to SA-DLLME and instrumental conditions were studied systematically. Under the optimal conditions, the limit of detection (LOD) for Cr(VI) was 0.016 µg L^?1, with sensitivity enhancement factor (EF) of 107. The relative standard deviation (RSD) for seven replicate measurements of 0.5 µg L^?1 of Cr(VI) was 4.6%. The recoveries for the spiked samples were in the acceptable range of 96.8–104%. The rapid, simple and high effective method greatly improved the sensitivity of this portable spectrometer for the determination of Cr(VI) and was applied to the analysis of ultra-trace Cr(VI) in real and certified water samples with satisfactory results.