Template-directed self-assembly of 10-microm-sized hexagonal plates

This article presents a strategy for the fabrication of ordered microstructures using concepts of design inspired by molecular self-assembly and template-directed synthesis. The self-assembling components are 4-microm-thick hexagonal metal plates having sides 10 microm in length ("hexagons"), and each template consists of a 4-microm-thick circular metal plate surrounding a central cavity, the perimeter of which is complementary in shape to the external edges of a two-dimensional, close-packed array of hexagons. The hexagons and templates (collectively, "pieces") were fabricated via standard procedures and patterned into hydrophobic and hydrophilic regions using self-assembled monolayers (SAMs). Templated self-assembly occurs in water through capillary interactions between thin films of a nonpolar liquid adhesive coating the hydrophobic faces of the pieces. The hexagons tile the cavities enclosed by the templates, and the boundaries of the cavities determine the sizes and shapes of the assemblies. Curing the adhesive with ultraviolet light furnishes mechanically stable arrays having well-defined morphologies. By allowing control over the structures of the resulting aggregates, this work represents a step toward the development of practical methods for microfabrication based on self-assembly.     

Computer Handling of Chemical and Biological Data of Traditional Chinese Medicines

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Concentration profiles of cocaine, pyrolytic methyl ecgonidine and thirteen metabolites in human blood and urine: determination by gas chromatography-mass spectrometry

When cocaine is smoked, a pyrolytic product, methyl ecgonidine (anhydroecgonine methyl ester), is also consumed with the cocaine. The amount of methyl ecgonidine formed depends on the pyrolytic conditions and composition of the illicit cocaine. This procedure describes detection of cocaine and 10 metabolites--cocaethylene, nor-cocaine, nor-cocaethylene, methyl ecgonine, ethyl ecgonine, benzoylecgonine, nor-benzoylecgonine, m-hydroxybenzoylecgonine, p-hydroxybenzoylecgonine and ecgonine--in blood and urine. In addition, the detection of pyrolytic methyl ecgonidine and three metabolites--ecgonidine (anhydroecgonine), ethyl ecgonidine (anhydroecgonine ethyl ester) and nor-ecgonidine (nor-anhydroecgonine)--are included. The newly described metabolites, ethyl ecgonidine and nor-ecgonidine, were synthesized and characterized by gas chromatography-mass spectrometry (GC-MS). All 15 compounds were extracted from 3 mL of blood or urine by solid-phase extraction and identified by a GC-MS method. The overall recoveries were 49% for methyl ecgonine, 35% for ethyl ecgonine, 29% for ecgonine and more than 83% for all other drugs. The limits of detection were between 0.5 and 4.0 ng/mL except for ecgonine, which was 16 ng/mL. Linearity for each analyte was established and in all cases correlation coefficients were 0.9985-1.0000. The procedure was applied to examine the concentration profiles of analytes of interest in post-mortem (PM) blood and urine, and in urine collected from living individuals (LV). These specimens previously were shown to be positive for the cocaine metabolite, benzoylecgonine. Ecgonidine, the major metabolite of methyl ecgonidine, was present in 77% of PM and 88% of the LV specimens, indicating smoking as the major route of cocaine administration. The new pyrolytic metabolites, ethyl ecgonidine and nor-ecgonidine, were present in smaller amounts. The urine concentrations of nor-ecgonidine were 0-163 ng/mL in LV and 0-75 ng/mL in PM specimens. Ethyl ecgonidine was found only in PM urine at concentrations 0-39 ng/mL. Ethanol-related cocaine metabolites, ethyl ecgonine or cocaethylene, were present in 69% of PM and 53% of cocaine-positive LV specimens, implying alcohol consumption with cocaine use. The four major metabolites of cocaine--benzoylecgonine, ecgonine, nor-benzoylecgonine and methyl ecgonine--constituted approximately 88 and 97% of all metabolites in PM and LV specimens, respectively. The concentrations of nor-cocaine and nor-cocaethylene were consistently the lowest of all cocaine metabolites. At benzoylecgonine concentrations below 100 ng/mL, ecgonine was present at the highest concentrations. In 20 urine specimens, benzoylecgonine and ecgonine median concentrations (range) were 54 (0-47) and 418 ng/mL (95-684), respectively. Therefore, detection of ecgonine is advantageous when benzoylecgonine concentrations are below 100 ng/mL.     

Lensless diffractive imaging using tabletop coherent high-harmonic soft-X-ray beams

We present the first experimental demonstration of lensless diffractive imaging using coherent soft x rays generated by a tabletop soft-x-ray source. A 29 nm high harmonic beam illuminates an object, and the subsequent diffraction is collected on an x-ray CCD camera. High dynamic range diffraction patterns are obtained by taking multiple exposures while blocking small-angle diffraction using beam blocks of varying size. These patterns reconstruct to images with 214 nm resolution. This work demonstrates a practical tabletop lensless microscope that promises to find applications in materials science, nanoscience, and biology.     

Delta13C analyses of calcium carbonate: Comparison between the GasBench and elemental analyzer techniques

Measurements of stable carbon isotopic composition (delta13C) of carbonates or carbonate-rich soils are seldom performed in a continuous-flow isotope ratio mass spectrometer (IRMS) using an elemental analyzer (EA) as an online sample preparation device. Such analyses are routinely carried out with an external precision better than 0.1 per thousand using a GasBench II (GB) sample preparation device coupled online with a continuous-flow IRMS. In this paper, we report and compare delta13C analyses (86 total analyses) of calcium carbonates obtained by using both the GB and the EA. Using both techniques, the delta13C compositions of two in-house carbonate standards (MERCK carbonate and NR calcite) and ten selected carbonate-rich paleosol samples (of variable CaCO3 content) were analyzed, and data are reported in the VPDB scale calibrated against international standards, NBS 18 and 19. For the in-house standards analyzed by both techniques, a precision better than 0.08 per thousand is achieved. The analytical errors (1sigma) computed from multiple analyses of the delta13C of both the MERCK and NR obtained by the above two techniques are nearly identical. In general, the 1sigma (internal error) of paleosol analyses obtained in the GB is better than 0.06 per thousand, whereas that for the analyses in the EA (three repetitive analyses of the same sample) varies in the range 0.05-0.21 per thousand. However, for paleosols having more than 85% CaCO3, 1sigma is better than 0.15 per thousand (similar to the instrument precision), and in this case the delta13C(VPDB) of samples obtained by the GB is similar to that obtained by the EA. Our results suggest that the delta13C of pure calcium carbonate samples can also be analyzed using the EA technique.     

Ultraviolet radiation as a limiting factor in leaf expansion and development

Reductions in leaf growth are a commonly observed response to ultraviolet radiation, but the underlying mechanisms remain poorly defined. This study examined the response of leaves exposed to a UV environment across a range of organizational scales, including leaf expansion rate, epidermal cell size and number, biomechanical properties, leaf–water relations and activity of cell-wall peroxidases. Two experimental approaches were used; Lettuce ( Lactuca sativa L.) plants were propagated under (a) supplementary UV-B (9 kJ m⁻² day⁻¹) in controlled environment (CE) conditions, and (b) field conditions, where plants were placed under three horticultural films with differing UV transmissions. In both experiments, UV-B caused the greatest reductions in leaf expansion and final leaf size, with some reductions attributable to UV-A wavelengths. In supplementary UV-B conditions, adaxial cell size was reduced, while in field plants, both cell size and cell number were lower in an increased UV environment, as was the case with abaxial cells in CE plants. Although leaf turgor and leaf extensibility were not affected by UV wavelengths, breaking strain of leaf tissue was decreased under supplementary UV-B. Cell-wall peroxidase activity was increased in both supplementary UV conditions and in the field, where only a zero UV environment showed no upregulation of cell-wall peroxidase.     

Theory of Frequency-Dependent Polarization of General Planar Electrodes with Zeta Potentials of Arbitrary Magnitude in Ionic Media

Electrode polarization effects have long aggravated the efforts of low frequency analysis, particularly those investigations carried out on biological material or in highly conductive media. Beginning from elementary equations of electrostatics and hydrodynamics, a comprehensive model is devised to account for the screening of a general planar electrode by an ionic double layer. The surface geometry of the planar electrode is left unspecified to include any type of micromachined array. Building on the previous work by DeLacey and White (1982, J. Chem. Soc. Faraday Trans. 2 78, 457) using a variational theorem, we extend their numerical results with compact analytic solutions, analogous to the Debye-Hückel potential for dc systems, but applicable now to dynamic ac experiments. The variational approach generates functions that are not restricted by perturbation expansions or numerical convergence, representing optimal approximations to the exact solutions. Copyright 2000 Academic Press.     

化学、大分子、与人类的需要

化学自从成为一门成熟的科学以来,在对自然界中小而又小的实体的追根究底方面,不再处在第一线了。但是,作为与分子关系最深的科学,化学仍然处在首要地位。它在阐明物质最常见的形式方面,在培养对常见物质的性质及其所经历的变化更广泛的鉴别方面,既有义务,又有可能。此外.化学科学必须对新技术有所帮助,也应该促使现有的技术更适合今天与明天的需要。因而,化学在文化与技术方面,起了双重的作用。在这两方面,大分子的重要性都是突出的.它的组成物质很平凡。大分子构成所有生物物质的组织,并执行生命过程所赖以实现的主要调节功能。在工业领域内,近年来看到的合成聚合物用途的飞速发展。看来肯定还会继续下去,以至于代替金属及其他的不能从更新来源所得的材料。能结合到长分子链中的分子构造花样繁多,因而所提供的可能性实际上是无限的。生命科学与聚合物工艺在未来年代所需要的有关聚合物的知识,是不扎实而有限的。所以,当务之急是取得对大分子更为深入的理解。     

A molecular dynamics simulation study of the alpha-relaxation in a 1,4-polybutadiene melt as probed by the coherent dynamic structure factor

The dynamic coherent structure factor Scoh(q,t) for a 1,4-polybutadiene (PBD) melt has been investigated using atomistic molecular dynamics simulations. The relaxation of Scoh(q,t) at q = 1.44 angstroms(-1) and q = 2.72 angstroms(-1), corresponding to the first and second peaks in the static structure factor for PBD, was studied in detail over a wide range of temperature. It was found that time-temperature superposition holds for the alpha-relaxation for both q values over a wide temperature range and that the alpha-relaxation can be well described by a stretched (Kohlrauch-William-Watts) exponential with temperature independent but q dependent amplitude and stretching exponent. The alpha-relaxation times for both q values were found to exhibit the same non-Arrhenius temperature dependence, indicating that the same physical processes are responsible for relaxation on both length scales. The alpha-relaxation time was found to depend strongly upon the dynamical range of data utilized in determining the relaxation time, accounting for qualitative discrepancies between alpha-relaxation times reported here and those extracted for PBD from experimentally measured Scoh(q,t).