Polymer monoliths with low hydrophobicity for strong cation-exchange capillary liquid chromatography of peptides and proteins

Two polymer monoliths were designed and synthesized from commercially available monomers with an attempt to decrease hydrophobicity for strong cation-exchange chromatography. One was prepared from the copolymerization of sulfoethyl methacrylate and poly(ethylene glycol) diacrylate, and the other was synthesized from vinylsulfonic acid and poly(ethylene glycol) diacrylate. Both of the monoliths were synthesized inside 75-microm i.d., UV-transparent fused-silica capillaries by photopolymerization. The hydrophobicities of the two monoliths were systematically evaluated using standard synthetic undecapeptides under ion-exchange conditions and propyl paraben under reversed-phase conditions. The poly(sulfoethyl methacrylate) monolith demonstrated similar hydrophobicity as a monolith prepared from copolymerization of 2-acrylamido-2-methyl-1-propanesulfonic acid and poly(ethylene glycol) diacrylate, and 40% acetonitrile was required to suppress any hydrophobic interactions with peptides under ion-exchange conditions. However, with the use of vinylsulfonic acid as the functional monomer, a monolith with very low hydrophobicity was obtained, making it suitable for strong cation-exchange liquid chromatography of both peptides and proteins. It was found that monolith hydrophobicity could be adjusted by selection of monomers that differ in hydrocarbon content and type of vinyl group. Finally, excellent separations of model protein standards and high-density lipoproteins were achieved using the poly(vinylsulfonic acid) monolith. Five subclasses of high-density lipoproteins were resolved using a simple linear NaCl gradient.     

Determination of mean diameter and particle size distribution of acrylate latex using flow field-flow fractionation, photon correlation spectroscopy, and electron microscopy

Flow field-flow fractionation (flow FFF) was employed to determine the mean diameter and the size distribution of acrylate latex materials having diameters ranging from 0.05 to 1 μm. Mean diameters of the samples determined by flow FFF are in good agreement with those obtained from photon correlation spectroscopy (PCS). Scanning electron microscopy (SEM) yielded a mean diameter that is about 20% lower than those obtained from flow FFF or PCS, probably due to the shrinkage of particles during sample drying and high-vacuum measurements. It was found that flow FFF is particularly useful for the determination of particle size distributions of latex materials having broad size distributions. Flow FFF separates particles according to their sizes and yields an elution curve that directly represents the particle size distribution of the sample. In PCS, measurements had to be repeated at more than one scattering angle to obtain an accurate mean diameter for the latex having a broad size distribution. Flow FFF was fast (less than 12 min of run time) and showed an excellent repeatability in measuring the mean diameter with ±5% relative error.     

Surface-alkylated polystyrene monolithic columns for peptide analysis in capillary liquid chromatography-electrospray ionization mass spectrometry

Macroporous poly(styrene-divinylbenzene) (PS-DVB) monoliths were prepared by in situ polymerization in PEEK, fused silica, or stainless steel tubing having an inner diameter of 75 or 125 microm. A process is described for subsequent alkylation of the flow-contacting surfaces of the monoliths. The process treats all the surfaces including through-pore surfaces of the rigid macroporous monolith with a solution containing a dissolved Friedel-Crafts catalyst, an alkyl halide (1-chlorooctadecane), and an organic solvent. This process produces an improved reversed-phase liquid chromatographic separation of peptides compared to an unmodified monolithic PS-DVB column. The surface octadecylation is not necessary for a reversed-phase separation of proteins since both unmodified and modified columns provide comparable results. Tryptic protein digests, standard proteins, and standard peptides were used to evaluate the monolithic columns by employing electrospray mass spectrometry detection. Potential applications in proteomics studies by mass spectrometry, which use the alkylated monolithic column engaged onto the nanofabricated electrospray ionization chip, are also discussed.     

大孔钙铝石块体材料的制备及表征

以无机盐二水氯化钙(CaCl₂·2H₂O)和六水氯化铝(AlCl₃·6H₂O)为原料, 1,2-环氧丙烷(PO)为凝胶促进剂, 粘均分子量M_w= 100000的聚氧化乙烯(PEO)为相分离诱导剂, 乙二醇为络合剂, 甲酰胺为干燥控制化学添加剂(DCCA), 采用溶胶-凝胶伴随相分离制备了大孔钙铝石块体。利用扫描电镜(SEM)、压汞、X射线衍射(XRD)等测试技术对所得的块体进行了表征。结果表明: 加入PEO能诱导体系发生相分离; PEO用量和溶剂中醇水比会对多孔结构产生明显影响; 在合适凝胶温度下, 当加入适量PEO和溶剂时, 可以获得共连续大孔结构的钙铝石块体; 1000℃热处理后, 干凝胶由无定型转变为钙铝石晶型Ca₁₂Al₁₄O₃₂Cl₂, 块体的共连续大孔结构在热处理后被完整保留, 其大孔孔径分布在1~2 μm, 孔隙率为73.0%; 热处理前后的钙铝石块体均能保持光滑且致密的骨架。     

整体型环氧树脂大孔聚合物的制备与表征

用三亚乙基四胺(TETA)作为固化剂,通过双酚A环氧树脂在聚乙二醇(PEG)介质中的聚合反应诱导相分离制备具有三维骨架结构的整体型环氧树脂大孔聚合物。固定PEG1000与PEG2000的质量比为6∶1,分别研究了环氧树脂与PEG的比例关系和TETA的用量对整体型大孔聚合物孔结构的影响,用FT-IR、SEM、BET和MIP对整体型大孔聚合物进行表征并将其用于重金属离子的吸附。结果表明,改变环氧树脂与PEG的比例关系或者TETA的用量都可以调控大孔聚合物的孔结构,其孔径为0.1~1μm。孔径最小的整体型大孔聚合物比表面积最大,约84.4m~2/g,但孔径较大的整体型大孔聚合物对重金属离子(Cu~(2+))的吸附性能更好,吸附量高达113.1mg/g。     

单分散苯乙烯/丙烯酸丁酯共聚微球的制备

以苯乙烯和丙烯酸丁酯为反应单体,聚乙烯吡咯烷酮为分散剂,偶氮二异丁腈为引发剂,乙醇/水为分散介质,采用分散聚合法制备了微米级苯乙烯/丙烯酸丁酯共聚微球,通过红外光谱、核磁共振氢谱和扫描电镜对产物进行了表征,并且对不同聚合条件下,产物微球的粒径和粒径分布进行了研究。结果表明,随着苯乙烯/丙烯酸丁酯比值增大,粒子平均粒径和分布都减小;分散剂用量增加,粒子平均粒径减小,分布变窄;增加引发剂用量或提高温度,粒子平均粒径增大,分布变宽;随着乙醇/水比值增大,粒子平均粒径增大,分布有个极小值。     

Efficient polymer monolith for strong cation-exchange capillary liquid chromatography of peptides

A stable poly[2-acrylamido-2-methyl-1-propanesulfonic acid-co-poly(ethylene glycol) diacrylate] monolith was synthesized inside a 75-microm-i.d. capillary by photoinitiated copolymerization with water, methanol, and ethyl ether as porogens. The resulting monolith was evaluated for strong cation-exchange capillary liquid chromatography of both synthetic and natural peptides. Although the monolith possessed relatively strong hydrophobicity due to the use of 2-acrylamido-2-methyl-1-propanesulfonic acid as one monomer, the monolith had a high dynamic binding capacity of 157 microequiv of peptide/mL, or 332 mg of cytochrome c/mL. Exceptionally high resolution resulting from extremely narrow peaks was obtained, resulting in a peak capacity of 179 when using a shallow salt elution gradient. Although a second, naturally formed gradient might contribute to the sharp peaks obtained, high efficiency was mainly due to the use of poly(ethylene glycol) diacrylate as a biocompatible cross-linker.     

On the growth sequence of highly ordered nanoporous anodic aluminium oxide

Anodic aluminium oxide films were fabricated by well known two-step anodizing process in oxalic acid electrolyte. The ordering characteristics (ordered pore domains, average pore diameter size and through-pore arrangement) of anodic aluminium oxide films, obtained in different growth sequences, were identified by microscopic analysis such as ex situ contact-mode atomic force microcopy and scanning electron microscopy. Flattened areas in which some pits are seen mostly cover the electropolished surface of aluminium. Single anodizing of aluminium produces a broad distribution of nanopore size, whereas induces a highly ordered hemispherical pattern, which plays the ordered nucleation sites for the second anodizing step. Moreover, a quasi-linear growth behavior exists for the ordered domain growth versus the duration of first step anodizing. The through-pore arrangement of ideally grown membranes is not influenced by increasing the duration of second step anodizing.     

三维网笼状聚N-羟甲基丙烯酰胺/聚乙二醇半互穿网络复合相变微球的制备及热性能

以N-羟甲基丙烯酰胺(N-MA)和聚乙二醇(PEG)共晶为原料,通过乳液聚合制得聚N-羟甲基丙烯酰胺(PN-MA)/PEG半互穿网络(SIPN)复合相变材料(CPCM).利用FTIR、XRD、差示扫描量热仪(DSC)、SEM、EDS等方法对PN-MA/PEG SIPN型CPCM的结构与性能进行了研究.结果 表明:所得P...     

High-efficiency solvating gas chromatography using packed capillaries

In this study, column efficiency in packed capillary column solvating gas chromatography (SGC) was investigated. Long (>3 m) fused silica capillaries with an inner diameter of 250 μm were packed with 10 and 15 μm spherical porous (300 ?) octadecyl bonded silica particles using a CO(2) slurry packing method. A 336 cm × 250 μm i.d. fused silica capillary containing 10 μm particles provided a total column efficiency of 264?000 plates (k = 0.41), corresponding to a reduced plate height of 1.27, using CO(2) as the mobile phase at a column inlet pressure of 260 atm. A minimum plate height of 12.7 μm and a maximum plate number per unit time of 813 plates/s were obtained using packed capillary SGC. Retention factors were dependent on the column inlet pressure but independent of the pressure gradient along the column. Gasoline and diesel samples were separated under SGC conditions, and the results were comparable to those obtained using typical open tubular column gas chromatography.     

Application of dynamic light scattering to the study of small marine particles

Small particles ranging from approximately 0.1 μm to several micrometers in size, which include detrital material, bacteria, and other planktonic microorganisms, make a significant contribution to light scattering in the upper ocean. The scattering properties of these particles are strongly dependent on their size, which is difficult to measure in the submicrometer range with commonly used electronic resistive counters and microscopic techniques. We examined the size of small marine particles by application of the dynamic light scattering (DLS) method. In this method the time-dependent autocorrelation function of scattered intensity by particles undergoing Brownian motion provides information about the size of particles. The samples were collected in clear oceanic waters off the coast of Southern California. The mean hydrodynamic diameter of particles, determined from the DLS measurements at a scattering angle of 45°, was 0.54μ m. This indicates that the major contribution to scattering at this angle comes rom submicrometer particles. We also described an inverse method for estimating the general slope of the size distribution of small marine particles from the mean hydrodynamic diameter. This method is based on calculations of the size distribution weighted by distribution from Mie theory and assumes that a power-law approximation represents the actual particle scattered intensity. These calculations suggested that particulate assemblage in our seawater samples was best characterized by a differential size distribution with a slope of -4.35. This estimation was supported by independent measurements of particle size distribution and the spectral beam attenuation coefficient taken from the same samples as those used for the DLS measurements. We also demonstrated that multiangle DLS measurements may be used to determine the representative value of the refractive index of particles.     

A novel method for the synthesis of polyamide 6 magnetic microspheres

Polyamide 6 (PA6) magnetic microspheres were firstly prepared via successively in situ polymerization using phase inversion technology of polymer pairs polyamide 6/polystyrene (PA6/PS) at extremely low PS content. The properties of PA6 magnetic microspheres, such as morphologies, diameter size distribution, magnetic properties, thermal stability, and the functional groups of the magnetic microspheres, were investigated by different techniques (i.e. SEM, TEM, DLS, VSM, FTIR, and DSC). The results indicated that the diameter distribution of PA6 magnetic microspheres was narrow, and the mean diameter size was about 7.7 μm. The saturation magnetization of magnetic microspheres reached 12.50 emu/g. Furthermore, the magnetic microspheres had abundant functional groups and better thermal stability.     

交联剂对可膨胀小球制备的影响

以丙烯腈为主要单体,以氢氧化镁为无机分散剂,采用常压聚合法,制备了膨胀倍率达到20-30倍的可膨胀小球。系统研究了二丙二醇二丙烯酸酯(DPGDA)、三缩丙二醇二丙烯酸酯(TPGDA)、新戊二醇二丙烯酸酯(NPGDA)、三羟甲基丙烷三丙烯酸酯(TMPTA)和二乙烯基苯(DVB)等5种交联单体对可膨胀小球制备的影响。通过扫描电子显微镜、热重分析、交联密度测定等手段研究了可膨胀小球的形貌、粒径、发泡剂的含量、交联密度、发泡倍率。确定DPGDA为最佳的交联剂种类,用量为1.7%。采用DPGDA作为交联剂的小球既具有较完好的球状形貌,又有较小的粒径,较高的发泡剂含量和较高的交联度,膨胀倍率可达30倍。     

PLLA-PEG-PLLA/Fe_3O_4磁性微球的制备及性能

以聚乙二醇为引发剂,L-丙交酯为单体,开环聚合得到聚乳酸-聚乙二醇三嵌段共聚物(PLLA-PEG-PLLA),采用溶剂挥发法制备了PLLA-PEG-PLLA/Fe_3O_4磁性微球,并通过扫描电镜对其形态进行了表征。利用振动样品磁强计和Tg研究了微球的磁含量和磁性能,结果发现,相同粒径不同磁含量的磁性微球,磁含量越高,升温速率越快,当磁含量为70.57%时,升温速率最快,能达到磁热疗的有效温度42℃。对于磁含量相同,粒径不同的微粒,粒径越小,升温速率越快,粒径约为10μm时升温速率最快。     

西北戈壁地区气溶胶的浓度及粒度分布特征

为了获取西北戈壁地区气溶胶随着粒径变化的概率分布函数,对该地区的2次现场取样进行调查。结果表明,采样点气溶胶的质量浓度为0.03~0.1 mg/m3;气溶胶的粒径分布遵循双峰分布的规律,第1个峰值出现在约0.5μm处,第2个峰值出现在约3μm处,其差异主要表现在第2个峰值的面积大小;大多数采样点气溶胶粒子数量中位粒径小于1μm,质量中位粒径位于2~5μm之间。     

A model to predict the fracture distance of cleavage fracture as a function of temperature

We propose a model which computes the fracture distance of materials (reactor pressure vessel steel, C–Mn steel, and four heat-treated HSLA steels) as a function of temperature. The fracture distance, an important length scale for predicting cleavage fracture, is determined using the parameters such as mean grain size, fracture toughness and yield stress of the material in the range of −250 to 0 °C. The fracture distances computed from the proposed model agreed with measurements for the materials. Some differences between the predictions and the measurements were observed for HSLA steel with fine grain size (30 μm) and coarse grain size (55 μm).     

水基钻井液用碳酸钙微米颗粒的分散状况

为了研究水基钻井液用碳酸钙微米颗粒在水溶液中的分散状况,使用扫描电镜对碳酸钙微米颗粒的微观形貌进行了分析,而后在不同搅拌速度、不同p H、不同超声时间等物理分散因素下研究了碳酸钙微米颗粒在水溶液中的粒径分布与Zeta电位变化,又利用不同的分散剂对碳酸钙微米颗粒进行了化学分散.结果表明:长期放置的碳酸钙微米颗粒会发生团聚,中径达6~7μm;采用物理方法分散时,搅拌速度越高,分散效果越好,在10 000 r/min时可使中径达3~4μm;超声作用则使碳酸钙微米颗粒粒径先减小后增大,中径最小可达2.6μm,p H小于10时,粒径随p H的增大而增大,大于10时则随p H的增大而减小;化学分散剂对提高碳酸钙微米颗粒的分散具有显著的作用,其中,无机类分散剂六偏磷酸钠可使碳酸钙微米粒子中径达到1.5μm,并且Zeta电位绝对值显著提高.     

Correlation Between Physico-Chemical Properties and Cohesive Behavior of Furosemide Crystal Modifications

Abstract

This study reports the influence of changes in crystal form, with subsequent changes in physicochemical properties, on the cohesive properties of furosemide powders. Two known polymorphs and three crystal habits were prepared by changing the crystallisation solvent and velocity. Crystallised products were characterised by their XRD profiles. Powder properties including solid-state photochemical reactivity, particle size and distribution, density, wettability and dissolution were measured. Fine particles of form I, mean size 3 μm, were extremely cohesive, mean size of agglomerates 108 μm, and poorly wettable, contact angle > 90°. Changes in the crystal habit of form I led to the crystallisation of large (mean size > 50 μm) tabular and rod shape, less cohesive but also poorly wettable (contact angle > 90°) particles. These large particles although not cohesive had poor dissolution properties. Milled particles with a mean size of smaller than 10 μm, obtained from the large crystals were again cohesive. The method of preparation of form II produced small plate like crystals, mean size 8 μm, fractionally more wettable, contact angle 75°, and not as cohesive, mean size agglomerates 25 μm. Milling to a mean size of 4 μm increased the cohesive properties because the mean size of agglomerates was then 53 μm. Different crystal habits of form I did not show a difference in degradation during the nucleation period, mean rate constant 1.4×10^?2 h^?1, and the growth period, mean rate constant 2.4×10^?2h^?1. In summary crystal modification improved the wettabillity and cohesive properties of furosemide particles without changing the solid-state stability of the drug. The dissolution properties of larger less cohesive particles were however poor and milling, to increase the surface area available for dissolution, increased the cohesive properties of particles.     

粒径对Ni/硅橡胶复合材料压敏性及介电性质的影响

采用不同粒径的Ni粉与硅橡胶(110型)按质量比2.4∶1.0制成Ni/硅橡胶复合材料, 分别测量了其压敏导电性及介电性质, 并结合扫描电镜照片对其微观导电机制进行了分析。结果表明随着填料Ni粉粒径的减小, Ni/硅橡胶复合材料的直流电阻率对外加压强更加敏感: 在低压强下, 粒径为74、48和18 μm的样品的电阻率随压强的变化率分别为1.73×104、2.59×104和3.71×10 4 Ω·m/kPa。样品直流电阻率陡降的区域随粒径的减小向压强较小的方向移动, 显示出复合材料的渗流阈值与填充粒子的粒径有关: 粒径越小, 渗流阈值也越小。Ni/硅橡胶复合材料的交流电导率、介电常数、介电损耗均随填料Ni粉粒径的减小而变大: Ni粉粒径为18 μm的Ni/硅橡胶复合材料的电导率约为10-2 S·m-1, 比74 μm粒径样品的电导率(约10-7 S·m-1)提高了5个数量级; 对应的介电常数由约102提高到约103。改变填料Ni粉粒径可以有效地调节复合材料的弹性和压敏、电输运特性。      

表面活性剂对相反转法制备金属颗粒的影响

采用相反转悬浮液体系中不同表面活性剂同步修饰的方法制备超细低熔点金属颗粒,研究阳离子和阴离子表面活性剂对金属颗粒的影响。通过沉降实验观察不同表面活性剂修饰的金属颗粒在水中的分散及稳定性,并采用激光粒度仪、扫描电镜对低熔点金属颗粒的粒径和形貌进行表征分析。结果表明:表面活性剂的种类对制备低熔点金属颗粒有重要的影响,其中阴离子表面活性剂的效果最好。对几种阴离子表面活性剂的研究表明:油酸钠的作用最明显,其浓度大小对低熔点金属颗粒的粒径、形貌和分散效果有显著的作用。采用质量分数为1%的油酸钠水溶液可制备出分散稳定、粒径分布窄和球状的超细低熔点金属颗粒,平均粒径为0.343μm。