Gas adsorption sites in a large-pore metal-organic framework

The primary adsorption sites for Ar and N2 within metal-organic framework-5, a cubic structure composed of Zn4O(CO2)6 units and phenylene links defining large pores 12 and 15 angstroms in diameter, have been identified by single-crystal x-ray diffraction. Refinement of data collected between 293 and 30 kelvin revealed a total of eight symmetry-independent adsorption sites. Five of these are sites on the zinc oxide unit and the organic link; the remaining three sites form a second layer in the pores. The structural integrity and high symmetry of the framework are retained throughout, with negligible changes resulting from gas adsorption.     

Hydrocarbon separations in a metal-organic framework with open iron(II) coordination sites

The energy costs associated with large-scale industrial separation of light hydrocarbons by cryogenic distillation could potentially be lowered through development of selective solid adsorbents that operate at higher temperatures. Here, the metal-organic framework Fe(2)(dobdc) (dobdc(4-) : 2,5-dioxido-1,4-benzenedicarboxylate) is demonstrated to exhibit excellent performance characteristics for separation of ethylene/ethane and propylene/propane mixtures at 318 kelvin. Breakthrough data obtained for these mixtures provide experimental validation of simulations, which in turn predict high selectivities and capacities of this material for the fractionation of methane/ethane/ethylene/acetylene mixtures, removal of acetylene impurities from ethylene, and membrane-based olefin/paraffin separations. Neutron powder diffraction data confirm a side-on coordination of acetylene, ethylene, and propylene at the iron(II) centers, while also providing solid-state structural characterization of the much weaker interactions of ethane and propane with the metal.     

Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores

Use of amphiphilic triblock copolymers to direct the organization of polymerizing silica species has resulted in the preparation of well-ordered hexagonal mesoporous silica structures (SBA-15) with uniform pore sizes up to approximately 300 angstroms. The SBA-15 materials are synthesized in acidic media to produce highly ordered, two-dimensional hexagonal (space group p6mm) silica-block copolymer mesophases. Calcination at 500 degrees C gives porous structures with unusually large interlattice d spacings of 74.5 to 320 angstroms between the (100) planes, pore sizes from 46 to 300 angstroms, pore volume fractions up to 0.85, and silica wall thicknesses of 31 to 64 angstroms. SBA-15 can be readily prepared over a wide range of uniform pore sizes and pore wall thicknesses at low temperature (35 degrees to 80 degrees C), using a variety of poly(alkylene oxide) triblock copolymers and by the addition of cosolvent organic molecules. The block copolymer species can be recovered for reuse by solvent extraction with ethanol or removed by heating at 140 degrees C for 3 hours, in both cases, yielding a product that is thermally stable in boiling water.     

High frictional anisotropy of periodic and aperiodic directions on a quasicrystal surface

Strong friction anisotropy is found when the twofold surface of an atomically clean aluminum-nickel-cobalt quasicrystal slides against a thiol-passivated titanium-nitride tip. Friction along the aperiodic direction is one-eighth as much as that along the periodic direction. This anisotropy, which is about three times as large as the highest value observed in anisotropic crystalline surfaces, disappears after the surface is oxidized in air. These results reveal a strong connection between interface atomic structure and the mechanisms by which energy is dissipated, which likely include electronic or phononic contributions, or both.     

Segmentation of pores in wood microscopic images based on mathematical morphology with a variable structuring element

A set of pores is one of the key features in the process of wood identification. A novel method to segment pores in a wood microscopic image is proposed in this paper. The method has three steps. In the first step, structuring elements with several sizes are employed in a mathematical morphology algorithm to enhance the pores and remove other tissues in a wood microscopic image. Then the best structuring element size is determined according to the results obtained from the previous step. Finally, a binary image that includes only pores is obtained by an adaptive thresholding. Experimental results show the efficiency of the method.     

Imaging and manipulating molecules on a zeolite surface with an atomic force microscope

The adsorption of neutral molecules and ions on the surfaces of zeolites was observed in real time with an atomic force microscope (AFM). Direct imaging of the surface of the zeolite clinoptilolite was possible by using a diluted tert-butyl ammonium chloride solution as a medium. Images of the crystal in different liquids revealed that molecules could be bound to the surface in different ways; neutral molecules of tert-butanol formed an ordered array, whereas tert-butyl ammonium ions formed clusters. These absorbed molecules were not rearranged by the AFM tip when used in an imaging mode. However, when a sufficiently large force was applied, the tip of the AFM could rearrange the tert-butyl ammonium ions on the zeolite surface. This demonstration of molecular manipulation suggests new applications, including biosensors and lithography.     

Linear alkane polymerization on a gold surface

In contrast to the many methods of selectively coupling olefins, few protocols catenate saturated hydrocarbons in a predictable manner. We report here the highly selective carbon-hydrogen (C-H) activation and subsequent dehydrogenative C-C coupling reaction of long-chain (>C(20)) linear alkanes on an anisotropic gold(110) surface, which undergoes an appropriate reconstruction by adsorption of the molecules and subsequent mild annealing, resulting in nanometer-sized channels (1.22 nanometers in width). Owing to the orientational constraint of the reactant molecules in these one-dimensional channels, the reaction takes place exclusively at specific sites (terminal CH(3) or penultimate CH(2) groups) in the chains at intermediate temperatures (420 to 470 kelvin) and selects for aliphatic over aromatic C-H activation.     

示范引领促发展 以点带面共提升

邵鹏飞名师工作室系无锡市教育局授牌成立的名师工作室,成立于2013 年3 月,在省 特级教师邵鹏飞老师的带领下,汇聚成员力量,凝聚团队合力,大幅提升了团队的教学水平,有 效改善了本专业的教学环境,为培养“现代班组长”型人才作出了贡献。本工作室的工作宗旨是 “示范引领促发展,以点带面共提升”。     

Structure of a Langmuir film on a liquid metal surface

The structure of organic monolayers on liquid surfaces depends sensitively on the details of the molecular interactions. The structure of a stearic acid film on a mercury surface was measured as a function of coverage with angstrom resolution. Unlike monolayers on water, the molecules were found here to undergo a transition from surface-parallel to surface-normal orientation with increasing coverage. At high coverage, two condensed hexatic phases of standing-up molecules were found. At low coverage, a two-dimensional (2D) gas phase and condensed single- and double-layered phases of flat-lying molecular dimers were revealed, exhibiting a 1D longitudinal positional order. This system should provide a broader tunability range for nanostructure construction than solid-supported self-assembled monolayers.     

Real-time observation of molecular motion on a surface

The laser-induced movement of CO molecules over a platinum surface was followed in real time by means of ultrafast vibrational spectroscopy. Because the CO molecules bound on different surface sites exhibit different C-O stretch vibrational frequencies, the site-to-site hopping, triggered by excitation with a laser pulse, can be determined from subpicosecond changes in the vibrational spectra. The unexpectedly fast motion--characterized by a 500-femtosecond time constant--reveals that a rotational motion of the CO molecules, rather than pure translation, is required for this diffusion process. This conclusion is corroborated by density functional theory calculations.     

Light-driven motion of liquids on a photoresponsive surface

The macroscopic motion of liquids on a flat solid surface was manipulated reversibly by photoirradiation of a photoisomerizable monolayer covering the surface. When a liquid droplet several millimeters in diameter was placed on a substrate surface modified with a calix[4]resorcinarene derivative having photochromic azobenzene units, asymmetrical photoirradiation caused a gradient in surface free energy due to the photoisomerization of surface azobenzenes, leading to the directional motion of the droplet. The direction and velocity of the motion were tunable by varying the direction and steepness of the gradient in light intensity. The light-driven motion of a fluid substance in a surface-modified glass tube suggests potential applicability to microscale chemical process systems.     

高比表面积炭基固体酸催化剂的制备及应用

【目的】制备清洁环保且高效的高比表面积炭基固体酸催化剂。【方法】以椰壳基、木粉基、煤基3种活性炭为原料,通过重氮盐还原法制备催化剂,比较3种催化剂的理化性质及性能,以选择最佳的活性炭催化剂。探讨乙醇与油酸物质的量比、反应温度、反应时间、催化剂用量等因素对油酸酯化率的影响,确定油酸酯化反应的最佳条件。【结果】以煤基活性炭制备的催化剂磺酸密度最大(0.64mmol/g),其催化效果也最好,在反应6h后,油酸的酯化率可达69.7%。油酸酯化反应的最佳条件为:乙醇与油酸物质的量比10∶1,反应温度80℃,反应时间12h,催化剂用量为油酸质量的6%,在此条件下,油酸的酯化率可达87.3%。煤基磺化活性炭催化剂在油酸酯化反应中可以稳定地重复使用3次。【结论】以煤基活性炭为原料,用重氮盐还原法可制得高效廉价且清洁环保的炭基固体酸催化剂。     

基于生态-产业共生关系的林业生态安全测度方法构想

通过对林业生态安全内涵构成的研究和对现有测度方法的比较分析,发现国内外林业生态安全测度研究中存在“就生态论生态”的预警滞后性、评价指标体系及权重设定的主观性、指标体系和特征指数难以优势互补、生态安全性判据缺乏客观依据等问题.为解决这些问题,需要基于生态与产业系统的共生关系研究林业生态安全测度的新方法.首先,研究林业生态安全的压力-状态-影响-响应结构模型和结构方程模型(SEM)的构建方法,从而为评价指标体系的构建和权重的确定提供了理论依据和结构化、定量化方法.然后,通过寻求指标体系和特征指数的有机结合,得出描述林业生态安全演变趋势的性质和程度的特征指数——生态-产业共生度和成熟度.由此提出确定林业生态安全阈值和底线的定量化方法,并建立林业生态安全双特征判断矩阵,从而将林业生态安全度分为3个安全区间、6个安全等级和4个预警级别.最后,综合以上成果,构建了基于生态-产业共生关系的林业生态安全测度方法的整体框架:目标-手段树和技术路线.根据新方法的构建机理,所得出的林业生态安全测度和预警信息具有主观性弱、预测性强、特征指数值的生态经济意义明确、便于追溯问题的原因等技术优势,有利于林业生态安全的监控和管理.     

Cell surface molecule associated with lymphocyte homing is a ubiquitinated branched-chain glycoprotein

Partial amino acid sequence analysis of a purified lymphocyte homing receptor demonstrates the presence of two amino termini, one of which corresponds precisely to the amino terminus of ubiquitin. This observation extends the province of this conserved polypeptide to the cell surface and leads to a proposed model of the receptor complex as a core polypeptide modified by glycosylation and ubiquitination. Independent antibodies to ubiquitin serve to identify additional cell surface species, an indication that ubiquitination of cell surface proteins may be more general. It is proposed that functional binding of lymphocytes to lymph node high endothelial venules might involve the ubiquitinated region of the receptor; if true, cell surface ubiquitin could play a more general role in cell-cell interaction and adhesion.     

The force needed to move an atom on a surface

Manipulation of individual atoms and molecules by scanning probe microscopy offers the ability of controlled assembly at the single-atom scale. However, the driving forces behind atomic manipulation have not yet been measured. We used an atomic force microscope to measure the vertical and lateral forces exerted on individual adsorbed atoms or molecules by the probe tip. We found that the force that it takes to move an atom depends strongly on the adsorbate and the surface. Our results indicate that for moving metal atoms on metal surfaces, the lateral force component plays the dominant role. Furthermore, measuring spatial maps of the forces during manipulation yielded the full potential energy landscape of the tip-sample interaction.     

Confinement of electrons to quantum corrals on a metal surface

A method for confining electrons to artificial structures at the nanometer lengthscale is presented. Surface state electrons on a copper(111) surface were confined to closed structures (corrals) defined by barriers built from iron adatoms. The barriers were assembled by individually positioning iron adatoms with the tip of a 4-kelvin scanning tunneling microscope (STM). A circular corral of radius 71.3 A was constructed in this way out of 48 iron adatoms. Tunneling spectroscopy performed inside of the corral revealed a series of discrete resonances, providing evidence for size quantization. STM images show that the corral's interior local density of states is dominated by the eigenstate density expected for an electron trapped in a round two-dimensional box.     

Reversible rotation of antimony dimers on the silicon (001) surface with a scanning tunneling microscope

The scanning tunneling microscope (STM) was used to control the configuration of antimony clusters on the (001) surface of silicon. In particular, the STM tip induced a reversible rotation between two orthogonal orientations of individual antimony dimers on the surface. This simple rotation can be explained by an atomic-scale torque exerted on the antimony dimers by the STM tip. The reversibility of this process could provide a basis for making atomic-scale memory cells.     

基于响应面法的不同锯料角锯齿的木材切削力模型

木材锯切为闭式切削,其中侧刃的作用不可忽视。为探寻锯切过程中侧刃对切削力的影响并将其量化,采用不同锯料角锯齿对樟子松Pinus sylvestris和水曲柳Fraxinus mandshurica做单齿切削力试验,利用响应面分析法中的四因素三水平的Box-Behnken Design（BBD）试验设计和建模方法,研究了锯料角、切削厚度、含水率和刀具前角等参数对切削力的影响,并建立切削力模型。结果发现:采用响应面法建立的木材切削力多元回归数学模型,可较为有效地反映切削力与各因素之间的关系（R2=0.92和R2=0.94）;在闭式切削过程中,锯齿的锯料角对切削力有一定影响,且随着锯料角的增加,切削力缓慢降低;切削厚度对切削力影响显著,其次是刀具前角,木材含水率、锯料角对切削力的影响最小。