NH_4Y_3F_(10)多孔纳米晶的制备及其在MALDI-TOF-MS中的应用(英文)

利用水热法合成出NH4Y3F10多孔纳米晶。由于Y3+离子的激发态能量可以转移给具有较高振动能的有机分子,因此这些多孔纳米晶可以作为基质辅助激光解析电离飞行时间质谱的基体材料,用于检测小分子和聚乙二醇。通过与商品化的基体材料(CHCA、DHB)对比,证明NH4Y3F10多孔纳米晶是一种性能优异的基体材料。这种新型基体材料已经成功应用于有机分子、小肽、C60、缺氧诱导因子(HIFs)和聚乙二醇的分子量的检测,显示出这种基体材料具有广泛的应用前景。     

Surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS) of low molecular weight organic compounds and synthetic polymers using zinc oxide (ZnO) nanoparticles

We have developed surface-assisted laser desorption/ionization mass spectrometry using zinc oxide (ZnO) nanoparticles with anisotropic shapes (ZnO-SALDI-MS). The mass spectra showed low background noises in the low m/z, i.e. less than 500 u region. Thus, we succeeded in SALDI ionization on low molecular weight organic compounds, such as verapamil hydrochloride, testosterone, and polypropylene glycol (PPG) (average molecular weight 400) without using a liquid matrix or buffers such as citric acids. In addition, we found that ZnO-SALDI has advantages in post-source decay (PSD) analysis and produced a simple mass spectrum for phospholipids. The ZnO-SALDI spectra for synthetic polymers of polyethylene glycol (PEG), polystyrene (PS) and polymethylmethacrylate (PMMA) showed the sensitivity and molecular weight distribution to be comparable to matrix-assisted laser desorption/ionization (MALDI) spectra with a 2,5-dihydroxybenzoic acid (DHB) matrix. ZnO-SALDI shows good performance for synthetic polymers as well as low molecular weight organic compounds.     

基质辅助激光解析电离飞行时间质谱分析合成聚合物样品制备的研究进展

基质辅助激光解析电离飞行时间质谱（MALDI-TOF-MS）在合成聚合物的表征手段中具有不可替代的优点,可以提供聚合物的质量分布、嵌段长度、端基等信息.但由于合成聚合物的离子化效率通常不佳,因此样品制备是分析成功的关键.从基质、基质添加剂以及混样方式3个方面综述了MALDI-TOF质谱分析合成聚合物样品制备的研究进展.     

高分子材料的微波辅助合成研究进展

微波加热以其省时、高效、清洁环保的显著优势而使微波辅助合成成为一种广受欢迎的合成技术。高分子材料的传统合成反应时间长、耗能大。将微波辐射应用于高分子材料的合成可缩短反应时间、降低反应能耗,已成为有机合成领域的研究热点。本文简要综述了微波辅助合成技术在工程材料高分子聚酰胺、聚酰亚胺、聚丙烯酸苄基酯以及在医用功能高分子、吸附功能高分子、导电功能高分子和光学功能高分子合成中的研究进展,并展望了微波辅助合成在高分子材料合成中的发展前景。     

Direct chemical analysis of uv laser ablation products of organic polymers by using selective ion monitoring mode in gas chromatography/mass spectrometry

Trace quantities of laser ablated organic polymers were analyzed by using commercial capillary column gas chromatography/mass spectrometry; the instrument was modified so that the iaser ablation products could be introduced into the capillary column directly and the constituents of each peak in the chromatogram were identified by using a mass spectrometer. The present study takes advantage of the selective ion monitoring mode for significantly improving the sensitivity of the mass spectrometer as a detector, which is critical in anatyzing the trace quantities and confirming the presence or absence of the species of interest in laser ablated polymers. The initial composition of the laser ablated polymers was obtained by using an electron impact reflectron time-of-flight mass spectrometer and the possible structure of the fragments observed in the spectra was proposed based on the structure of the polymers.     

Oximation reaction induced reduced graphene oxide gas sensor for formaldehyde detection

High-performance gas sensors can offer great potentials for monitoring and detection of volatile organic compounds (VOCs) in both domestic and industrial environment. In the present work, a new HCHO gas sensor was constructed with reduced graphene oxide (RGO) induced by the oximation reaction. The gas-sensing performance test results suggested that the RGO hydroxylamine hydrochloride (RGO/HA-HCl) sensor presented a high response of 75% at 16 ppm HCHO at room temperature, and a high selectivity for HCHO suffering little interference with high concentrations of volatile organic compounds, including methanol, ethanol, and methylbenzene, dichloromethane and water. Additionally, the RGO/HA-HCl sensor also showed a good long-term stability with RSD of 5.83% for a 15-day continuous sensing test, and the detection limit (DL) could reach 0.023 ppm under ambient conditions. Moreover, the mechanism for the high sensitivity and selectivity of formaldehyde was further established by in-situ gas chromatography mass spectrometry (GC–MS). This work would provide a reliable new HCHO gas sensor which could be used for monitoring and forewarning the emission of HCHO for a better protection and improvement of our environment.     

PAMAM-containing semiconducting polymers: Effect of dendritic side chains on optoelectronic and solid-state properties

Dendronized polymers are a particularly interesting platform for the preparation of advanced semiconductors given their high degree of functionalization, monodispersity, and bulkiness. Despite advantageous features, the incorporation of dendritic moieties in semiconducting polymers is still relatively underexplored, and the impact on the optoelectronic, thermomechanical, and solid-state properties are difficult to predict. This work focuses on the incorporation of polyamidoamine (PAMAM) dendritic side chains to semicrystalline polymers based on diketopyrrolopyrrole. Using a versatile synthetic strategy based on the azide-alkyne Huisgen 1,3-dipolar cycloaddition, dendronized semiconducting polymers were prepared and the effect of the dendritic side chains on different properties were carefully characterized using different techniques. The dendritic side chains were found to reduce aggregation and crystallinity of the polymers in thin films. PAMAM-containing semiconducting polymers were also shown to have good charge transport properties in organic field-effect transistors, within the same order of magnitude to that of diketopyrrolopyrrole-based polymers bearing branched alkyl chains. This new design approach is particularly interesting to develop advanced semiconducting polymers given its synthetic versatility and the structural diversity of the dendronized moieties. Furthermore, the utilization of dendritic moieties in semiconducting polymers is a promising approach to fine-tune the thermomechanical properties toward semiconducting polymers for next-generation organic electronics.     

Molecularly imprinted polymers for bisphenol A for HPLC and SPE from water and milk

Molecularly imprinted polymers (MIPs) for bisphenol A (BPA) were prepared by two synthetic routes: semi-covalent and noncovalent methodology. The molecular imprinting effect was evaluated using the polymers in HPLC and SPE. Polymers prepared with noncovalent mode were proven more effective. These polymers were applied in SPE facilitating selective retention of BPA from bottled water and milk. The developed sample preparation was simple and efficient comprising only dilution of milk and MISPE prior to LC-MS analysis. Overall MISPE enhanced sample clean-up. Compared with control nonimprinted polymers and conventional C18 SPE cartridges, the MIPs exhibited selective analyte recognition. The method provided quantitative BPA recoveries, very good reproducibility (% RSDs lower than 7%), and low LOD (0.2 ng/g). MIP interacts similarly with deuterated BPA allowing its use as internal standard in LC-MS. The most critical parameters of MISPE were the organic content in loading-washing medium and the washing volume. Low flow rates in the elution step enhanced extraction recovery. Important advantages of the MIP were: the high breakthrough volumes (> 500 mL of water), high mass capacity (> 10 ng/mg of MIP sorbent), good linearity, and good stability in performance for over 35 cycles of use.     

Investigating the effect of mixing ratio on molar mass distributions of synthetic polymers determined by MALDI-TOF mass spectrometry using design of experiments

It is well known that the mixing ratio affects the molar mass distribution of synthetic polymers determined by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). Surely, the molar mixing ratio determines whether a mass spectrum will be obtained or not. However, depending on the mass range, several effects such as multimer formation occur, which might be a source of errors in molar mass distribution calculations. In this study, the effect of mixing ratio was investigated for several synthetic polymers, including polystyrene (PS), poly(dimethylsiloxane) (PDMS), poly(ethylene glycol) (PEG), and poly (methyl methacrylate) (PMMA) using statistical designs of experiments. The 2³ full factorial design was found to be suitable in the study of more than 1000 samples. The obtained MALDI mass spectra as well as the ANOVA statistics show that the mixing ratio affects the molar mass distribution. The optimal mixing ratio for a defined synthetic polymer depends on the studied combination (matrix, cationization reagent, solvent).     

Recent developments in asymmetric catalysis using synthetic polymers with main chain chirality

Some recent developments in the use of main chain chiral polymer catalysts are summarized. These polymers are different from the traditional polymer catalysts that are prepared by anchoring monomeric chiral catalysts to an achiral polymer backbone. Three classes of synthetic main chain chiral polymers are discussed including: (1) helical polymers represented by polypeptides; (2) polymers with flexible chiral chains such as polyesters and polyamides; and (3) polymers of rigid and sterically regular chiral chains represented by chiral conjugated polybinaphthyls. Some of these polymer catalysts have shown high enantioselectivity in asymmetric organic transformations.     

Production of biological polymers from organic wastes

Biologically-produced polymers, from microbial fermentation are naturally biodegradable and are potential environment-friendly substitutes for some synthetic plastics. However, broader applications are restricted by the high production costs and limitations in physical and mechanical properties. In this study, activated sludge bacteria in a conventional wastewater treatment system treating a wastewater that contained organic pollutants, were induced by nitrogen deficiency to accumulate intracellular storage polymers, which can be extracted as a low-cost source of biodegradable plastics. Chromatographic analysis of the extracted polymers revealed a composition of poly-hydroxyalkanoate and a number of related co-polymers. Alcaligene spp. in the activated sludge microbial consortium was identified as the main genus accumulated these polymers. When the C:N ratio was increased from 20 to 140, the specific polymer yield increased to a maximum of 0.39 g polymer/g dry cell while specific growth yield decreased to 0.26 g dry cell/g carbonaceous matter consumed. The highest overall polymer production yield of 0.11 g polymer/g carbonaceous matter consumed was achieved when the C:N ratio was maintained at a nitrogen-deficient level of 100. The specific polymer yield in the isolated Alcaligene spp. cells were as high as 0.7 g polymer/g dry cell mass. The composition of the co-polymers, and hence the physical and mechanical properties, could be controlled by manipulating the influent organic compositions.     

Synthesis and characterization of water-soluble PEGylated lignin-based polymers by macromolecular azo coupling reaction

Water-soluble PEGylated lignin polymers were efficiently synthesized by macromolecular azo coupling reaction between alkali lignin and PEG based macromolecular diazonium salts in alkaline water.     

Recent advances of CuAAC click reaction in building cyclic polymer

Cyclic polymers have attracted more and more attentions in recent years because of their unique topological structures and characteristic properties in both solution and bulk state. There are relatively few reports on cyclic polymers, partly because of the more demanding synthetic procedures. In recent years, “click” reaction, especially Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC), has been widely utilized in the synthesis of cyclic polymer materials because of its high efficiency and low susceptibility to side reactions. In this review, we will focus on three aspects: (1) Constructions of monocyclic polymer using CuAAC “click” chemistry; (2) Formation of complex cyclic polymer topologies through CuAAC reactions; (3) Using CuAAC “click” reaction in the precise synthesis of molecularly defined macrocycles. We believe that the CuAAC click reaction is playing an important role in the design and synthesis of functional cyclic polymers.     

Weighing synthetic polymers of ultra‐high molar mass and polymeric nanomaterials: What can we learn from charge detection mass spectrometry?

Advances in soft ionization techniques for mass spectrometry (MS) of polymeric materials make it possible to determine the masses of intact molecular ions exceeding megadaltons. Interfacing MS with separation and fragmentation methods has additionally led to impressive advances in the ability to structurally characterize polymers. Even if the gap to the megadalton range has been bridged by MS for polymers standards, the MS‐based analysis for more complex polymeric materials is still challenging. Charge detection mass spectrometry (CDMS) is a single‐molecule method where the mass and the charge of each ion are directly determined from individual measurements. The entire molecular mass distribution of a polymer sample can be thus accurately measured. Described in this perspective paper is how molecular weight distribution as well as charge distribution can provide new insights into the structural and compositional studies of synthetic polymers and polymeric nanomaterials in the megadalton to gigadalton range of molecular weight. The recent multidimensional CDMS studies involving couplings with separation and dissociation techniques will be presented. And, finally, an outlook for the future avenues of the CDMS technique in the field of synthetic polymers of ultra‐high molar mass and polymeric nanomaterials will be provided.     

Pyrolysis field desorption mass spectrometry of polymers: II. Pyrolysis field ionization and field desorption mass spectrometry of aliphatic and aromatic poly(4,4′-dipiperidylamides)

The first combined use of field ionization and field desorption mass spectrometry for the identification of pyrolysis produtcs and the characterization of technical polymers is reported.Pyrolysis with a specially designed inlet probe at temperature between 600 and 700°C generates gaseous products which can be ionized in a high electric field. The field ions are electrically recorded by low-resolution mass spectrometry and give a detailed insight into the pyrolysis mechanisms and the structure of the monomer unit. Mass shifts and changes in the relative abundances of significant ions allow one to determined the diamine and acid components in a homologous series of twelve polymers. Distinct differences in the thermal cleavages of aliphatic and aromatic poly (4,4′-dipiperidylamides) are observed.Direct submicro-pyrolysis of the polymers adsorbed on the surface of high-temperature-activated tungsten wires also shows clear differences for polymers with aliphatic and aromatic moieties. Electrical registration and integrating ion recording on photoplates under high mass resolution conditions yield sequences of singly and multiply charged ions which allow the detection of thermally produced, high-molecular-weight fragments >2000 mass units) of the synthetic polymers. A basic rule for the interpretation of pyrolysis-field desorption mass spectra of heteroatom-linked polymers is proposed and the characteristic features of ion formation are discussed.     

Uniform polyolefin and polymethacrylate

Preparations and properties of synthetic uniform polyolefins and polymethacrylates are described with emphasizing the necessity of their utilization for understanding the fundamental problems in polymer chemistry. Uniform polymer is a polymer composed of molecules uniform with respect to molecular weight and constitution. While classical organic chemistry provides means of constructing uniform polymers such as poly(methylene)s in stepwise manners, recent advances in separation technology such as supercritical fluid chromatography (SFC) have made it possible to isolate synthetic uniform polymers from its homologous mixture. Combinations of stereospecific polymerizations and the SFC technique have enabled us to prepare uniform polystyrenes and poly(methyl methacrylate)s with high stereoregularities, which are very useful for systematic studies on the nature of polymers. The thermal properties of these uniform polymers are discussed in some detail.     

A Novel Strategy for the Construction of Covalent Organic Frameworks from Nonporous Covalent Organic Polymers

The field of covalent organic frameworks (COFs) has been developed significantly in the past decade on account of their important characteristics and vast application potential. On the other hand, the discovery of novel synthetic methodology is still a challenging task to further promote the preparation of COFs. Herein, an interesting protocol for the conversion of amorphous nonporous covalent organic polymers (COPs) to COFs was established, affording four COFs with high crystallinity and porosity. Specifically, imine‐linked amorphous COP‐1 was successfully converted to COF‐1–4 by replacing one type of linker with other organic building blocks. The realization of this conversion provides a facile method for constructing COFs from COPs.     

SYNTHESIS AND CHARACTERIZATION OF POLY(PHTHALAZINONE ETHER PHOSPHINE OXIDE)S BY N―C COUPLING REACTION

<正>Based on several unsymmetrical,twist,noncoplanar phthalazinone-containing monomers 2a-2e and an active bis(4-fluorophenyl)phenyl phosphine oxide(BFPPO) monomer,a series of novel poly(phthalazinone ether phosphine oxide)s (PPEPO) was synthesized by anhydrous K_2CO_3 mediated N—C coupling reaction in DMAc.The polymers exhibited good thermal properties with T_gs ranging from 267℃to 306℃and 5%weight loss temperatures in nitrogen higher than 430℃, together with high char yield upon prolonged heating at 800℃(35%—56%).Moreover,the polymers were readily soluble in common organic solvents,such as N-methyl-2-pyrrolidone,chloroform and m-cresol.These polymers had inherent viscosities in the range of 0.45-0.72 dL/g and could be cast into flexible and colorless films by spin coating or casting approach.     

New monomers and polymers via Diels-Alder cycloaddition

The series of new bis(naphthalic anhydrides) was prepared through Diels-Alder cycloaddition. The Diels-Alder cycloaddition was used as a synthetic route to new phenylated monomers as well as to polymers. All polymers synthesized revealed to be soluble in a wide range of organic solvents such as toluene, THF, chloroform, and displayed high thermostability. Therefore, they can be processed easily and are promising candidates for advanced coating systems as well as for electrooptical applications.     

Characterization of polyether mixtures using thin-layer chromatography and matrix-assisted laser desorption/ionization mass spectrometry

Thin-layer chromatography (TLC) and matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) were combined to achieve characterization of polyether mixtures. Three polyethers, polyethylene glycol (PEG), polypropylene glycol (PPG) and polytetramethylene glycol (PTMG), or mixtures of these compounds, were studied. One shortcoming of mixture analysis of synthetic polymers using MALDI-MS is that individual polymers in the mixture may display different detection sensitivities. For example, the MALDI mass spectrum of an equimolar mixture of PEG, PPG and PTMG displayed a high intensity of PPG ions, while no PTMG ions were detectable; however, PTMG ions were detected after the mixture had been separated by TLC. This combined TLC and MALDI-MS analysis of a PPG polymer bearing reactive epoxy groups showed that the polymer contained byproducts with different end-groups. These byproducts were identified as chloro-substituted polymers formed during polymer synthesis. Our study shows TLC to be a rapid and low-cost separation technique, and that it can be combined with MALDI-MS to achieve effective analysis of synthetic polymers.