Characterization of nanocrystalline CdSe by size exclusion chromatography

High-performance size exclusion chromatography (HPSEC) is a powerful tool for probing the size and size distribution of complex materials. Here we report its application to the analysis of cadmium selenide nanocrystals produced in organic solvents. If nanocrystal-column interactions are minimized, this method provides an accurate measure of nanocrystal hydrodynamic diameter directly in solution; such information is complementary to TEM in that it can measure the thickness of various capping agents. While the resolution of single-pass HPSEC is limited to 1 nm, we show here that recycling size exclusion chromatography can be applied to assess the fine details of a sample's distribution. Finally, semiconductor nanocrystals can be made a variety of shapes whose optical characteristics are difficult to distinguish. HPSEC can be applied to the general problem of shape separations which we demonstrate with a tetrapod material.     

Recycling size exclusion chromatography for the analysis and separation of nanocrystalline gold

Recycling size exclusion chromatography (RSEC) provides a high-resolution technique for the analysis and separation of materials based on size. We show here the application of this method to gold nanocrystals stabilized by thiols. Alternate recycling is more effective at separating nanomaterials as compared to closed-loop recycling because of its improved efficiency and high resolution. With the use of this technique, we find the resolution ratio of nanocrystal separation increases with the square root of the cycle number, in good agreement with theory. The increased resolution of the size exclusion chromatograms permits the use of RSEC in the baseline separation of nanocrystals which differ by only 6 A in size. In addition to separations, RSEC is valuable as an analytical tool. For example, after recycling processes an initially broad and chromatographic feature from a gold nanocrystal solution resolves into three distinct peaks. Transmission electron microscopy of collected fractions reveals that these peaks correspond to distinct populations of gold nanoparticles with narrowly defined sizes.     

Multidimensional analysis of poly(ethylene glycols) by size exclusion chromatography and dynamic surface tension detection

Substantial improvements in a multidimensional dynamic surface tension detector (DSTD) are presented. Rapid, online calibration and measurement of the dynamic surface tension for high-performance liquid chromatography separations is achieved. Dynamic surface tension is determined by measuring the differential pressure across the liquid-air interface of repeatedly growing and detaching drops. Continuous surface tension measurement throughout the entire drop growth (50 ms to 2 s) is achieved, for each eluting drop, providing insight into the kinetic behavior of molecular orientation processes at the liquid-air interface. Three-dimensional data are obtained, with surface tension first converted to surface pressure, which is plotted as a function of elution time axis versus drop time axis. Two key innovations will be reported. First, a novel calibration procedure is described and implemented. Differential pressure signals from three drops (mobile phase, standard in mobile phase, and analyte in mobile phase) are utilized to make the dynamic surface tension measurement, thereby eliminating the need for optical imaging, and viscosity and hydrostatic pressure corrections, as required by other methods. Only pressure signals from one mobile-phase drop and one standard drop pressure signal are required, while the analyte drop pressure signal is measured along the chromatographic time axis. Second, corrections for drop elongation are not required, because the drops are precisely detached by an air burst actuation method in a regime were the surface tension forces significantly dominate gravitational forces. Drops that would fall with a volume of approximately 10 microL due to gravity are precisely and repeatedly detached earlier at a volume of 2 microL. The sensitivity and unique selectivity of the DSTD opens up new possibilities in the analysis of small molecular weight polymers of varying degrees of surface activity, as illustrated for the size-exclusion chromatography analyses of complex poly(ethylene glycol) (PEG) samples. Using partial least squares for data analysis, polydispersity of complex PEG samples is determined at a relative precision of approximately 1%.     

Formation of 1D and 2D gold nanoparticle arrays by divalent DNA-gold nanoparticle conjugates

Divalent DNA-AuNP (gold nanoparticle) conjugates comprising two DNA strands at diametrically opposed positions are prepared. Highly linear 1D and tetragonal lattice-like 2D AuNP arrays are constructed using the conjugates and DNA assemblies based on T- and double-crossover motifs and the Holliday junction.     

Nonaqueous capillary electrochromatographic separation of synthetic neutral polymers by size exclusion chromatography using polymeric stationary phases

In this paper, we report the separations of large, neutral, synthetic polymers using primarily a nonaqueous mobile phase without the use of a supporting electrolyte. The size- exclusion-based mechanism for separation was achieved on sulfonated polystyrene/divinylbenzene stationary phases. The effect of water, voltage, stationary phase exchange capacity, and pore size were investigated. The stationary phase and solvent interactions were studied by attenuated total reflectance Fourier transform infrared spectroscopy (ATR FT-IR) and a possible mechanism for the generation of EOF in the THF/water system is provided. Linear calibration curves were obtained for polystyrenes ranging in MW from 5K to 2M, for columns made using a combination of high capacity ion exchanger and a neutral polystyrene/divinylbenzene material of varied pore sizes. Analysis of polyurethane, polystyrene, and other polymer samples using CEC correlated well with results obtained by conventional HPLC. The size exclusion CEC separations provide an alternative mode for determining the relative molecular weights of polymers, with reduced solvent consumption.     

Determination of lead and other trace element species in blood by size exclusion chromatography and inductively coupled plasma/mass spectrometry.

The combination of liquid chromatography and inductively coupled plasma/mass spectrometry (ICP/MS) was employed in an exploratory study to determine lead and other trace element species in blood components. In human blood serum, lead was found in at least three molecular weight fractions at greater than 600,000, 260,000, and 140,000. The major part of lead was coincident with the main copper signal at a molecular weight of 140,000. This fraction, binding both copper and lead, was proven to be ceruloplasmin by the application of an immunological reaction prior to chromatographic separation. In rat serum, lead could be detected in four fractions with molecular weights of greater than 600,000, 400,000, 145,000, and 11,000. In human red blood cell hemolysate, the major fraction of lead was found at 250,000, with minor fractions at 140,000 and at 30,000 together with iron in hemoglobin and zinc in carbonic anhydrase. In rat red blood cell hemolysate, lead was detected at greater than 600,000, 145,000, 30,000, and 11,000. Lead isotope ratios were determined in lead binding protein fractions with a precision of +/- 10%. The detection limit for lead in protein fractions was 0.15 micrograms.L-1.     

A mathematical model for hydrodynamic and size exclusion chromatography of polymers on porous particles

When packed columns filled with porous particles are used for the separation of macromolecules, either size exclusion chromatography (SEC), hydrodynamic chromatography (HDC), or a combination of both determine the macromolecule retention mechanism. This paper develops a simple mathematical model to describe a molecular weight calibration graph, which includes both HDC and SEC. There is a transition between the HDC calibration region at higher molecular weights to an SEC region at lower molecular weights. The degree to which SEC and HDC are mixed depends on the particle diameter, the relative size of the pores, and the macromolecule size. In addition, using fractal considerations, the fractal character of the apparent selectivity between two adjacent peaks on the chromatogram is shown. This model constitutes an attractive tool to enhance the expansion of these two chromatographic techniques for the separation of biological or synthetical macromolecules.     

Determination of molecular weight distributions of diblock copolymers with conventional size exclusion chromatography

A convenient method that enables determination of molecular weight distributions of diblock copolymers with conventional size exclusion chromatography (SEC) without referring to any kind of calibration curve or molar mass-sensitive detecting devices is described. It is based on the well-established procedure to calculate the number-average molecular weight of copolymers from their chemical composition and the molar mass of the first block segment (precursor), applied on an ensemble of monodisperse copolymer fractions. The chemical composition of SEC fractions is calculated from their UV and RI detector traces, and the number-average molecular weight of the precursor, which is to be known from independent measurements, is taken as the molar mass of the first block segment. The molecular weight distributions and averages obtained by this method for selected copolymer samples were found to be in reasonably good agreement with the ones determined by NMR and SEC with on-line viscosity or multiangle laser light scattering detection.     

Stochastic theory of size exclusion chromatography: peak shape analysis on single columns

The stochastic theory of size exclusion chromatography (SEC) was applied to analyze the peak shape of chromatograms obtained with a wide range of polystyrene standards on various columns. The columns were packed with stationary phases of different pore sizes. The stochastic-dispersive model of SEC results in a peak shape model that fits well the symmetrical and asymmetrical peaks observed in SEC. From the peak shape parameters obtained after nonlinear parameter estimation, information can be gained regarding the fundamental characteristics of the size exclusion process. When a series of polymer standards are analyzed on one column-in a manner similar to other methods of inverse chromatography-the stationary phase can be characterized. The dependence of the ingress and the egress processes on the relative size of the macromolecule to the pore size was determined. We found that for small molecules the selectivity in SEC arises from the ingress process, while when the size of the macromolecule is comparable to that of the pore-i.e., close to the exclusion limit-the egress process will also strongly affect the selectivity.     

Characterization of water-soluble conjugates of polyacrylic acid and antigenic peptide of FMDV by size exclusion chromatography with quadruple detection

Intermolecular complex by electrostatic interaction and specifically coupled conjugates between polyacrylic acid (PAA) and a synthetic peptide representing 170-188 sequence from the GH loop of VP1 protein of foot-and-mouth disease virus (FMDV) were investigated as an intermolecular model system due to their importance in biotechnology and immunology. In this study, polyacrylic acid (PAA) with a synthetic peptide representing 170-188 sequence from the GH loop of VP1 protein of foot-and-mouth disease virus at a wide range of mixing ratios of components (C_Peptide/C_PAA 0.1, 0.25, 0.5, 0.75 and 1.0, respectively) were characterized by size-exclusion high performance liquid chromatography with on-line refractive index, UV, light scattering and viscometer detectors. The results revealed that two molecules are both negatively charged as a result of repulsive forces preventing complex formation at neutral pH. Therefore, these molecules bound covalently to each other by using water-soluble carbodiimide when pH levels are higher than the pI of the peptide. High performance liquid chromatography analysis showed that the amount of protein-polymer complex increased and free peptide amount decreased with the increase in molar ratio of the peptide. Also, this paper presents that number of the bound peptide molecules with one PAA molecule was expressed by a Langmuir-type equation as a function of the amount of excess synthetic peptide existing free in the solution.     

Scattering of electromagnetic radiation by a metal nanoparticle

The scattering cross section of electromagnetic radiation by a small spherical metal particle has been calculated in the framework of the standard kinetic theory in a dipole approximation. The calculation has been performed for relatively small (～10 nm) particles, which allows the skin effect to be ignored. A mechanism of mixed specular-diffuse reflection of conduction electrons from the particle surface is considered. It is established that, at certain angles of scattering, the mechanism of magnetic-dipole scattering becomes dominating. The influence of kinetic effects on the differential scattering cross section is analyzed.     

Imaging surface plasmon of gold nanoparticle arrays by far-field Raman scattering

We present Raman spectra and Raman images of the methylene blue molecule adsorbed as a single layer on gold nanoparticles regularly arranged in periodic arrays. Spectra and images are recorded in the same spatial and spectral regions using an excitation under total internal reflection. Images of the Raman scattering appear as spots of circular shape located at the particle positions with size defined by the diffraction limit. It appears that all excited particles contribute equally to the Raman signal if the Gaussian intensity distribution of the laser beam is taken into account. These results demonstrate that Raman scattering can be a useful technique to study plasmon properties.     

2D nanoparticle arrays by partial dissolution of ordered pore films

A low cost and simple route was presented to fabricate large-scale ordered nanoparticle arrays by partial dissolution of ordered pore films (or monolayer inverse opal) in a solution. By this method, we have fabricated Fe₂O₃ and In₂O₃ hexagonal close-packed nanoparticle arrays. This method is also applicable for synthesis of other material nanoparticle arrays. The particle size in the arrays can be controlled by the dissolution time, which is, additionally, beneficial to study size dependent optical, magnetic, electrochemical, thermodynamic, catalytic properties of nanoparticls.     

纳米金属微粒催化制备的洋葱状富勒烯的结构表征

采用金属Cu，Al做粒／石墨混合材料．用直流电弧放电方法制备了洋葱状富勒烯。对两种产物进行了XRD、SEM、HRTEM和Raman结构表征。结果表明：两种纳米金属微粒均可催化得到洋葱状富勒烯；所得产物中有单纯洋葱状富勒烯和内包纳米金属微粒洋葱状富勒烯，且石墨化程度都很高；纳米金属微粒尺寸大小不同决定洋葱状富勒烯的直径分布不均匀，从而造成其拉曼谱峰相对于石墨特征峰1582cm^-1发生了频移；用汽-液-固(VLS)生长模型描述了洋葱状富勒烯生长机理，解释了汽态碳原子通过在液态催化剂中扩散和析出，逐渐长大成形的现象。     

Effect of metal ions on the molecular weight distribution of humic substances derived from municipal compost: ultrafiltration and size exclusion chromatography with spectrophotometric and inductively coupled plasma-MS detection

The effect of metal ions (Co, Cu, Ni, Pb, Zn) on the molecular weight distribution of humic substances (HSs) obtained from compost is studied. We believe this is the first of this type of study applied in this way to humic substances. Size exclusion chromatography is coupled with two on-line detection systems (spectrophotometric and ICPMS) to study the binding of metal ions by humic substances leached from compost. ICPMS provided highly specific, sensitive, and multielement analytical information that enabled obtaining direct experimental evidence for the participation of metal ions in molecular size distributions of humic compounds. The compost extract or its high molecular weight fraction (>5,000) was put in contact with EDTA or citrate ions, thereby competing with HSs for binding metals. The experiments were carried out by varying the pH maintained by Tris-HCl or CAPS buffer (pH 8.0 and 10.3) and keeping the ionic strength constant. The elution profile of humic substances using UV/ visible detection was compared with those from ICPMS detection of Co, Cu, Ni, Pb, and Zn in the same chromatographic runs. The results obtained suggested that both bridging between small molecules and complexation/ chelation by individual molecules are involved in metal ion binding to humic substances. The use of ICPMS to study the role of metal ions in aggregation/disassociation of humic substances proposed in this work is promising. Coupling element-specific detection with SEC or other separation systems allows better understanding of the mobility and bioaccessibility of elemental species in the environment and further elucidation of the dissolved humic structure.     

Measurement of urine crystallites and its influencing factors by nanoparticle size analyzer

The difference of urine crystallites under 1000 nm in 10 patients with urolithiasis and 10 healthy subjects with no history of urolithiasis was comparatively studied with the nanoparticle size analyzer. By comparing the differences of intensity-autocorrelation curve, polydispersity index (PDI), Zeta potential, and relative error of average diameter of the two kinds of urine crystallites, it was concluded that the urine crystallites of healthy subjects were more stable than those of patients. The urine crystallites of healthy subjects had a narrower size distribution from 100 nm to 350 nm and a better dispersion (PDI < 0.3). However, the urine crystallites of patients with urolithiasis had a wider distribution from dozens of nanometers to 1000 nm and a worse dispersion (PDI > 0.5). The best processing method for urine crystallites detection was found: after antisepticising and protein-coagulating with formaldehyde, the urine was diluted with distilled water of the same volume, then filtrated through a micropore film of 3 microm, and the filtrate was centrifugalized at 4000 rpm for 15 minutes. This method can remove the cell fragments and macromolecular substances in the urine without affecting the detection of the urine crystallites under 1000 nm. The results were consistent with those obtained by transmission electron microscope (TEM).     

Application of the general height equivalent to a theoretical plate equation to size exclusion chromatography. Study of the mass transfer of high-molecular-mass compounds in liquid chromatography

The mass transfer of nonretained, high-molecular-weight polystyrene standards in a chromatographic column packed with 4-microm-diameter silica particles for SEC (average pore size 80 A) and eluted with tetrahydrofuran was investigated. The HETPs of nine polystyrene standards (MW 560, 760, 1780, 3680, 6400, 13,200, 19,300, 31,600, and 90,000) and of ethylbenzene were measured by the method of moments. These HETPs were accounted for by a general HETP equation previously derived for the mass transfer of low-molecular-weight compounds in RPLC (Gritti, F.; Guiochon, G. Anal. Chem. 2006, 78, 5329.). The best fit between the experimental and the theoretical HETPs allowed the estimation of the internal restricted diffusion coefficients of the polymers. The internal diffusion coefficients of the polystyrene standards were also measured, using the peak parking method. Both methods give comparable results and show that the restriction diffusion coefficient gammapKD decreases linearly with increasing logarithm of the polymer mass, from 0.56 for Log MW = 2.0 to 0 for Log MW = 4.8. Interestingly, the C term or limit slope of the high-velocity branch of the HETP curve passes through a maximum (highest mass-transfer resistance) for a polymer mass of 10 kDa. This maximum is well accounted for by the theoretical expression of the trans-particle mass-transfer contribution.     

Inherently reproducible fabrication of plasmonic nanoparticle arrays for SERS by combining nanoimprint and copolymer lithography

We present an inherently reproducible route to realizing high-performance SERS substrates by exploiting a high-throughput top-down/bottom-up fabrication scheme. The fabrication route employs self-assembly of amphiphilic copolymers to create high-resolution molds for nanoimprint lithography (NIL) spanning entire 100 mm Si wafers. The nanoporous polymer templates obtained upon NIL are subjected to galvanic displacement reactions to create gold nanorod arrays. Nanorods are subsequently converted to nanodiscs by thermal annealing. The nanodiscs were found to perform as robust SERS substrates as compared with the nanorods. The SERS performance of these substrates and its generality for catering to diverse molecules is demonstrated through the excellent Raman peak resolution and intensity for three different molecules, exhibiting different interaction modes on surface. Numerical simulations using FDTD shows plasmonic coupling between the particles and also brings out the influence due to size distribution. The approach combines distinct advantages of high-precision and repeatability offered by NIL with low-cost fabrication of high-resolution NIL molds by copolymer self-assembly.     

无电金属沉积法硅纳米线阵列的制备研究

采用无电金属沉积法在硅衬底上制备出了大面积规整的硅纳米线阵列,并对其形貌控制的影响因素和形成机理进行了研究。用扫描电子显微镜(SEM)、X射线衍射仪(XRD)对硅纳米线阵列和相应银枝晶的形貌和结构进行了表征。结果表明,硅纳米线阵列的形貌受水热体系中溶液配比、温度和时间的影响,在温度为50℃、HF和AgNO3浓度分别为4.6和0.02mol/L的条件下,容易得到大面积排列规整的硅纳米线阵列,并且硅纳米线的长度为30～50μm,直径为200nm左右。无电金属沉积法为硅纳米线及其阵列的制备提供了一种设备简单、条件温和的制备方法。