基于无基底扣除的数据趋势累积谱峰检测算法

谱峰的检测分析在色谱技术研究中具有十分重要的作用,但在色谱数据采集、传输的过程中,不同程度的噪声干扰给谱峰检测带来了极大的困难。目前传统的谱峰检测算法普遍通过基底扣除的方式对谱峰的形态进行预定义,将谱峰分为单峰、重叠峰等多个种类。针对不同种类的谱峰采用不同的检测方法,这就导致了传统的谱峰检测算法具有高复杂度、低自动化程度以及容易失真等缺点。因此,该文从另一个角度出发提出了一种新型的谱峰检测算法。该算法取消基底扣除以及谱峰分类这一步骤,直接在源数据曲线的基础上进行谱峰检测,主要分为离散差分、趋势累积以及遍历寻峰3个步骤。首先通过信号量表征数据升降趋势;然后进行数据趋势累积,根据累积总和定位谱峰,采用三点定位的方式,即峰起点、极值点和峰终点描述一个谱峰的位置;最后根据遍历排序的方式进行谱峰的筛选。此外,通过谱峰扣除的方式得到曲线基底部分。采用C语言设计编写了算法程序,并对多个动态比表面积分析仪测定的色谱图进行了检测分析,结果显示使用该算法可以精准区分谱峰部分与基底部分,受数据曲线毛刺、震荡等噪声干扰很小,谱峰的三点定位十分准确,且不受其复杂形态的影响,具有很强的普适性。与其他算法相比,该算法定位准确,结构清晰,具有较好的稳定性以及可靠性。该文报道了无基底扣除以及趋势累积等新型谱峰检测思想在吸脱附色谱曲线中的应用,证明了其在吸脱附色谱峰检测中的有效性和良好的应用前景。     

Polymer-surfactant and protein-surfactant interactions

The phase behavior and some physicochemical properties of homopolymers (HP) and hydrophobically modified (HMP) polymers, as well as of polyelectrolytes (PE) and proteins (PR), in the presence of aqueous surfactants, or their mixtures, are discussed. Mixing the above components gives rise to the formation of organized phases, whose properties are controlled by polymer and/or surfactant content, temperature, pH, and ionic strength. Depending on the nature, concentration, and net charge of both solutes, molecular solutions, polymer-surfactant complexes, adsorption onto micelles and vesicles, gels, liquid crystalline phases, and precipitates are observed. Such rich polymorphic behavior is the result of a complex balance between electrostatic, excluded volume, van der Waals, and other contributions to overall system stability. It is also modulated by the molecular details and architecture of both the polymer and the surfactant. Different experimental methods allow investigation of the above systems and getting information on the nature of polymer-surfactant interactions (PSI). Surface adsorption and thermodynamic methods, together with investigation of the phase diagrams, give information on the forces controlling PSI and on the existence of different phases. Conductivity, QELS and viscosity allow estimating the size and shape of polymer-surfactant (protein-surfactant) complexes. Optical microscopy, cryo-TEM, AFM, NMR, fluorescence, and relaxation methods give more information on the above systems. Use of the above mixtures in controlling gelation, surface covering, preparing dielectric layers, and drug release is suggested.     

环境样品中双酚类化合物的固相萃取研究进展

双酚类化合物作为一类内分泌干扰物广泛存在于环境介质中,经过多种途径迁移至人体后,可对人体产生内分泌毒性、细胞毒性、基因毒性、生殖毒性、二噁英毒性和神经毒性,已被加拿大政府风险评估识别为进一步优先控制名录。随着环境领域对双酚类化合物的广泛关注,相关研究工作逐渐向水、沉积物、灰尘和生物样品等多介质开拓。但是,由于不同环境样品在基质复杂性和污染物浓度水平等方面存在显著差异,开发提取效率高、净化选择性好、普适性强、操作简单、高通量的提取和净化方法,有助于实现环境介质中双酚类化合物的高灵敏、批量检测。近年来,新型前处理技术发展迅速,尤其是固相萃取技术,在双酚类化合物提取与净化方面取得了长足的发展,不仅在一定程度上克服了传统提取净化方法存在的耗时、耗力和耗溶剂等不足,而且为新型污染物分析提供了更多的技术支持。该文简述了典型双酚类化合物的理化性质、用途用量和环境危害,重点围绕新型固相萃取吸附剂开发和固相萃取模式转变两个方面,总结了固相萃取在双酚类化合物提取净化方法方面取得的进展。商品化固相萃取产品普适性强,在环境监测领域应用范围较广,适用于双酚类化合物的产品种类有限;新型吸附剂研发聚焦吸附容量(如介孔硅材料、碳纳米材料、金属-有机框架材料、环糊精)和选择性(如分子印迹聚合物和混合模式离子交换聚合物)两个方面,种类多样化可满足不同检测需求;越来越多的高灵敏分析仪器不断推向市场,为适应新的发展形势,固相萃取模式正逐渐向微型化、自动化、简易化等方向发展,如QuEChERS、固相微萃取、磁固相萃取等。     

超声提取-高温燃烧吸收-离子色谱法测定纺织品中可吸附有机卤化物北大核心CSCD

建立了一种对纺织品中可吸附有机卤化物(AOX)的超声提取-高温燃烧吸收-离子色谱定量检测分析新方法。该方法采用超声方式提取纺织品中的AOX,提取液加入活性炭进行振荡吸附,并用酸性硝酸钠溶液对无机卤化物进行去除。采用程序升温的氧化燃烧方式对吸附AOX的活性炭进行裂解、燃烧及气化,其产生的卤化氢等气体随载气进入吸收液并完全转化为无机卤素阴离子,采用离子色谱分离测定,外标法定量。实验优化了超声提取时间、活性炭用量、燃烧气及其流量、燃烧升温程序、吸收液和吸收方式等前处理条件,并对离子色谱的仪器分析条件如色谱柱、柱温及淋洗液流速等进行优化。结果表明,氟、氯、溴、碘4种卤素离子的标准溶液在0.02~10 mg/L范围内呈线性关系,线性相关系数(R^(2))均在0.999以上;AOX测定的方法定量限为0.10~0.50 mg/kg。以棉、毛和涤纶3种不同种类的阴性纺织样品作为样品基质,选取典型的有机卤化物进行加标,在低、中、高3个加标水平下测得AOX的平均回收率为82.3%~98.7%,相对标准偏差(RSD,n=7)为2.0%~5.7%,表明方法具有良好的回收率和精密度。将该方法应用于实际纺织样品的测定,检出了不同含量的AOX,且重复性好。研究建立的方法通过采用活性炭的振荡吸附、程序升温的高温氧化燃烧方式和多孔吸收瓶的二级吸收方法,提高了AOX转化为无机卤素的回收率;同时利用离子色谱仪器选择性好、灵敏度高的特点成功地一次性分离检测4种AOX,且无杂质离子的干扰。该方法简单、准确、可靠,满足国内外法规和标准对纺织品中AOX的限量要求,适用于纺织品中AOX的分析测定。     

基于低共熔溶剂的萃取分离技术及其应用研究进展

随着绿色化学的发展,开发和应用符合绿色化学要求的溶剂和方法备受关注。作为离子液体类似物,低共熔溶剂(deep eutectic solvent, DES)是通过氢键受体(hydrogen bond acceptor, HBA)和氢键供体(hydrogen bond donator, HBD)的氢键作用而形成的一种混合物,具有环境友好、制备简单、成本低、可生物降解等优点,在很多领域均有越来越广泛的应用。DES可以从不同样品中萃取和分离不同的目标化合物,其作为萃取溶剂具有独特的优势,可以获得较高的萃取效率且样品基质对分析过程的影响较小。在分散液液微萃取(dispersive liquid-liquid micro-extraction, DLLME)程序中,DES可以萃取复杂基质中的残留药物、金属离子和生物活性成分;与传统的萃取方法相比,该方法具有对有机试剂需求少,萃取效率更高等明显优势。而且,在DLLME中加入DES作为分散剂,能够加速萃取剂在样品溶液中的扩散,具有小型化、成本低等优点。相比于传统分散剂甲醇、乙腈的高挥发性、易燃性,DES的高稳定性、低毒性使其在绿色化学领域中更具有优势,应用更广。因此,DES与DLLME的结合近年来发展迅速。不仅如此,DES与固相萃取联合应用也具有广泛的应用前景,在与固相萃取小柱和搅拌棒联合应用时,DES可以作为洗脱剂,氢键供体及氢键给体的用量之比是洗脱效率的重要考察因素之一。在与磁性材料联用时,DES能与磁性多壁碳纳米管、磁性氧化石墨烯等纳米复合材料结合,通过氢键、π-π作用力和静电作用力等特异性吸附目标分析物。并且能够参与磁性凝胶和分子印迹聚合物的合成,推动磁性材料向绿色化学的方向发展,进一步拓展DES的应用。作为一类新兴的绿色溶剂,DES在化合物的萃取分离技术方面受到广泛关注,在不同的萃取技术中扮演了不同的角色,并表现出良好的性能,因此逐渐成为绿色化学领域的研究重点。该文整合了DES在萃取分离技术中的研究进展,介绍了DES的制备、性质和分类,对DES在DLLME和固相萃取中的应用进行了总结和归类,并展望了DES在萃取分离技术中的应用前景,为DES未来的应用提供参考。     

低温等离子体在锂离子电池材料中的应用

综合评述了低温等离子体技术的基本原理、 常用方法及其在锂离子电池材料领域中的研究进展, 重点评述了等离子体技术在锂离子电池正极、 负极、 隔膜及固态电解质等重要组分中的材料制备与表面改性方面的主要研究结果和应用优势, 并对其所面临的挑战和未来的应用方向进行了展望.     

Fabrication of open‐porous PCL/PLA tissue engineering scaffolds and the relationship of foaming process,morphology, and mechanical behavior

Tissue engineering scaffolds should provide a suitable porous structure and proper mechanical strength, which is beneficial for the delivery of growth factor and regulation of cells. In this study, the open‐porous polycaprolactone (PCL)/poly (lactic acid) (PLA) tissue engineering scaffolds with suitable porous scale were fabricated using different ratios of PCL/PLA blends. At the same time, the relationship of foaming process, morphology, and mechanical behavior in the optimized batch microcellular foaming process were studied based on the single‐factor experiment method. The porous structures and mechanical strength of the scaffolds were optimized by adjusting foaming parameters, including the temperature, pressure, and CO₂ dissolution time. The results indicated that the foaming parameters influence the cell morphology, further determine the mechanical behavior of PCL/PLA blends. When the PCL content is high, with the increase of temperature and time, the cell diameter and the elastic modulus increased, and the tensile strength and elastic modulus increased with the increase of the average cell size, and decreased as the increase of the cell density. While when the PLA content was high, the cell diameter showed the same trend, and the tensile strength and elastic modulus were higher, and the elongation at break was lower, and tensile strength and elastic modulus decreased with the increase of the average cell size and increased with the increase of cell density. This work successfully fabricated optimized porous PCL/PLA scaffolds with excellent suitable mechanical properties, pore sizes, and high interconnectivity, indicating the effectiveness of modulating the batch foaming process parameters.     

Poly(lactide) stereocomplexes: formation, structure, properties, degradation, and applications

Poly(lactide)s [i.e. poly(lactic acid) (PLA)] and lactide copolymers are biodegradable, compostable, producible from renewable resources, and nontoxic to the human body and the environment. They have been used as biomedical materials for tissue regeneration, matrices for drug delivery systems, and alternatives for commercial polymeric materials to reduce the impact on the environment. Since stereocomplexation or stereocomplex formation between enantiomeric PLA, poly(L-lactide) [i.e. poly(L-lactic acid) (PLLA)] and poly(D-lactide) [i.e. poly(D-lactic acid) (PDLA)] was reported in 1987, numerous studies have been carried out with respect to the formation, structure, properties, degradation, and applications of the PLA stereocomplexes. Stereocomplexation enhances the mechanical properties, the thermal-resistance, and the hydrolysis-resistance of PLA-based materials. These improvements arise from a peculiarly strong interaction between L-lactyl unit sequences and D-lactyl unit sequences, and stereocomplexation opens a new way for the preparation of biomaterials such as hydrogels and particles for drug delivery systems. It was revealed that the crucial parameters affecting stereocomplexation are the mixing ratio and the molecular weight of L-lactyl and D-lactyl unit sequences. On the other hand, PDLA was found to form a stereocomplex with L-configured polypeptides in 2001. This kind of stereocomplexation is called "hetero-stereocomplexation" and differentiated from "homo-stereocomplexation" between L-lactyl and D-lactyl unit sequences. This paper reviews the methods for tracing PLA stereocomplexation, the methods for inducing PLA stereocompelxation, the parameters affecting PLA stereocomplexation, and the structure, properties, degradation, and applications of a variety of stereocomplexed PLA materials.     

Density functional theory study of the hydrogen bond interaction between lactones, lactams, and methanol

The structure and relative stability of methanol complexes with various cyclic ketones, lactones, lactams, and N-methyl lactams from three- to seven-membered rings have been investigated using the density functional theory method. The geometries, harmonic frequencies, and energies were calculated at the B3LYP/6-311+G(d,p) level. Three stable structures, cis-a, cis-b, and trans, with respect to the ring oxygen (nitrogen) atom, were found to be local minima of the potential energy surface. For lactones and N-methyl lactams, the most stable structure is trans; it is stabilized, as in cyclic ketones, through the conventional hydrogen bond (HB) interaction between the basic carbonyl oxygen and the acidic methanolic hydrogen and an unconventional HB interaction between the methanolic oxygen and the CH hydrogen, in the alpha position of the carbonyl group. For unsubstituted lactams, the cis-a structure, stabilized through a HB interaction between the NH group and the methanol oxygen in addition to the conventional HB interaction, is the most stable. The topological properties of the electron density ratify the existence of conventional (N,O-H. . .O) and unconventional (C-H. . .O) hydrogen bonding. A good correlation was found between the HB distances and the electron density at the HB critical point. The unsubstituted lactams yield more stable complexes with methanol than N-methyl lactams, lactones, and cyclic ketones. In the most stable complexes, both components behave simultaneously as a HB donor and as a HB acceptor.     

History of Adhesives

Adhesives are the diplomats of the polymer world. They exist for the purpose of bringing other materials together; their success is measured by the production cost, properties, and permanence of the assembly. Historically, the starches, protein glues, and natural rubber were supplemented or replaced by phenolics and amino resins for plywood and particleboard; synthetic rubbers for construction, textile bonding, and pressure-sensitives; poly-vinyl acetate for packaging, gypsum board, and the home handy-person's “white glue”; hot melts for bookbinding. Three of the newer families of adhesives are outstanding in performance: the epoxies; the isocyanates and polyurethanes; and the versatile acrylics, including the spectacularly growing cyanoacrylates and anaerobics. They are especially useful for the bonding of metals, synthetic fibers, plastic film, and other “difficult” substrates in product assembly, aerospace, textiles, construction, furniture, film laminates, and pressure-sensitives. Synergism and hybrid functionality are hallmarks of many of the new adhesives. Controlled cross-linking, improved adhesion, and other characteristics are attained through adroit blending of functional groups: vinyl unsaturation, carboxyl, glycidyl, hydroxyl, isocyanate, and methylol amide.     

丝素蛋白纤维及功能化材料的设计与构筑

随着环境污染、资源枯竭和医疗健康等问题的加剧,研发同时满足特定使用性能、安全性及可再生性的新型材料成为当前的发展趋势.而丝素蛋白材料正是以天然蚕丝为基本原材料,经一定的加工和功能化而形成的具有特殊结构、独特性能和广泛应用的生物质材料,近年来在生物医药、生物电子、智能传感等领域展现出巨大的应用潜力.本专论总结了丝素蛋白纤维及功能化材料的最新成果,结合本课题组相关工作,重点阐述了再生丝素蛋白纤维的仿生制备、生物医用支架的构筑与功能化、智能电子材料的设计以及天然多功能蚕丝及其构筑基元制备的研究进展,以期为高性能丝素蛋白材料的设计与构筑提供指导和借鉴.     

An integrated strategy of secondary metabolomics and glycomics to investigate multi-component variations in wine-processing of medicinal herbs and functional foods: A case study on Fructus Corni

Fructus Corni (FC), as a promising Chinese medicinal herb, has aroused considerable interest. Generally, FC needs to be processed according to the limited standard policy in China before clinical application, while the investigations on the specific processing methods (such as wine steaming or high-pressure wine steaming) are unclear. A comprehensive metabolomics strategy based on integrated non-targeted metabolomics and targeted glycomics in this paper was implemented to investigate the influences of the different processing technologies such as steaming, wine steaming, high-pressure steaming, high-pressure wine steaming, wine immersion, and wine stir-frying on FC, respectively. UHPLC-Q-TOF-MS/MS was employed for identifying and distinguishing the secondary metabolites. A total of 85 components were identified in all groups. The results of PCA score plots showed that the crude and processed samples had a complete separation, and wine steamed and high-pressure wine steamed samples could be a category, indicating that the two processed products had a similar quality. Multiple chromatography including HPLC (C₁₈)-PDA, HPLC (NH₂)-ELSD, and HPGPC-ELSD was used for determining the molecular weight distributions, the monosaccharide compositions of polysaccharides, and the contents of free monosaccharides and oligosaccharides. The results indicated that the content and composition of saccharides were different in crude and different processed FC. The polysaccharides were composed of fucose, arabinose, galactose, glucose, galacturonic acid, mannose and rhamnose, and the free monosaccharides were composed of fucose, arabinose, galactose, glucose, mannose, rhamnose and fructose in all FC samples. The PCA score plots of the glycomics indicated that the crude and high-pressure wine steamed FC could be a category, showing that the two groups had similar chemical compositions. Ultimately, the simulation processing experiments indicated that the transformation of morroniside, polysaccharides, oligosaccharides, fructose, and glucose to 5-HMF through the reactions of dehydration and deglycosylation was the potential mechanism of enhancing the effects by processing. Conclusionly, the saccharides should be investigated as thoroughly as the secondary metabolites, and the high-pressure wine steamed FC could be an alternative to wine steamed FC.     

我国胶体与界面化学的发展

胶体与界面化学在能源、材料、生物、化学制造和环境科学等领域具有广泛的应用,并渗透到国民经济的各个主要领域中。所涉及到其中的一些重大科学问题,如土壤改良、功能与复合材料、三次采油、人造血浆、药物缓释与定向、润滑和油漆涂料等,与国家安全、能源开发、环境保护和人民生活等方面密切相关,发展胶体与界面化学学科对社会与经济的可持续发展具有重要的意义。本文综述了我国胶体与界面化学学科30年来的研究进展,尤其是近10年所取得的成就,主要包括新型两亲分子有序组合体的设计与构建、界面化学与有序分子膜、胶体与界面化学在微纳米功能材料合成中的应用新进展、胶体与界面化学在生物医药中的研究新进展,以及胶体与界面化学的研究新方法,并对该学科的发展前景与趋势进行了分析。     

Atmospheric aerosols: composition, transformation, climate and health effects

Aerosols are of central importance for atmospheric chemistry and physics, the biosphere, climate, and public health. The airborne solid and liquid particles in the nanometer to micrometer size range influence the energy balance of the Earth, the hydrological cycle, atmospheric circulation, and the abundance of greenhouse and reactive trace gases. Moreover, they play important roles in the reproduction of biological organisms and can cause or enhance diseases. The primary parameters that determine the environmental and health effects of aerosol particles are their concentration, size, structure, and chemical composition. These parameters, however, are spatially and temporally highly variable. The quantification and identification of biological particles and carbonaceous components of fine particulate matter in the air (organic compounds and black or elemental carbon, respectively) represent demanding analytical challenges. This Review outlines the current state of knowledge, major open questions, and research perspectives on the properties and interactions of atmospheric aerosols and their effects on climate and human health.     

Identification of ginsenoside metabolites in plasma related to different bioactivities of Panax notoginseng and Panax ginseng

Although the chemical components of Panax notoginseng (PN) and Panax ginseng (PG) are similar, their bioactivities are different. In this study, the differential bioactivities of PN and PG were used as the research object. First, the different metabolites in the plasma after oral administration of PN and PG were analyzed using a UPLC-Q/TOF-MS-based metabolomics approach. Afterward, the metabolite-target- pathway network of PN and PG was constructed, and thus the pathways related to different bioactivities were analyzed. As a result, 7 different metabolites were identified in PN group, and 10 different metabolites were identified in the PG group. In the PN group, the metabolite N1 was related to hemostasis, N1 and N3 were related to inhibiting the nerve center, antihypertensive, and abirritation. The metabolites N1, N3, N4, N5, and N6 were related to liver protection. The results showed that the metabolites G1, G2, G3, G5, and G6 in PG group were related to heart protection, and G1, G2, G6, and G9 were related to increased blood pressure. There were 13 signaling pathways related to different biological activities of PN (8 pathways) and PG (5 pathways). These pathways further clarified the mechanism of action that caused the different bioactivities between PN and PG. In summary, metabolomics combined with network pharmacology could be helpful to clarify the material basis of different bioactivities between PN and PG, promoting the research on PN and PG.     

无机钙材料在石灰岩文物表面防护中的应用

由于碳酸盐矿物的质地特点,石灰岩文物在露天环境中极易发生表面溶蚀,其上赋存文化信息的文字、纹饰和符号等雕刻痕迹也随之湮灭,对其文物价值造成了严重减损。从耐候性和兼容性角度考虑,无机保护材料显然更适合于石灰岩文物的表面防护处理。近年来,基于草酸钙、磷灰石和碳酸钙等钙基材料的石灰岩文物表面防护研究逐渐兴起并开始走向应用。本文就上述钙基保护材料的特点、防护膜制备和应用实践等做了归纳和评述,以期为石灰岩文物保护研究提供参考和借鉴。     

聚氧化乙烯絮凝-电感耦合等离子体发射光谱法测定土壤中水溶性钾、钠、钙、镁、硫酸根

建立了聚氧化乙烯絮凝-4000r/min离心,电感耦合等离子体发射光谱法（ICP-AES）测定土壤水溶性钠钾钙镁硫酸根离子的方法。本法在常规方法浸提的基础上,加入聚氧化乙烯絮凝剂使溶液中的胶体形成絮凝物聚沉,制得澄清溶液,消除了胶体对钾、钠、钙、镁吸附的干扰;采用电感耦合等离子体发射光谱法一次性测定钾、钠、钙、镁、硫酸根,相较传统方法简便快速,结果准确可靠。本法各离子检出限为0.37-2.91g/g,相对标准偏差小于5.55%,完全满足检测要求。该法操作简便,快速,实用性强,对环境无二次污染,已成功应用于土壤水溶性钾、钠、钙、镁、硫酸根离子的测试分析中,适合土壤批量样品分析。     

Optimization of throughput and desorbent consumption in simulated moving-bed chromatography for paclitaxel purification.

In simulated moving-bed (SMB) applications, throughput and desorbent consumption are two key factors that control process cost. For a given adsorbent volume and product purity requirements, throughput and desorbent consumption depend on desorbent composition, column configuration, column length to diameter ratio, and adsorbent particle size. In this study, these design parameters are systematically examined for paclitaxel purification. The results show that if adsorbent particle size, column dimensions and column configuration are fixed, the higher the product purity required, the lower the throughput. If product purity and yield are fixed, the larger the solute migration speed ratio, the higher the throughput, and the lower the desorbent consumption. If total bed volume and product purities are fixed, the longer the separation zones, the higher the throughput, but the higher the desorbent flow-rate. An intermediate configuration gives the minimum desorbent consumption. If there are no limits on pressure drop or zone flow-rate, the larger the column length to diameter ratio, the smaller the adsorbent particle size, the higher the throughput, and the lower the desorbent consumption. If the maximum zone flow-rate is controlled by the pressure drop limit and not by the standing waves requirement, the longer the columns, the lower the zone flow-rates and the lower the throughput. For 150 microns adsorbent particles and a maximum zone flow-rate of 300 ml/min, a design with optimal throughput and desorbent consumption is found for paclitaxel purification.