Mesoporous titania films with adjustable pore size coated on stainless steel substrates

Mesoporous layers of titania were prepared on stainless steel substrates of defined roughness by dip coating. Ordered arrays of micelles formed from amphiphilic block copolymers served as pore templates during film drying. Coating of the precursors solution on freshly grinded steel resulted in extensively fractured films with severely distorted templated porosity. In contrast, films produced on precalcined steel showed good integrity, high substrate coverage and narrow pore size distribution with pores interconnected and ordered in a short range. This difference in film quality and morphology was ascribed to the reaction between template polymers and metal ions leached from the steel of grinded substrate surfaces. Films were ca. 700 nm thick and composed of nanocrystalline titania. The pore size of titania coatings was varied between 5 and 16 nm employing polymer templates of different structure and molecular weight.     

An automated on-line multidimensional HPLC system for protein and peptide mapping with integrated sample preparation

A comprehensive on-line two-dimensional 2D-HPLC system with integrated sample preparation was developed for the analysis of proteins and peptides with a molecular weight below 20 kDa. The system setup provided fast separations and high resolving power and is considered to be a complementary technique to 2D gel electrophoresis in proteomics. The on-line system reproducibly resolved approximately 1000 peaks within the total analysis time of 96 min and avoided sample losses by off-line sample handling. The low-molecular-weight target analytes were separated from the matrix using novel silica-based restricted access materials (RAM) with ion exchange functionalities. The size-selective sample fractionation step was followed by anion or cation exchange chromatography as the first dimension. The separation mechanism in the subsequent second dimension employed hydrophobic interactions using short reversed-phase (RP) columns. A new column-switching technique, including four parallel reversed-phase columns, was employed in the second dimension for on-line fractionation and separation. Gradient elution and UV detection of two columns were performed simultaneously while loading the third and regenerating the fourth column. The total integrated workstation was operated in an unattended mode. Selected peaks were collected and analyzed off-line by MALDI-TOF mass spectrometry. The system was applied to protein mapping of biological samples of human hemofiltrate as well as of cell lysates originating from a human fetal fibroblast cell line, demonstrating it to be a viable alternative to 2D gel electrophoresis for mapping peptides and small proteins.     

Development of an automated sample preparation module for environmental monitoring of biowarfare agents

An automated sample preparation module, based upon sequential injection analysis (SIA), has been developed for use within an autonomous pathogen detection system. The SIA system interfaced aerosol sampling with multiplexed microsphere immunoassay-flow cytometric detection. Metering and sequestering of microspheres using SIA was found to be reproducible and reliable, over 24-h periods of autonomous operation. Four inbuilt immunoassay controls showed excellent immunoassay and system stability over five days of unattended continuous operation. Titration curves for two biological warfare agents, Bacillus anthracis and Yersinia pestis, obtained using the automated SIA procedure were shown to be similar to those generated using a manual microtiter plate procedure.     

Influence of controlled particle size on pore size distribution and mechanical resistance of agarose beads for bioadsorption application

ABSTRACT

In this work the influence of fabrication conditions (ion strength, surfactant utilization) on the macro- (particle size distribution, PSD) and microscopic [pore size distribution (PoSD), specific surface area] structure of agarose beads was investigated. The main purpose was achieving uniform sized and porous beads with improved mechanical strength for bioseparation and chromatography applications. Therefore, PSD, PoSD, mechanical resistance, and flux through packed bed of the fabricated beads (4, 6, and 8% wt/wt) were analyzed. Based on porosimetry results, it was found that increasing ion concentration or presence of surfactant (the key variable for narrowing PSD) decreases the span value of PSD (p-value <0.05); thus, leading to a more uniform distribution. Moreover, as a result of controlling PSD, the PoSD changes from micro- to meso- and macropores in higher ion charged solutions. Furthermore, the obtained PoSD affects mechanical resistance of the prepared microspheres either as single beads or packed in a column. Mesoporous 6%-agarose beads showed the highest flux due to elevated mechanical resistance and elastic characteristic. Mesoporous 4%-beads showed the highest elasticity, and thus lower flux through column. These results demonstrate that manipulation of both macro- and microscopic characteristics of the beads should be commensurate with the intended application i.e., bioadsorption chromatography.     

前驱体粒径控制与氧化镁活性粉体制备

以卤水和石灰乳为原料,采用晶种循环长大的方法控制不同粒径氢氧化镁的析出,分别于不同热工制度下分解制备氧化镁粉体,研究前驱体粒径与氧化镁粉体活性的关系.结果表明,小粒径氢氧化镁(一次性快速反应获得)在较低的分解温度(如500～600℃)和适当的分解时间(4h)条件下,制得的氧化镁具有较高的烧结活性,由此获得的高温烧结体-镁砂具有优良的高致密性(体积密度达3.47g/cm3).     

特定孔径分布活性炭的制备及电容性能研究

在酚醛树脂中掺杂二茂铁可制得特定孔径分布的活性炭,炭化样品孔径主要在 3~4nm 之间分布,双层容量高达 0.26F/m2。水蒸气活化不同时间,树脂炭在10~20nm之间有较大孔容产生,同时比表面积增加。炭化样品碳含量高,但活化后,随碳氢含量的降低,结构破坏,双层容量降低。     

腐蚀添加剂对Cu-Mn合金制备孔径可控纳米多孔铜的影响

以铜锰单相固溶体为前躯体合金,利用去合金化法,在盐酸腐蚀液中添加适量不同的络合剂、金属盐可制备出成分纯净、孔形貌可控的三维连通纳米多孔铜(NPC)。采用X射线衍射仪(XRD)、扫描电镜能谱(SEM-EDS)、图像分析软件(Image-Pro Plus)对样品的物相、组分、微观形貌和平均孔径尺寸进行表征。结果表明：腐蚀添加剂的种类和浓度对孔结构形成过程和孔形貌具有重要影响。与未添加络合剂相比,添加硫脲、柠檬酸等络合剂后,腐蚀后的样品的孔径和韧带尺寸都发生不同程度的细化,络合常数越大,铜原子表面扩散系数越小,细化效果越明显;添加硫脲后能显著细化多孔结构,NPC平均韧带尺寸可在18～90 nm之间调控,且其浓度越高,孔径、韧带尺寸越小;添加适量金属盐Fe₂(SO₄)₃、CuSO₄、ZnSO₄后腐蚀液中出现副反应,反应速率大幅度提高,孔结构发生粗化,出现韧带尺寸分布呈纳米级和微米级共存的多孔结构,当CuSO₄添加浓度超过20 mmol/L时,多孔样品断裂截面失去初...     

粒子滤波算法在静止目标定位时的数学建模

粒子滤波算法在目标定位中主要用于目标跟踪,对静止目标定位的应用研究鲜有报道,尤其是针对具体的无线电移动监测车,已知数据只有车的位置坐标和目标示向度情况,数学模型的建立还没有文献可供参考。在熟悉粒子滤波机理的基础上,参考粒子滤波在目标跟踪时建立数学模型的方法,结合无线电移动监测车对静止目标定位的实际需要,建立粒子滤波算法在静止目标定位时的数学模型,模型中融合分类和择优的措施以提高定位精度。最后在LabVIEW平台下对所建立的模型进行仿真实验,结果表明所建立的模型准确可行。     

Nanoporous carbide-derived carbon with tunable pore size

Porous solids are of great technological importance due to their ability to interact with gases and liquids not only at the surface, but throughout their bulk. Although large pores can be produced and well controlled in a variety of materials, nanopores in the range of 2 nm and below (micropores, according to IUPAC classification) are usually achieved only in carbons or zeolites. To date, major efforts in the field of porous materials have been directed towards control of the size, shape and uniformity of the pores. Here we demonstrate that porosity of carbide-derived carbons (CDCs) can be tuned with sub?ngstr?m accuracy in a wide range by controlling the chlorination temperature. CDC produced from Ti3SiC2 has a narrower pore-size distribution than single-wall carbon nanotubes or activated carbons; its pore-size distribution is comparable to that of zeolites. CDCs are produced at temperatures from 200-1,200 degrees C as a powder, a coating, a membrane or parts with near-final shapes, with or without mesopores. They can find applications in molecular sieves, gas storage, catalysts, adsorbents, battery electrodes, supercapacitors, water/air filters and medical devices.     

A 96-well screen filter plate for high-throughput biological sample preparation and LC-MS/MS analysis

A novel 96-well screen filter plate (patent pending) has been invented to eliminate a time-consuming and labor-intensive step in preparation of in vivo study samples--to remove blood or plasma clots. These clots plug the pipet tips during a manual or automated sample-transfer step causing inaccurate pipetting or total pipetting failure. Traditionally, these blood and plasma clots are removed by picking them out manually one by one from each sample tube before any sample transfer can be made. This has significantly slowed the sample preparation process and has become a bottleneck for automated high-throughput sample preparation using robotic liquid handlers. Our novel screen filter plate was developed to solve this problem. The 96-well screen filter plate consists of 96 stainless steel wire-mesh screen tubes connected to the 96 openings of a top plate so that the screen filter plate can be readily inserted into a 96-well sample storage plate. Upon insertion, the blood and plasma clots are excluded from entering the screen tube while clear sample solutions flow freely into it. In this way, sample transfer can be easily completed by either manual or automated pipetting methods. In this report, three structurally diverse compounds were selected to evaluate and validate the use of the screen filter plate. The plasma samples of these compounds were transferred and processed in the presence and absence of the screen filter plate and then analyzed by LC-MS/MS methods. Our results showed a good agreement between the samples prepared with and without the screen filter plate, demonstrating the utility and efficiency of this novel device for preparation of blood and plasma samples. The device is simple, easy to use, and reusable. It can be employed for sample preparation of other biological fluids that contain floating particulates or aggregates.     

多农药残留的茶叶自制质控品的研究

目的:研究多农药残留的茶叶质控品自制方法。方法:采用定量喷施法自制了20种茶叶中常检农药残留质控品。结果:该方法的制成的农药残留质控品的回收率在定量喷施量的68.4%~92.5%,RSD均小于10%(n=6),该质控品2个月内的定值结果无显著性差异。结论:该方法操作简便,可用于茶叶中常检农药残留量的测定时的质控品。     

Determining sample size for specification limits verification with tolerance intervals

In the traditional industrial verification process, when the aim is the compliance to assigned specifications, it is difficult to find an affordable statistical method for the purpose. Most data tables in industrial procedures and standards deal with tolerance limits neglecting the potential needs to verify assigned specification limits. A two-sided tolerance interval, combined with a bivariate statistical hypothesis test can be used to address this problem. The proposed risk-based approach leads to the determination of the minimum sample size with preestablished probabilities of Type I and Type II errors, that are essential elements for estimating the safety and reliability risk. A novel method is proposed for determination of the tolerance interval testing factors. This approach calculates the testing factors based on the deviation of the mean and the variance from the null hypothesis when a specified value of Type II error is found. The deviations of the mean and variance are determined in such a way that an assigned proportion of the population falls within the specification limits. Additional studies are provided to assess the robustness of the method for nonnormal environments and to compare it with other methods.     

粒径分布对氧化铝多孔支撑体孔结构的影响

采用中位粒径(D50)分别为(20±2)μm、(15±2)μm、(10±2)μm的α-Al2O3粉体为原料,通过调整其粒径分布,考察了粒径分布参数δ的变化对片状支撑体孔结构的影响.研究表明,在本研究的三种中位粒径(D50)下,当δ＜4.0时,随δ值的增大,支撑体的孔隙率由40%下降到30%左右;当δ＞4.0以后,支撑体的孔隙率基本稳定在28%.对于采用中位粒径分别为(20±2)μm和(15±2)μm的原料制备的支撑体,当δ＜3.0时,随δ值的增大,支撑体的平均孔径分别从3.5μm减小到1.1μm,从2.0μm减小到1.3μm;而对D50为(10±2)μm的原料制备的支撑体,δ在1.5～8.0范围内变化时,支撑体的平均孔径基本稳定在0.8μm.采用中位粒径D50为(20±2)μm、(15±2)μm、(10±2)μm的三种原料制备的支撑体,随δ值的增大,其孔径分布变窄,最可几分布峰高变高,分布向小孔径方向移动.     

Optimal and effective technique for particle packing

In various fields ranging from manufacturing or pharmaceutical industry to agriculture or automotive industry air filters and -dryers filled with porous desiccant media are used for industrial air preparation. It is necessary to increase the mass of particulate material filled into the dryer for improving its efficiency. Practically this means decreasing porosity of the filler media. In order to achieve this, mechanical excitation (ensured by a vibration platform) is commonly used. However, applying outer excitation decreases the efficiency of filling procedure because of the high energy consumption of the vibratory device. To avoid unnecessary energy consumption it is recommended to examine the possibility of filling more particles into the canister without outer excitation. According to this in our present paper the gravitational deposition of particulate materials was investigated from viewpoint of porosity. Main idea of this research was the usage of the so called “snowstorm” filling technique. A conical hopper and under this multiple cylindrical rods were used to reach uniform deposition and high value of particle packing density. Thus efficiency of air preparation units may be increased as it is possible to fill more material into the container without additional energy usage compared to normal gravitational deposition.     

A particle packing algorithm for packed beds with size distribution

A particle packing algorithm for simulating realistic packed beds of spheres with size distribution is described. The algorithm used the Monte Carlo method combined with the simulated annealing minimisation algorithm to solve the packed bed simulations. The objective function which was minimised was a combination of two functions, one describing the deviation from the target mean coordination number of the spheres in each size interval and the other the average fraction of overlapping volume of the spheres per contact. In this way a realistic bed structure was maintained while at the same time controlling the coordination number of the spheres. The algorithm used an experimentally validated model to predict the mean coordination number of the spheres in each size interval.     

Characterization of silica-based monoliths with bimodal pore size distribution

Band dispersion was studied and the retention thermodynamics addressed for insulin and angiotensin II on C18 silica monoliths with a bimodal pore size distribution, covering linear mobile-phase velocities up to 1 cm/s and different temperatures. These data suggest that the influence of average column pressure on retention (between 0 and 10 MPa) is not negligible. Plate height curves were interpreted with the van Deemter equation by assuming an independent contribution from mechanical and non-mechanical dispersion mechanisms. This analysis revealed diffusion-limited mass transfer in the mesoporous silica skeleton which, in turn, allowed us to calculate an equivalent dispersion particle diameter (d(disp) = 3 microm) using the C-term parameter of the van Deemter equation. The resulting superposition of reduced plate height curves for monolithic and particulate beds confirmed that this view presents an adequate analogy. The macroporous interskeleton network responsible for the hydraulic permeability of a monolith was translated to the interparticle pore space of particulate beds, and an equivalent permeability particle diameter (d(perm) = 15 microm) was obtained by scaling based on the Kozeny-Carman equation.     

Collection, storage, and filtration of in vivo study samples using 96-well filter plates to facilitate automated sample preparation and LC/MS/MS analysis

The benefits of high-throughput bioanalysis within the pharmaceutical industry are well established. One of the most significant bottlenecks in bioanalysis is transferring in vivo-generated study samples from their collection tubes during sample preparation and extraction. In most cases, the plasma samples must be stored frozen prior to analysis, and the freeze/thaw (F/T) process introduces thrombin clots that are capable of plugging pipets and automated liquid-transfer systems. A new approach to dealing with this problem involves the use of Ansys Captiva 96-well 20-microm polypropylene filter plates to collect, store frozen, and filter plasma samples prior to bioanalysis. The samples are collected from the test subjects, and the corresponding plasma samples are placed directly into the wells of the filter plate. Two Duoseal (patent pending) covers are used to seal the top and bottom of the plate, and the plate is stored at down to -70 degrees C. Prior to sample analysis, the seals are removed and the plate is placed in a 96-well SPE manifold. As the plasma thaws, it passes (by gravity or mild vacuum) through the polypropylene filter into a 96-well collection plate. A multichannel pipet or automated liquid-transfer system is used to transfer sample aliquots without fear of plugging. A significant advantage of this approach is that, unlike other methods, issues related to incomplete pipetting are virtually eliminated. The entire process is rapid since thawing and filtering take place simultaneously, and if a second F/T cycle is required for reanalysis, it is not necessary to refilter the samples (additional clotting was not observed after three F/T cycles). This technique was tested using monkey, rat, and dog plasma and sodium heparin and EDTA anticoagulants. To assess the possibility of nonspecific binding to the polypropylene filter, a variety of drug candidates from diverse drug classes were studied. Validation data generated for two Lilly compounds from distinct classes, before and after filtering, are presented in this paper as practical examples of this technique. While LC/MS/MS is the primary method of bioanalysis in our laboratory, the technique presented in this paper is applicable to other forms of detection as well.