Chromatographic evaluation of poly (trans-1,2-cyclohexanediyl-bis acrylamide) as a chiral stationary phase for HPLC

Chiral stationary phases (CSPs) based on polymeric (R,R)- or (S,S)-1,2-diaminocyclohexane (DACH) derivatives are synthesized. When bonded to 5 microm porous spherical silica gel, the poly (trans-1,2-cyclohexanediyl-bis acrylamide) based poly-cyclic amine polymer (P-CAP) stationary phases is proved to be effective chiral stationary phases that could be used in the normal-phase mode, polar organic mode and with halogenated solvents mobile phases, if desired. Since these are entirely synthetic CSPs, the elution order of all enantiomers can be reversed between the (R,R) P-CAP and (S,S) P-CAP columns. Because of the high loading of chiral selectors, the columns exhibit very high sample capacities. Thus, P-CAP columns are useful for preparative and semi-preparative enantiomeric separations. The application of these CSPs and optimization of their separations are discussed.     

基于时空感知的用户角色推理

随着大数据和信息技术的发展,更好地理解用户的行为轨迹在个性化推荐、广告推荐等方面越来越重要。该文依据大数据环境下的城市计算理论,提出一种基于情境感知的用户角色推理模型。通过用户的行为轨迹分析其行为的时空特性;结合时间、语义分析等构造识别用户角色概率推理模型;通过算法克服识别用户角色的主观性、动态适应性差等问题。实验结果证明了该文所提模型的可行性、精确性和预测准确性。     

Secrecy Outage Performance Analysis of DF Cognitive Relay Network With Co-channel Interference

Wireless Personal Communications - In this paper, we investigate the secrecy outage performance of the decode-and-forward cognitive relay network with the existence of the co-channel interference,...     

Self-aggregated nanoparticles from methoxy poly(ethylene glycol)-modified chitosan: synthesis; characterization; aggregation and methotrexate release in vitro

Methoxy poly(ethylene glycol)-grafted-chitosan (mPEG-g-CS) conjugates were synthesized by formaldehyde linking method and characterized by Fourier transform infrared (FT-IR) and proton nuclear magnetic resonance (¹H-NMR). The degree of substitution (DS) of methoxy poly (ethylene glycol) (mPEG) in the mPEG-g-CS molecules determined by ¹H-NMR ranged from 19% to 42%. The critical aggregation concentration (CAC) was determined by fluorescence spectroscopy using pyrene as fluorescence probe and its value was 0.07 mg/mL in water. mPEG-g-CS formed monodisperse self-aggregated nanoparticles with a roughly spherical shape and a mean diameter of 261.9 nm were prepared by the dialysis method. mPEG-g-CS self-aggregated nanoparticles were used as carriers of poorly water-soluble anticancer drug methotrexate (MTX). MTX was physically entrapped inside mPEG-g-CS self-aggregated nanoparticles by dialysis method and the characteristics of MTX-loaded mPEG-g-CS self-aggregated nanoparticles were analyzed using dynamic laser light scattering (DLLS), transmission electron microscopy (TEM). Moreover, in vitro release behavior of MTX was also investigated and the results showed that MTX was continuously released more than 50% in 48 h.     

Incorporation of carboxylation multiwalled carbon nanotubes into biodegradable poly(lactic-co-glycolic acid) for bone tissue engineering

Biodegradable poly(lactic-co-glycolic acid) (PLGA)/carboxyl-functionalized multi-walled carbon nanotube (c-MWCNT) nanocomposites were successfully prepared via solvent casting technique. Rat bone marrow-derived mesenchymal stem cells (MSCs) were employed to assess the biocompatibility of the nanocomposites in vitro. Scanning electron microscopy (SEM) observations revealed that c-MWCNTs gave a better dispersion than unmodified MWCNTs in the PLGA matrix. Surface properties were determined by means of static contact angle, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) analysis. The presence of c-MWCNTs increased the mechanical properties of the nanocomposites. Seven-week period in vitro degradation test showed the addition of c-MWCNTs accelerated the hydrolytic degradation of PLGA. In addition, SEM proved that the cells could adhere to and spread on films via cytoplasmic processes. Compared with control groups, MSCs cultured onto PLGA/c-MWCNT nanocomposites exhibited better adhesion and viability and also displayed significantly higher production levels of alkaline phosphatase (ALP) over 21 days culture. These results demonstrated that c-MWCNTs modified PLGA films were beneficial for promoting cell growth and inducing MSCs to differentiate into osteoblasts. This work presented here had potential applications in the development of 3-D scaffolds for bone tissue engineering.     

Development of dinitrophenylated cyclodextrin derivatives for enhanced enantiomeric separations by high-performance liquid chromatography

The synthesis and evaluation of new dinitrophenyl (DNP) substituted beta-cyclodextrin (beta-CD) chiral stationary phases (CSPs) for the enantioseparation of various classes of chiral analytes by HPLC are presented. The dinitrophenyl substituted beta-CD derivatives are synthesized and covalently bonded to functionalized 5 microm spherical porous silica gel. These are the first reported derivatized cyclodextrin which contains pi-electron deficient substituents (i.e., pi-acidic moieties). The column performance in terms of their ability to separate enantiomers is evaluated. A variety of different dinitro-substituted aryl groups are investigated and compared. The pH of the mobile phase buffers, the buffer composition, the number and position of the dinitro groups on the phenyl ring substituent, the degree of substitution, and the bonding strategy all greatly affect the performance of the CSPs. A large variety of racemic compounds have been separated successfully on these CSPs. The bonded dinitrophenyl-derivatized cyclodextrins are stable in all three mobile phase modes, namely, the reversed-phase, polar organic, and normal phase modes. No degradation in column performance was observed in any mode of operation even after more than 1000 injections. The analytical applicability of these types of CSPs for enantiomeric separations is discussed in detail.     

Variation analysis of affinity-membrane model based on Freundlich adsorption

The variation analysis of membrane properties including membrane thickness and pore-size was carried out theoretically by using affinity-membrane model based upon the Freundlich adsorption equation. As the percentage variation of membrane thickness and distribution of pore-size increase, we find that (1) the time of total saturation is delayed; (2) the loading capacity at the point of breakthrough are decreased; (3) solute recovery efficiency and ligand utilization efficiency is decreased; (4) the thickness of unused membrane is increased. The results show that even small variations of thickness and distribution of pore size may severely degrade the membrane performance.     

Random partition masking model for censored and masked competing risks data

We consider the parametric estimation with right-censored competing risks data and with masked failure cause. We propose a new model, called the random partition masking (RPM) model. The existing model based on the so called symmetry assumption, but the RPM model does not need the symmetry assumption. We propose a wide class of parametric distribution families of the failure time and cause, which does not need the assumption of independence between the components of the system. We also study the asymptotic properties of the maximum likelihood estimator under the new model, and apply our procedure to a medical and an industrial data sets.     

Heparin‐Controlled Growth of Polypyrrole Nanowires

Summary: Heparin, a potent anticoagulant, has been used for the first time for the synthesis of PPy nanowires serving not only as an anion dopant but also as an effective morphology‐directing agent. The obtained PPy nanowires exhibit long and fine structures with smooth surface and the average diameter of the nanowires is about 90–100 nm and lengths are several hundred nanometers to micrometers. The possible formation mechanism of PPy nanowires may be related to the chain structure of heparin with functional groups ( SO and  COO⁻) on the surface. The effect of concentrations of pyrrole monomers and heparin on the morphology and size of PPy nanowires has been investigated.

SEM image of PPy nanowires synthesized in the presence of heparin.