Synthesis of organic one-dimensional nanomaterials by solid-phase reaction

The synthesis of anthracene (AN) nanowires and perylene (PY) nanorods on the basis of solid-phase organic reactions under controlled conditions is discussed, and the structures are confirmed by SEM, TEM, and XRD. The dimension-dependent emission properties of the AN nanowires and PY nanorods is observed. This approach is expected to form a new general route for the controlled morphosynthesis of organic molecular materials in restricted dimensions, with controlled size and shape, the solid-state physical properties of which are of great interest. It should have outstanding potential in providing customized 1D nanomaterials for a broad range of applications for molecule devices and nanoscience and is expected to be applicable other functionalized nanomaterials (i.e., organic, inorganic, and polymer).     

Bottom up,solid-phase syntheses of inorganic nanomaterials by mechanochemistry and aging

1. Download : Download high-res image (114KB)
2. Download : Download full-size image

     

Capillary electrophoresis for analyzing pesticides in fruits and vegetables using solid-phase extraction and stir-bar sorptive extraction

Two procedures based on solid-phase extraction (SPE) and stir-bar sorptive extraction (SBSE) in combination with micellar electrokinetic chromatography (MEKC)--diode array detection (DAD) were compared for the simultaneous extraction of acrinathrin, bitertanol, cyproconazole, fludioxonil, flutriafol, myclobutanil, pyriproxyfen, and tebuconazole in lettuce, tomato, grape, and strawberry. Selectivity and resolution of the MEKC procedure were studied changing the pH and the molarity of the buffer, the type and the concentration of surfactant, and the methanol content in the mobile phase. A buffer consisting of 6 mM sodium tetraborate decahydrate with 75 mM of cholic acid sodium solution (pH 9.2) gave the best results. Linearity, extraction efficiencies and limits of quantitation (LOQs) of both extraction methods were compared. The recoveries obtained by SPE ranged from 40 to 106% with relative standard deviations (R.S.D.s) from 10 to 19% whereas by the SBSE method, the recoveries were 12-47% and the R.S.D.s 3-17%. The LOQs were much better by SPE (0.2-0.5 mg kg(-1) depending on the processed sample amount) than those obtained by SBSE (1 mg kg(-1) for each compound). Advantages and disadvantages of both procedures are also discussed. As SPE is more robust, rapid, and sensitive than SBSE, its application in combination with MEKC is recommended because provided LOQs below the MRLs established, which is not always attained by SBSE.     

New algorithm and software for analyzing the vibronic spectra of polyatomic molecules

A new algorithm for automatic assignment of the resolved vibrational structure of the electronic absorption spectra of diatomic and polyatomic molecules is suggested. Translated fromZhurnal Struktumoi Khimii, Vol. 38, No. 2, pp. 363–368, March–April, 1997.     

A fast clustering algorithm for analyzing highly similar compounds of very large libraries

As a result of the recent developments of high-throughput screening in drug discovery, the number of available screening compounds has been growing rapidly. Chemical vendors provide millions of compounds; however, these compounds are highly redundant. Clustering analysis, a technique that groups similar compounds into families, can be used to analyze such redundancy. Many available clustering methods focus on accurate classification of compounds; they are slow and are not suitable for very large compound libraries. Here is described a fast clustering method based on an incremental clustering algorithm and the 2D fingerprints of compounds. This method can cluster a very large data set with millions of compounds in hours on a single computer. A program implemented with this method, called cd-hit-fp, is available from http://chemspace.org.     

An improved method for analyzing chlormequat and mepiquat in source waters by solid-phase extraction and liquid chromatography-mass spectrometry

A liquid chromatography-mass spectrometry (LC-MS) method for the identification and quantification of chlormequat (CQ) and mepiquat (MQ) in source waters with high sensitivity and specificity was established using WCX cartridges (150 mg/6 mL) for pre-concentration of the samples and using the CAPCELL PAK CR 1:4 (2.0 mm × 150 mm 5 μm, SCX:C18 = 1:4) column containing strong cationic exchange resins and C18 for separation. The method could solve the problem for pre-concentrating ionic compounds from water samples and avoid the MS instrument fouling problem accompanied with the use of ion-pair reagents. After the optimization of analytical conditions, quantification was achieved in the positive electrospray ionization mode using selected ion monitoring. The samples were analyzed with multi-channel mode with quantification performed at 30 V cone voltage to ascertain the sensitivity and qualitative analysis performed at 60 V cone voltage simultaneously. The method detection limits (MDLs) of CQ and MQ in source water were determined to be 14 and 22 ng L⁻¹. Finally, the method was used to quantify CQ and MQ in several source waters, which gave a level ranging from below the quantitation limit to 28 ng L⁻¹.     

Design of molecular precursors for nanomaterials

This work is focused on the synthesis of bimetallic oxide prepared by non-hydrolytic sol–gel method using the chemie douce approach. The bimetallic oxide was characterized by using various analytical techniques. Elemental analysis showed consistency with the formulation. From XRD, SEM and TEM studies, it is concluded that precursor chemistry has a significant effects on the surface chemistry of metal oxide on calcinations and as well as synthetic routes. XRD patterns show that an enhanced homogeneity on calcinations. Use of these metal oxides has commercial importance in future for sensor devices.     

Engineering of chiral nanomaterials for biomimetic catalysis

Chiral nanomaterial-based biomimetic catalysts can trigger a similar biological effect to natural catalysts and exhibit high performance in biological applications. Especially, their active center similarity and substrate selectivity promoted their superior biocatalytic activity. Here, modification of critical elements, such as size, morphology, nanocrystal facets, chiral surface and active sites, for controlling the catalytic efficiency of individual chiral nanoparticles (NPs) and chiral nanoassemblies has been demonstrated, which had a synergistic effect on overcoming the defects of pre-existing nanocatalysts. Noticeably, application of external forces (light or magnetism) has resulted in obvious enhancement in biocatalytic efficiency. Chiral nanomaterials served as preferable biomimetic nanocatalysts due to their special structural configuration and chemical constitution advantages. Furthermore, the current challenges and future research directions of the preparation of high-performance bioinspired chiral nanomaterials for biological applications are discussed.

Chiral nanomaterial-based biomimetic catalysts can trigger a similar biological effect to natural catalysts and exhibit high performance in biological applications.     

Gold nanomaterials for treatment of metastatic cancer

Nanomedicine has shown good potentials for cancer diagnosis and treatment since the last decades. Among the various nanoparticles exploited for cancer management so far, gold nanomaterials (e.g., spherical gold nanoparticles and gold nanorods) were extensively investigated due to their unique chemo-physical properties. We herein summarize the emerging application and discuss the challenges of using gold nanomaterials for therapy of metastatic cancer.     

有机纳米材料在肿瘤光热治疗中的应用

光热治疗是利用在近红外具有较强光吸收的材料将光能转化为热能从而杀死癌细胞,与传统的化疗、放疗相比具有副作用小、治疗特异性好的优点。近年来各种不同的纳米材料被用于肿瘤光热治疗,并在动物肿瘤模型实验中取得了令人鼓舞的治疗效果。本文重点介绍几种典型的有机纳米材料在光热治疗中的应用,并讨论这一新兴领域的发展趋势。     

Green solvent-based approaches for synthesis of nanomaterials

The use of green solvents (including supercritical fluids and ionic liquids) in the synthesis of nanomaterials is highlighted. The methods described can not only reduce or eliminate the use or generation of substances hazardous to health and the environment, but can also be used to efficiently prepare nanomaterials with high performances. The unique characteristics of green solvents are responsible for the green features and unusual advantages of these approaches.     

Development of a multiresidue method for analyzing herbicide and fungicide residues in bovine milk based on solid-phase extraction and liquid chromatography-tandem mass spectrometry

The adverse effect of reactive chemical residues on the quality of drug products has necessitated the determination of low-molecular-weight aldehydes in pharmaceutical excipients. An analytical methodology for the detection of trace amounts of C1-C8 aliphatic aldehydes and benzaldehyde in excipients is described. The proposed procedure is based on the derivatization of aldehydes in aqueous solution with O-2,3,4,5,6-(pentafluorobenzyl) hydroxylamine hydrochloride (PFBHA), followed by static headspace gas chromatographic (SHS-GC) analysis of PFBHA aldehyde oximes with negative chemical ionization (NCI) MS detection. The method developed was demonstrated to be simple, selective, sensitive, and was successfully applied to the screening of aldehydes at sub-microg/g levels in over 30 typical excipients. The most abundant aldehydes found in the samples were formaldehyde and acetaldehyde, for which a rapid and reliable routine quantification method by readily available SHS-GC instrumentation coupled with flame-ionization detection was also developed and validated.     

Rival penalized competitive learning (RPCL): a topology-determining algorithm for analyzing gene expression data

DNA arrays have become the immediate choice in the analysis of large-scale expression measurements. Understanding the expression pattern of genes provide functional information on newly identified genes by computational approaches. Gene expression pattern is an indicator of the state of the cell, and abnormal cellular states can be inferred by comparing expression profiles. Since co-regulated genes, and genes involved in a particular pathway, tend to show similar expression patterns, clustering expression patterns has become the natural method of choice to differentiate groups. However, most methods based on cluster analysis suffer from the usual problems (i) dead units, and (ii) the problem of determining the correct number of clusters (k) needed to classify the data. Selecting the k has been an open problem of pattern recognition and statistics for decades. Since clustering reveals similar patterns present in the data, fixing this number strongly influences the quality of the result. While there is no theoretical solution to this problem, the number of clusters can be decided by a heuristic clustering algorithm called rival penalized competitive learning (RPCL). We present a novel implementation of RPCL that transforms the correct number of clusters problem to the tractable problem of clustering based on the degree of similarity. This is biologically significant since our implementation clusters functionally co-regulated genes and genes that present similar patterns of expression. This new approach reveals potential genes that are co-involved in a biological process. This implementation of the RPCL algorithm is useful in differentiating groups involved in concerted functional regulation and helps to progressively home into patterns, which are closely similar.     

Development of a highly efficient in-tube solid-phase microextraction system coupled with UHPLC-MS/MS for analyzing trace hydroxyl polycyclic aromatic hydrocarbons in biological samples

Hydroxyl polycyclic aromatic hydrocarbons are considered active mutagenic and carcinogenic substances and are found in extremely low levels (ng/g) in biological samples. As a result, their determination in urine and blood samples is challenging, and a sensitive and effective method for the analysis of trace hydroxyl polycyclic aromatic hydrocarbons in complex biological matrices is required. In this work, a novel macroporous in-tube solid-phase microextraction monolith was prepared via a thiol-yne click reaction, and a highly efficient analytical method based on in-tube solid-phase microextraction coupled with UHPLC-MS/MS was developed to determine hydroxyl polycyclic aromatic hydrocarbons with low detection limits of 0.137–11.0 ng/L in complex biological samples. Four hydroxyl polycyclic aromatic hydrocarbons, namely, 2-hydroxyanthraquinone, 1-hydroxypyrene, 1,8-dihydroxyanthraquinone, and 6-hydroxychrysene, were determined in the urine samples of smokers, non-smokers, and whole blood samples of mice. Satisfactory recoveries were achieved in the range of 83.1–113% with relative standard deviations of 3.2–9.7%. It was found that implementation of the macroporous monolith gave a highly efficient approach for enriching trace hydroxyl polycyclic aromatic hydrocarbons in biological samples.     

Strategies of tailored nanomaterials for electrochemiluminescence signal enhancements

Nanomaterials and their applications were studied extensively over the past few decades due to their properties which are associated mainly with the nanoscale sizes and unique characteristics that they have. Among many applications, these nanomaterials have been playing great, multifaceted roles in increasing the analytical performances of electrochemiluminescence (ECL). In this article, we review the main possible approaches – based on nanoparticles – to modify the photophysical properties of the excited state generated as a consequence of the electrochemical stimulus and in particular taking profit of the so-called metal-enhanced fluorescence (MEF) and resonance energy transfer (RET) processes. We believe that these strategies will lead to the design of very efficient systems that can substantially increase the possible successful applications of ECL.     

Percolation of carbon nanomaterials for high-k polymer nanocomposites

This review summarized the recent progress towards high-k polymer composites bases on the near-percolated networks of carbon nanomaterials by focusing on the effects of distinct network morphologies on the dielectric properties. It is expected to give guidance on designing new near-percolated networks in polymer matrices towards next-generation polymer dielectrics.     

Double-template synthesis of platinum nanomaterials for oxygen reduction

Microchimica Acta - A new Hg(II)-imprinted thiol-functionalized silica gel sorbent was synthesized by a surface imprinting technique for selective solid-phase extraction of Hg(II). Compared to a...     

Wavelet algorithm for solving integral equations of molecular liquids. A test for the reference interaction site model

A new efficient method is developed for solving integral equations based on the reference interaction site model (RISM) of molecular liquids. The method proposes the expansion of site-site correlation functions into the wavelet series and further calculations of the approximating coefficients. To solve the integral equations we have applied the hybrid scheme in which the coarse part of the solution is calculated by wavelets with the use of the Newton-Raphson procedure, while the fine part is evaluated by the direct iterations. The Coifman 2 basis set is employed for the wavelet treatment of the coarse solution. This wavelet basis set provides compact and accurate approximation of site-site correlation functions so that the number of basis functions and the amplitude of the fine part of solution decrease sufficiently with respect to those obtained by the conventional scheme. The efficiency of the method is tested by calculations of SPC/E model of water. The results indicated that the total CPU time to obtain solution by the proposed procedure reduces to 20% of that required for the conventional hybrid method.