Mechanisms of retardation of rigid spherical particles with 3 to 1,085 nm radius in capillary electrophoresis, using buffered polyacrylamide (molecular weight 5 x 10(6)) solutions

Subjecting particles in the size range of 3 to 1085 nm radius (R) to capillary electrophoresis in buffered solution of entangled uncrosslinked polyacrylamide (M(r) 5 x 10(6)), it was found that particle size-dependent retardation ("molecular sieving") becomes electric field- and particle size range-dependent once the particle size exceeds 15-20 nm in radius. The field strength dependence of the retardation coefficient [KR = d(log mobility)/ d(polymer concentration] and the positive or negative sign of dKR/dR suggest the existence of two different mechanisms of molecular sieving depending on the particle size range: particles with diameters less than the screening length (or blob size) of the polymer network are thought to penetrate into the available spaces within a discontinuous polymer network; particles with diameters larger than the screening length (or blob size) of the polymer network are thought to undergo size-dependent retardation by exerting shear stress against polymer chains, and displacing them, so as to cause local deformations in a continuous polymer network. A limit in the separating capacity of molecular sieving, due to a sharp increase in the rate of band widening with polymer concentration, was found when the value of the retardation coefficient exceeded 60 (mL/g).     

Towards predicting mobility and resolution in polymeric media: some first steps

Particle size-dependent retardation ("molecular sieving") in electrophoresis can be achieved in polymer solutions or gels. In the semidilute concentration range of polymer solutions, mobility of "rigid, spherical" particles can be predicted from their size (in the size range less than 20 nm radius), the screening length specific for the particular polymer and a constant that can be experimentally determined for a polymer. That constant could be universal for all hydrophilic uncharged polymers. Band spreading in polymer solutions is constant over a range of particle sizes and polymer concentrations and increases beyond that range. Presumably, the critical division between the two ranges occurs when the diameter of the particle exceeds the screening length of the polymer network. Resolution, defined as separation divided by the sum of bandwidths, can thus be predicted for a limited particle size and polymer concentration range. In gels, resolution can be estimated from the slopes and free mobility intercepts of the Ferguson plot. However, the previous computation of resolution needs to be revised in view of the fact that band spreading in gels proceeds in proportion to time, presumably through interaction with the polymer, and not as a function of the square root of time as would be the case if band spreading resulted from diffusion.     

Parallelism between width and asymmetry of peaks of rigid, spherical particles in capillary zone electrophoresis using polymer solutions

Peak width and peak asymmetry of rigid spherical particles in the size range of 3-100 nm radius (R) were measured in capillary zone electrophoresis (CZE), using buffered uncross-linked polyacrylamide of Mr 5.0 X 10(6). Polymer concentration-dependent spreading of peak width and peak asymmetry were found to parallel one another. The parallelism holds whether the particle size is within the "small" (R < 20 nm) or "large" (R > 20 nm) size ranges previously found to differ in the mechanism of particle size dependent retardation of electrophoretic migration (S. P. Radko and A. Chrambach, Electrophoresis 1996, 17, 1094-1102). In application to the "small" particle size range, the parallelism between band width and band asymmetry can be qualitatively interpreted to be consistent with the Giddings-Weiss mechanism (G. H. Weiss et al., Electrophoresis 1996, 17, 1325-1332) of electrophoresis in polymer-containing media which postulates a dependence of band width and band asymmetry on the equilibrium between "stationary" and "mobile" states of the particle.     

Polyethyleneglycol-stabilized manganese-substituted hydroxylapatite as a potential contrast agent for magnetic resonance imaging: particle stability in biologic fluids

RATIONALE AND OBJECTIVES: Polymer-stabilized manganese(II)-substituted hydroxylapatite (MnHA) has been investigated as a particulate contrast agent for magnetic resonance imaging. The MnHA core requires a polymer coating to retard opsonization, thereby prolonging its systemic persistence. Therefore, the aim of this study was to assess the stability of various formulations in biologic media in vitro. METHODS: Polyethyleneglycol-coated manganese(II)-substituted hydroxylapatite particles were studied in bovine plasma as a function of the concentration of polymer in the formulation. Particle sizing techniques and nuclear magnetic resonance proton relaxometry were used to evaluate both in vitro and in vivo stability. RESULTS: A small-sized particle (approximately 10 nm diameter) that is stable in bovine plasma and rabbit whole blood was formed in formulations with high amounts of polymer concentration. In formulations with low amounts of polymer concentration, larger-sized particles (approximately 100 nm diameter) were present along with the small-sized population. The larger particles de-aggregated into the small-size particle distribution on dispersion in bovine plasma and rabbit whole blood. CONCLUSIONS: Ultrasmall particles with high surface coat were stable in plasma, whereas larger aggregates de-aggregated. Unlike Mn2+, the interaction of polyethyleneglycol-stabilized manganese(II)-substituted hydroxylapatite with plasma proteins was weak.     

Lidocaine-loaded biodegradable nanospheres. I. Optimization Of the drug incorporation into the polymer matrix

Spherical nanoparticulate drug carriers made of poly(d,l-lactic acid) with controlled size were designed. A local anesthetic, lidocaine, a small hydrophobic molecule, was incorporated in the core with loadings varying from about 7 to 32% (w/w) and increasing with the particle size. Particles with sizes from about 250 to 820 nm and low polydispersity were prepared with good reproducibility; the polymer concentration (at constant surfactant concentration) governed the particle size. The large particles with a high loading ( approximately 30%) showed under in vitro conditions a slow release over 24-30 h, the medium sized carriers (loading of approximately 13%) released the drug over about 15 h, whereas the small particles with small loading ( approximately 7%) exhibited a rapid release over a couple of hours. It seems that the drug release rate is related to the state (crystallized or dispersed) of the drug incorporated in the polymer matrix.     

Effect of gadolinium incorporation on optical characteristics of YNbO_4：Eu~（3＋） phosphors for lamp applications

Eu3+-doped (Y,Gd)NbO4 phosphor was synthesized by solid-state reaction for possible application in cold cathode fluorescent lamps. A broad absorption band with peak maximum at 272 nm was observed which was due to the charge transfer between Eu3+ ions and neighboring oxygen anions. A deep red emission at the peak wavelength of 612 nm was observed which could be attributed to the 5D0→7F2 transition in Eu3+ ions. The highest luminance for Y1-x-yGdyNbO4:Eux3+ under 254 nm excitation was achieved at Eu3+ concentration of 18 mol.% (x=0.18) and Gd3+ concentration of 8.2 mol.% (y=0.082). The luminance of Y0.738Gd0.082NbO4:Eu3+0.18 was higher than that of a typical commercial phosphor Y2O3:Eu3+ and the CIE chromaticity coordinate was (0.6490, 0.3506), which was deeper than that of Y2O3:Eu3+. The particle size of the synthesized phosphors was controlled by the NaCl flux and particle size as high as 8 μm with uniform size distribution of particles was obtained.     

Microstructures of the commercial 7075 Al alloy in the T651 and T7 tempers

The microstructures of the commercial 7075 Al alloy in the peak aged (T651) and overaged (T7) tempers were studied using transmission electron microscopy. The microstructure of 7075-T651 is characterized predominantly by the presence of a fine dispersion of the ? transition phase; the primarily plate-shaped ? particles have diameters ranging from 3 to 10 nm. The microstructure of 7075-T7 mainly consists of a bimodal size distribution of ? phase variants,i.e., plate-shaped ?₁ and ?₂ particles ranging from 12.5 to 30 nm in diameter and finer ?₁ particles 5 to 10 nm in diameter. The ? transition phase is identified as having a hexagonal crystal structure with lattice parameters, α = 0.496 nm andc = 1.403 nm. The maximum hardness of the 7075 alloy is believed to arise mainly from the fine dispersion of small ? particles.     

Application of spherical and other polymers in capillary zone electrophoresis: separation of antiviral drugs and deoxyribonucleoside phosphates by different principles

Soluble polymers of linear chains with limited branching and spherical polymers (limit dextrins and sucrose, such as Dextran and Ficoll (Pharmacia Chemicals), yielding lower viscosities, are examined here for the separation of different nucleotides and several anti-AIDS drugs by capillary zone electrophoresis (CZE). The linear polymer forms a network but spherical polymers appear to create a second pseudo-phase. In general, they tend to enhance the solute mobility and reduce peak width; thus, they improve the column efficiency. We observe that the beads of a spherical polymer produce a pseudo-phase even in a very low polymer concentration. The proposed method involving a spherical polymer yields the best separation for twelve deoxyribonucleoside mono-, di- and triphosphates in ca. 10 min. Common anti-AIDS drugs (ddA, ddC, ddI, d4T, AZT) and an AZT metabolite (AZT-glucuronate) are resolved by using conventional micellar electrokinetic capillary chromatography (MEKC). These results not only offer fast and highly sensitive detection techniques for the pharmacokinetics of nucleotides, drugs, and their metabolites, but they also demonstrate an application of the proposed second pseudo-phase involving spherical polymer beads in CZE separations.     

Melting behaviour of In and Pb particles embedded in an Al matrix

Microstructures of melt spun hypomonotectic Al−7wt%In, hypermonotectic Al−5wt%Pb and near monotectic Al−2wt%Pb alloys have been examined by transmission electron microscopy and consist of 10–150 nm diameter faceted In particles and 5–150 nm faceted Pb particles homogeneously distributed in an Al matrix. As-melt spun In and Pb particles exhibit near cube-cube and cube-cube orientation relationships with the Al matrix respectively, and truncated octahedral shapes bounded by {111} and {100} facets. The melting behaviour of In and Pb particles in as-melt spun Al−7wt%In, Al−5wt%Pb and Al−2wt%Pb alloys has been investigated by heating and cooling experiments in a differential scanning calorimeter and in situ heating experiments in a transmission electron microscope. In and Pb particles embedded within the Al matrix grains melt at superheatings in the range 0–40 K above the bulk equilibrium In and Pb melting points. Superheating of In and Pb particle melting within the Al matrix grains is caused by a kinetic difficulty of nucleating melting which increases with decreasing In and Pb particle size. In and Pb particles along the grain boundaries of the Al matrix melt at undercoolings in the range 0–7 K below the bulk equilibrium In and Pb melting points.     

Small low-density lipoproteins and vascular cell adhesion molecule-1 are increased in association with hyperlipidemia in preeclampsia

The pregnancy disorder preeclampsia is characterized by endothelial cell dysfunction that may be promoted by abnormal increases in circulating lipids, particularly triglycerides and free fatty acids. Serum triglyceride concentration is a major regulatory determinant of low-density lipoprotein (LDL) size and density distribution. Smaller, denser LDL particles have several intrinsic properties capable of inducing endothelial dysfunction. The present nested, case-control study of gestationally matched preeclamptic and normal pregnant women tested the hypothesis that hypertriglyceridemia in preeclampsia is accompanied by decreases in LDL peak particle diameter (predominant LDL size). Plasma LDL peak particle diameter was determined by nondenaturing 2% to 16% polyacrylamide gel electrophoresis. Correlations of LDL diameter with the concentration of serum triglycerides, free fatty acids, total cholesterol, LDL-cholesterol, and apolipoprotein B (apo B) were determined. In the same individuals, we measured serum concentrations of a marker of vascular dysfunction previously reported to be increased in preeclampsia, soluble vascular cell adhesion molecule-1 (VCAM-1), and examined the association of VCAM-1 with LDL diameter and serum lipids. LDL peak particle diameter was decreased in preeclampsia relative to normal pregnancy (P < .01). The LDL-cholesterol:apo B ratio, which frequently decreases with decreasing LDL diameter, was also decreased (P < .04). Triglyceride concentrations were increased in preeclampsia (P < .0002), and there was a significant inverse relationship between LDL peak particle diameter and triglycerides (r = -.55, P < .02). Serum soluble VCAM-1 concentrations were markedly increased in preeclampsia (P < .0003). Apo B (P < .004), free fatty acids (P < .01), total cholesterol (P < .01), and LDL-cholesterol (P < .02) were also increased. VCAM-1 correlated with apo B (r = .50, P < .03) and LDL-cholesterol (r = .50, P < .03), but showed no relationship with the LDL diameter, LDL-cholesterol:apo B ratio, or other lipids. We conclude that the predominance of smaller, denser LDL, a potential contributor to endothelial cell dysfunction, is a feature of preeclampsia. However, the serum VCAM-1 level, one indicator of endothelial involvement, may be influenced more by quantitative lipoprotein changes (serum apo B or LDL-cholesterol) than by LDL particle size.     

Capillary electrophoretic separation of 1 to 10 kbp sized dsDNA using poly(ethylene oxide) solutions in the presence of electroosmotic counterflow

DNA fragments of 1 to 10 kbp in length were separated by capillary electrophoresis (CE), using poly(ethylene oxide) (PEO) solutions in the presence of electroosmotic flow. The technique requires filling the capillary with the polymer solution by means of electroosmotic flow (EOF). Separation times of 6-7 min in PEO solutions ranging from 0.3 to 8 x 10(6) Mr at 375 V/cm were sufficient to separate the 11 components of the dsDNA ladder (0.5 to 10 kbp) by size. The migration behavior of the double-stranded (ds)DNA fragments, interpreted by "Ferguson plot analysis", in the system is indistinguishable from that previously reported for capillary zone electrophoresis (CZE) in a polyacrylamide solution without EOF. Potential advantages of conducting CZE using polymer solutions in the presence of EOF are: (i) Possibility of long migration times on short columns; (ii) possibility of introducing relatively viscous, high Mr polymer solutions into narrow capillaries; (iii) possibility of establishing polymer concentration gradients in capillaries; (iv) possibility of concentrating the starting zone by balancing electrophoretic migration and electroosmotic transport.     

均匀共沉淀法合成纳米Gd_2O_3:Eu粉体及其发光特性

以六次甲基网胺(hexamethylenetetramine,(CH2)6N4,HMT)为沉淀剂,在GdCl3和EuCl3混合溶液中,利用均匀共沉淀法制得了纳米颗粒.结果表明,获得的Gd2O3:Eu纳米颗粒近似为球形,尺寸均匀,平均粒径为100 nm,且每个球形颗粒由平均粒径为20 nm的微晶聚并而成.Gd2O3:Eu荧光粉在波长612 nm的红光发射来自Eu3+的5D0-7F2电偶极跃迁,发光强度随煅烧温度提高而增强,随Eu3+掺杂摩尔分数的提高而增强.Eu3+掺杂摩尔分数超过7%时,发生浓度淬灭,发光强度减弱.     

铁矿烧结过程微细颗粒物排放行为

 采用ELPI+设备(荷电低压撞击器)对铁矿烧结过程微细颗粒物进行在线检测与采样,利用场发射扫描电子显微镜(FESEM EDS)对采集的颗粒物形貌特征进行分析,研究铁矿烧结过程中微细颗粒物的排放行为。研究结果表明,PM10大量释放集中在烧结升温段,且颗粒物质量浓度与数目浓度在粒径分布上有较大差异,其中质量浓度峰值区间为5.37～10.00 μm,数目浓度峰值区间为0.10～0.16 μm;形貌特征上,微细颗粒物呈规则的球形、方块形和片状;不同粒径物质组成差异明显,其中颗粒物中的K、Na主要以KCl和NaCl的形式存在,含量随颗粒物粒级的增大而略有降低。     

基于固液两相流模拟的选矿循环水深度澄清装置优化

部分选矿循环水中含一定量的高分散性悬浮颗粒,仅依靠简单浓缩沉降难以澄清,无法达到回用要求。针对这一难题,提出了一种选矿循环水固体悬浮物澄清装置。为优化装置的结构参数与运行参数,建立了选矿循环水深度澄清装置的二维物理模型,基于计算流体力学（CFD）的方法,选用Mixture和RNG k?ε 模型对装置主要的结构参数与运行参数展开了数值模拟研究。研究发现适当降低水力循环区喷嘴长度,增加喉管与喷嘴管径比、颗粒沉降区开口尺寸、装置直径等结构,能够降低颗粒沉降区平均湍动能,由于湍动能为单位质量流体由于紊流脉动所具有的动能,故降低了颗粒沉降区流场的紊流程度,增加了水流的稳定性,提高了装置对悬浮颗粒的去除效果;同时发现降低入口流速、增加悬浮颗粒粒径有助于提高悬浮物的去除率,当进水流速为0.1 m·s?1、经过混凝的悬浮颗粒形成粒径大于100 μm时,装置对选矿循环水中的悬浮颗粒去除效果显著。      

Quantitative analysis of non-steroidal anti-inflammatory drugs by capillary zone electrophoresis

The potential utility of capillary zone electrophoresis (CZE) for the separation and quantitative determination of some non-steroidal anti-inflammatory drugs (NSAIDs) was investigated. The influence of different parameters on migration times, peak symmetry, efficiency and resolution was studied; these parameters included the nature and concentration of the anionic and cationic components of the separation buffer. A buffer consisting of 75 mM glycine adjusted to pH 9.1 with triethanolamine was found to provide a very efficient and stable electrophoretic system for the CZE analysis of NSAIDs, giving RSD values of about 0.1 and 0.5% for the within-day reproducibility of migration times and peak areas, respectively at a concentration of 25 micrograms ml-1 (n = 5). Response was linear from 2-100 micrograms ml-1 for both sulindac and tiaprofenic acid, for which the LOQ values were 2.8 and 1.9 micrograms ml-1, respectively, using UV detection at 280 nm. Accuracy for each drug was 102-103%.     

Microstructure of second-phase particles in Ti-5Al-4Sn-2Zr-1Mo-0.25Si-1Nd alloy

The microstructure of second-phase particles in the Ti-55 alloy (Ti-5Al-4Sn-2Zr-1Mo-0.25Si-1Nd) was studied by scanning electron microscopy, transmission electron microscopy (TEM), and high-resolution electron microscopy (HREM) observations. The second-phase particles in the conventional ingot-cast Ti-55 alloy of 1 to 15 μm in diameter and uniform distribution in matrix were observed, where the majority of these particles are elliptical. The mean free path between the particles is about 46 μm, and the volume fraction (pct) is 2.35. The second-phase particles typically contain Nd, Sn, and O in substantial amounts, and the content of Nd is the largest in the three elements. The elements Ti, Al, Zr, Mo and Si are depleted in the particles. The second-phase particle consists of either a dark or bright matrix and some small dark blocks dispersed within the matrix. Dark blocks match SnO (orthorhombic, a=0.500 nm, b=0.572 nm, and c=1.120 nm), and the matrix consists of a nanocrystalline phase with a stoichiometric Nd₃Sn structure having a space group of Pm3m and lattice parameter of a=0.344 nm. The grain size of the nanocrystalline Nd₃Sn phase is about 3 to 15 nm. The melting range of the second-phase particle is estimated to be 1042 °C to 1600 °C. The microstructure of the second-phase particles in the quenched Ti-55 alloy was also studied. Fine and uniform dispersoids (6 to 15 nm in diameter) were observed in the as-quenched state. Some lenslike particles occur at the grain boundaries, other elliptical particles appear within the grains, and some particles within the grains form rows which are parallel to the advancing liquid-solid interface. After annealing at 980 °C (1 to 10 hours), of the as-quenched Ti-55 alloy, coarse particles are 17 to 42 nm in average diameter, and the growth of the particles is very slow. The dispersoids in the as-annealed Ti-55 alloy are identified as nanocrystalline Nd₅Sn (orthorhombic, Pnmn, a=0.814 nm, b=1.732 nm, and c=0.814 nm) intermetallic compound, and the interface between the Nd₅Sn₄ phase and the matrix is a typical high-angle grain boundary.     

Dynamic Characteristics of Particle Size Distribution in Highway Runoff: Implications for Settling Tank Design

To understand the characteristics of particle size distribution (PSD) in highway runoff and to facilitate designing best management practices, PSD (2–1,000?μm) was monitored in seven rainfall events in the 2002–2003 rainy season at three highway sites in west Los Angeles. Most of the particles in number were less than 30?μm in diameter and more than 90% were less than 10?μm. Particle number concentration decreased rapidly to 6?mm of accumulated rainfall and then declined more slowly throughout the storm. Particle number concentration was correlated with total suspended solids (TSS) and turbidity. Grab sample particle median diameter increased with increasing TSS. A two-compartment settling tank was evaluated using the measured PSD and was effective in removing both small and large particles. Capturing and retaining the first 20% of the runoff volume on seasonal average can remove 40% of the total particulate load based on calculated particle mass. Using literature data for metal concentrations sorbed to particles, this size holding compartment coupled with a similar size continuous flow clarifier can achieve 65–90% removal for the metals investigated.     

Silver enhancement of gold antibody probes in pre-embedding electron microscopic immunocytochemistry

In pre-embedding EM immunocytochemistry with gold probes, the gold must be small enough to penetrate through cell membranes treated with mild detergents. Antibodies labeled with small gold probes (1-1.4 nm) are too small to be resolved in thin sections but can be seen if they are silver-enhanced after the gold has bound to the antigens in the cells. We investigated several aspects of gum arabic-silver lactate-hydroquinone enhancement solution (Danscher solution) by examining gold-conjugated antibodies embedded in agar, sectioned on a vibrotome, and enhanced with different solutions. The rate of silver enhancement was optimized in 50% gum arabic and 200 mM HEPES buffer, pH 5.8. We also examined chemicals used as developers and found that N-propyl gallate (NPG) gave a more uniform development than the routinely used hydroquinone (HQ). The diameter of the silver-enhanced particles after incubation in osmium tetratoxide (OSO4) decreased somewhat with longer incubation time and higher percentages, but the density (number per unit area) of silver-enhanced particles was little changed. The loss of silver-enhanced particle diameter was reduced by lowering the concentration of OSO4 to 0.1%. Comparison of commercial small gold probes showed that NPG enhancement of Nanogold gave more uniform particle size and a better correlation between enhancement time and particle density. When this procedure was applied to cell cultures with monoclonal antibodies, the silver-enhanced particles were similar to those in the agar sections. When free-floating tissue sections were used, longer silver enhancement times were needed to obtain similarly sized particles. This new NPG-silver-enhancement procedure offers a reliable and easy method to localize proteins in cultured cells and tissue sections by pre-embedding electron microscopic immunocytochemistry.     

高分子保护固相法制备纳米氧化镁

以六水氯化镁和草酸钠为原料,用聚乙二醇作保护剂,通过室温固相化学反应制备了纳米氧化镁的前驱物,真空干燥后,在500℃焙烧前驱物3 h,得到产物纳米氧化镁。采用热分析仪、红外光谱仪、X-射线粉末衍射仪和透射电镜等研究了纳米氧化镁的形成过程和结构;并考察了焙烧温度、焙烧时间和高分子用量对粒径大小的影响。结果表明:高分子保护固相法制备的纳米氧化镁为球形立方晶系结构,纯度高,粒径小,分布范围窄,分散性好,无硬团聚,平均粒径约7.8 nm;高分子保护固相法制备纳米氧化镁的适宜工艺条件为:焙烧温度500℃,焙烧时间3 h,高分子用量3 mL。     

Effect of size, concentration, surface area, and volume of polymethylmethacrylate particles on human macrophages in vitro

This study investigated effects of different sizes, concentrations, volumes, and surface areas of polymethylmethacrylate (PMMA) particles on human macrophages. Adherent peripheral blood monocytes isolated from five healthy individuals were exposed for 48 h to phagocytosable (0.325 micron and 5.5 microns) and nonphagocytosable (200 microns) spherical particles. Each particle size was tested over a range of concentrations (10(4)-10(11) particles per milliliter [0.325 micron], 10(2)-10(7) particles per milliliter [5.5 microns], 10(1)-10(4) particles per milliliter [200 microns]) to provide overlap in number, volume, and surface area. Primary human monocyte/macrophages were cultured in macrophage serum-free medium and 5% fetal calf serum. Macrophage viability was assessed by 3H-thymidine uptake and activation was quantified by release of interleukin-1 beta, interleukin-6, tumor necrosis factor-alpha, prostaglandin E2 (PGE2), and the lysosomal enzyme hexosaminidase. Medium alone served as a negative control; lipopolysaccharide (10 micrograms/mL) was also tested. PMMA particles were not toxic to human macrophages at any concentration tested. The smallest phagocytosable particles (0.325 micron) stimulated the release of interleukin-1 beta, interleukin-6, prostaglandin E2, and hexosaminidase at concentrations of 10(10)-10(11) particles/mL. The release of cytokines, PGE2, and hexosaminidase depended on the size, concentration, surface area, and volume of the phagocytosable particles. This study demonstrates that PMMA particle load Mi.e., the concentration of phagocytosable particles per tissue volume, characterized by size, surface area, and volume, rather than simply particle number-determines the degree of macrophage activation.