Application of optimization procedures for the separation of anabolic compounds by high-performance liquid chromatography

A simple systematic approach is presented for optimizing high-performance liquid chromatographic separations of anabolics with multi-component isocratic mobile phases. A computer program was obtained and adjusted for use with an IBM-compatible XT personal computer. The program requires experimental retention data with three quaternary solvent mixtures to calculate the optimum solvent composition using a geometric model of a prism. For each possible composition of the mobile phase the set of retention data can be calculated. Applications are shown for mixtures of anabolic compounds using a mobile phase composed of methanol, tetrahydrofuran and acetonitrile. The predicted retention data agreed very well with the experimental data.     

Mg/Mg1.8La0.2Ni纳米复合材料的吸放氢性能研究

应用高能球磨法制备Mg-x%Mg1.8La0.2Ni (x=10、20和30) 纳米复合储氢材料. X射线衍射(XRD)、透射电镜(TEM)和选区电子衍射(SAED)测试表明,该复合材料具有纳米晶和非晶态混合结构的性质,吸氢温度降低,较好的吸放氢动力学性能,在423K,2.5MPa氢压的条件下,50s内即可达到最大吸氢量.     

失活加氢精制催化剂中硫铁相的高分辨透射电镜研究

利用高分辨透射电镜(HRTEM)结合X射线能谱仪(EDS)和选区电子衍射(SAED)分析,对运转后的加氢精制催化剂中含有的微量未知相的化学组成、晶体结构进行了研究.通过X射线能谱仪确定该未知相主要成分为硫和铁.根据选区电子衍射结果,该硫铁相为单晶结构.采用样品倾转的方法,获得3幅不同取向的选区电子衍射图,根据衍射谱中衍射斑点对应的晶体学信息及3幅电子衍射图取向间的夹角关系,确定该硫铁化合物属于正交晶系的硫化亚铁,分子式为Fe0.91S.该催化剂应用于高温高压下的加氢环境中,其中原料油中的酸性物质,尤其是环烷酸对加氢设备材质的腐蚀是导致硫铁化合物相形成的主要原因,并由此探讨了硫铁化合物相的形成机制.     

Study of the structure of thin nanocrystalline films

Structure and phase composition of thin nanocrystalline films of semiconductors and insulators CdS, Cd_xZn_1?xS, SiC_xN_y, and BC_xN_y were studied using registration of weak diffraction intensities with synchrotron radiation. Three methods were developed and applied to obtain diffraction patterns, namely, θ—2-scan (Bragg—Brentano geometry); 2θ-scan (grazing incidence scheme); a scheme with an image plate as detector. The characteristic features of the diffraction patterns, obtained from the aforementioned samples, are discussed. The X-ray diffraction data are compared with the results obtained by HREM, SAED, electron spectroscopy, ellipsometry, IR and Raman spectroscopy. It is stated that: 1) the films are composed of nanocrystals, their size depending on the conditions of film deposition; 2) single crystalline substrate favors formation of oriented crystals, i.e., of the domains comprising uniformly oriented nanocrystals.     

Pyrolysis in the mesophase: a chemist's approach toward preparing carbon nano- and microparticles

A mild pyrolytic method is proposed for the generation of different carbon micro- and nanoparticles that are either unprecedented or have never been reported under the present experimental conditions. A hexa-alkyl-substituted hexa-peri-hexabenzocoronene serves as a graphite-like starting compound that melts into a discotic liquid crystalline phase prior to heat-induced cross-linking and dehydrogenation. An essential feature of the process is that the liquid crystalline order persists even above 400 degrees C, i.e., during alkyl chain cleavage. The present approach bears a resemblance to carbomesophase formation during graphitization starting from pitch. The pyrolysis products are characterized by matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry, optical microscopy, selected area electron diffraction (SAED), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HRTEM).     

Phase composition of nanosized oxide film structures based on lanthanum and scandium doped HfO<Subscript>2</Subscript>

X-ray photoelectron spectroscopy, X-ray diffraction, and high-resolution transmission electron microscopy (over thickness profiling of the elemental and phase compositions of the samples) are used to investigate the elemental and phase compositions, structures, and microstructures of films synthesized in La–Hf–O and Sc–Hf–O systems from organometallic volatile compounds. The dependence of the phase compositions and microstructures of films on the concentration of a doping rare earth element is determined. It is found that lanthanum and scandium doping of hafnium oxide results in the formation of solid solutions of a hightemperature cubic modification. The conditions for obtaining the pyrochlore phase are determined in the nanocrystalline Hf–La–O system.     

Calculation of the heat capacity of linear macromolecules from theta-temperatures and group vibrations

An automated computer program is presented for the calculation of heat capacity of macromolecules from skeletal vibration frequencies described by the Tarasov equation and group vibration frequencies. The heat capacities calculated for crystalline polyethylene and polytetrafluoroethylene fit well with the experimental data from our ATHAS data bank. The program will be part of the planned ATHAS Computation Center.     

Calculation of the surface excitation parameter for Si and Ge from measured electron backscattered spectra by means of a Monte-Carlo simulation.

A new Monte Carlo method has been developed for simulating backscattered electron spectra, and this was applied for determining the surface excitation parameter (SEP). The simulation is based on direct tracking of electron trajectories in the solid, taking into account elastic and inelastic events. The elastic scattering cross sections are taken from literature, while inelastic cross section data are obtained by a fitting procedure. After some iterations, the program produces electron spectra fitting well to the experimental ones. Si and Ge electron spectra were simulated and SEP values were calculated. The SEP values are compared to other ones from literature.     

乙烯在四氯化亚铜铝甲苯溶液中溶解度测定及其热力学模型

实测了乙烯在四氯化亚铜铝甲苯溶液中的溶解度。提出了一个处理伴有化学反应的气液平衡的热力学模型, 同时考虑了体系的相平衡和络合平衡, 将Scatchard-Hildebrand模型适当简化后, 计算其液相活度系数, 编制了计算程序, 模型应用方便。用该模型关联计算了溶解度实验数据, 结果令人满意。     

Structure and Transformation in Clusters: Computational Experiments

A very brief review of gas-phase electron diffraction and one of its offshoots is given. Parallels are drawn between experimental studies of molecules, including conformational changes, and studies of clusters, including phase changes, calling particular attention to the use of computers as the preferred experimental apparatus. A sketch is presented of what has been learned about matter in transition by the application of computer simulations.     

The integration of structure determination by computation,electron diffraction and microwave spectroscopy

The history of the interaction between experimental structure determinations by microwave spectroscopy and by gas phase electron diffraction is briefly reviewed in terms of three eras: (1) competition and antagonism, (2) comparison and correction, and (3) integration of analysis. A similar progression is noted for the relation between experimental and theoretical methods for studying molecular structure, with the present time straddling ages (2) and (3). Examples are given from a variety of studies involving various degrees of methodological interaction. The true integration of experimental and computational structural studies is still in its infancy with the primary illustrations involving the evaluation of theoretical structural offset values from experimental evidence, the transfer of theoretically determined parameters into the fitting of experimental data, and the current development of methods for utilizing vibrational information obtained from the combined analysis of computed theoretical and experimental infrared data in the further analysis of experimental diffraction and microwave information.     

Vibrational Spectroscopy and Analytical Electron Microscopy Studies of Fe–V–O and In–V–O Thin Films

Summary.  Orthovanadate (M ³⁺VO₄; M = Fe, In) and vanadate (Fe₂V₄O₁₃) thin films were prepared using sol-gel synthesis and dip coating deposition. Using analytical electron microscopy (AEM), the chemical composition and the degree of crystallization of the phases present in the thin Fe–V–O films were investigated. TEM samples were prepared in both orientations: parallel (plan view) and perpendicular (cross section) to the substrate. In the first stages of crystallization, when the particle sizes were in the nanometer range, the classical identification of phases using electron diffraction was not possible. Instead of measuring d values, experimentally selected area electron diffraction (SAED) patterns were compared to calculated (simulated) patterns in order to determine the phase composition. The problems of evaluating the ratio of amorphous and crystalline phases in thin films are reported. Results of TEM and XRD as well as IR and Raman spectroscopy showed that the films made at lower temperatures (300°C) consisted of nanograins embedded in the dominating amorphous phase. Characteristic vibrational spectra allowed to distinguish between the different crystalline phases, since the IR and Raman bands showed broadening due to the decreasing particle size of the films thermally treated at lower temperatures. Vibrational analysis also showed that the electrochemical cycling of crystalline films led to spectra that were in close agreement with the spectra of the nanocrystalline films prepared at lower temperatures. The formation of a nanocrystalline structure is therefore a prerequisite for obtaining a higher charging/discharging stability of Fe–V–O and In–V–O films. Received October 4, 2001. Accepted (revised) November 23, 2001     

Size and Spectroscopy of Silicon Nanoparticles Prepared via Reduction of SiCl4

Synthesis of silicon nanoparticles of various sizes from 3 to 9 nm in diameter was accomplished via a low temperature solution route. These nanoparticles are prepared via reduction of SiCl₄ with Na naphthalide in dimethoxyethane and capped with octasiloxane. The resulting nanoparticles were characterized by transmission electron microscopy (TEM), high resolution (HR) TEM, selected area electron diffraction (SAED), energy dispersive X-ray (EDX) spectroscopy, powder X-ray diffraction, UV–vis, photoluminescence, and their quantum yields were determined. TEM micrographs show that the nanoparticles are well dispersed and SAED and lattice fringes are consistent with diamond structured silicon. X-ray powder diffraction provides no diffraction peaks. UV–vis and photoluminescence show characteristic shifts corresponding to size, consistent with quantum confinement. The smallest sized nanoparticles show the largest quantum yield, consistent with an indirect bandgap nanoparticles.     

尺寸可控氢氧化镧纳米棒的水热合成及表征

以硝酸镧为镧源、三乙胺为碱源和络合剂,通过简便的水热法成功合成了大量均一的氢氧化镧纳米棒。详细研究了三乙胺的用量、表面活性剂、反应温度和时间对产物形貌及尺寸的影响。基于实验结果,提出了氢氧化镧纳米棒的形成机理。同时制备了稀土掺杂的氢氧化镧纳米棒。利用X射线衍射（XRD）、透射电子显微镜（TEM）、选区电子衍射（SAED）和高分辨透射电子显微镜（HRTEM）对所得产物的物相、结构和形貌进行了表征分析。     

Preparation and characterization of nanocrystalline CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> deposited on SiO<Subscript>2</Subscript>: in situ sol–gel process

In situ base catalyst assisted sol–gel process is used for the synthesis of nanocrystalline CoFe₂O₄ deposition on SiO₂ particles. The SiO₂ particles were prepared using base catalyst assisted sol–gel process and the consecutive formation and deposition of nanocrystalline CoFe₂O₄ on SiO₂ particles was monitored using Powder X ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Thermo Gravimetric And Differential Thermal Analysis (TG/DTA), Scanning Electron Microscopy and Energy Dispersive X ray Spectroscopy (SEM–EDS) and High Resolution Transmission Electron Microscopy (HRTEM). The crystallite size of CoFe₂O₄ is calculated using Scherrer’s formula and it is found to be 8 nm. The HRTEM images and selective area electron diffraction (SAED) results confirmed the formation of nanocrystalline CoFe₂O₄ particles deposited over SiO₂ spheres.     

Controlled Synthesis of Sea-urchin-like ZnO Nanomaterials with the Aid of Ethylene Glycol Using a Solvothermal Method

Sea-urchin-like ZnO nanomaterials were successfully synthesized by decomposition of zinc acetate precursor in the presence of sodium hydroxide and ethylene glycol(EG) in an ethanol solution using a solvothermal method at 180 ℃ for 12 h.The crystalline phase and morphology of the resultant nanomaterials were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM),selected-area electronic diffraction(SAED) and high-resolution electron microscopy(HRTEM).Interestingly,the sizes and prod length of the samples can be easily tuned by changing the amount of directing agent EG and keeping other reaction conditions unchangeable.On the basis of our experimental outcomes,EG-controlled-nucleation-growth formation mechanism was proposed to correspond for the sea-urchin-like ZnO growth processes.And the photoluminescence(PL) spectra of the as-selected samples were measured at room temperature,presenting two emission peaks centered at～388 and 480 nm.     

Three-dimensional analysis by electron diffraction methods of nanocrystalline materials

To analyze nanocrystalline structures quantitatively in 3D, a novel method is presented based on electron diffraction. It allows determination of the average size and morphology of the coherently scattering domains (CSD) in a straightforward way without the need to prepare multiple sections. The method is applicable to all kinds of bulk nanocrystalline materials. As an example, the average size of the CSD in nanocrystalline FeAl made by severe plastic deformation is determined in 3D. Assuming ellipsoidal CSD, it is deduced that the CSD have a width of 19 ± 2 nm, a length of 18 ± 1 nm, and a height of 10 ± 1 nm.     

Structural disorder in Ba0.6Sr0.4Al2O4

The structural disorder in Ba_0.6Sr_0.4Al₂O₄ (space group P6₃22) was investigated by X-ray powder diffraction and selected-area electron diffraction (SAED). The initial structural model was determined using direct methods, and it was further modified by the combined use of Rietveld method and maximum-entropy method (MEM). MEM-based pattern fitting method was subsequently applied, resulting in the final reliability indices of R_wp=9.61%, R_p=6.96%, R_B=1.40% and S=1.25. The electron density distribution was satisfactorily expressed by the split-atom model in which the strontium/barium and oxygen atoms were split to occupy the lower symmetry sites. The diffuse scattering in SAED was mainly attributable to the positional disorder of oxygen atoms.     

A simple route utilizing surfactant-assisted templating sol-gel process for synthesis of mesoporous Dy2O3 nanocrystal

A simple route of combined sol-gel process with surfactant-assisted templating technique was successfully employed for the first time to synthesize nanocrystalline mesoporous Dy(2)O(3) with narrow monomodal pore size distribution under mild conditions. The nanocrystalline Dy(2)O(3) with monomodal mesoporous characteristic was ultimately achieved by controlling the hydrolysis and condensation steps of dysprosium n-butoxide modified with acetylacetone in the presence of laurylamine hydrochloride surfactant aqueous solution. The synthesized material was methodically characterized by thermogravimetry and differential thermal analysis (TG-DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), selected-area electron diffraction (SAED), N(2) adsorption-desorption, Brunauer-Emmett-Teller (BET) surface area analysis, and Barrett-Joyner-Halenda (BJH) pore size distribution analysis. The particle size of the synthesized Dy(2)O(3) in nanosized range obtained from the SEM and HRTEM micrographs was in good accordance with the crystallite size estimated from the XRD result. The N(2) adsorption-desorption result exhibited hysteresis pattern with single loop, indicating the existence of monomodal mesopore. The extremely narrow pore size distribution with mean pore diameter in the mesopore region of the synthesized Dy(2)O(3) was also confirmed by the BJH result.     

感应熔炼高锰硅的结构和形貌特性

采用场发射扫描电镜(FESEM)和X射线能谱仪(EDXS)对感应熔炼高锰硅(HMS)中的第二相条纹的形貌和成份进行了研究,发现第二相条纹平行贯穿整个高锰硅晶粒,其条纹宽度约30nm,间距在5-30μm内,成份为MnSi.通过高分辨透射电镜(HRTEM)观察到MnSi条纹为短程有序而长程无序的非晶形态.采用选区电子衍射(SAED)确定了高锰硅的晶体结构,结果表明所获得的高锰硅为单一的Mn4Si7相,未观察到高锰硅其它的非公度结构.透射电镜(TEM)结果表明,熔炼的高锰硅经过球磨和热压后产生了大量缺陷和应力畴,与热压之前的熔锭材料相比有明显差异.