全文获取类型
收费全文 | 1340篇 |
免费 | 58篇 |
国内免费 | 17篇 |
专业分类
化学 | 1242篇 |
力学 | 10篇 |
综合类 | 2篇 |
数学 | 26篇 |
物理学 | 135篇 |
出版年
2023年 | 35篇 |
2022年 | 51篇 |
2021年 | 80篇 |
2020年 | 81篇 |
2019年 | 45篇 |
2018年 | 35篇 |
2017年 | 44篇 |
2016年 | 47篇 |
2015年 | 57篇 |
2014年 | 50篇 |
2013年 | 61篇 |
2012年 | 72篇 |
2011年 | 100篇 |
2010年 | 61篇 |
2009年 | 100篇 |
2008年 | 46篇 |
2007年 | 74篇 |
2006年 | 46篇 |
2005年 | 48篇 |
2004年 | 60篇 |
2003年 | 31篇 |
2002年 | 35篇 |
2001年 | 14篇 |
2000年 | 24篇 |
1999年 | 11篇 |
1998年 | 21篇 |
1997年 | 11篇 |
1996年 | 17篇 |
1995年 | 8篇 |
1994年 | 5篇 |
1993年 | 14篇 |
1992年 | 5篇 |
1991年 | 6篇 |
1990年 | 5篇 |
1989年 | 4篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1983年 | 1篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1974年 | 1篇 |
1970年 | 1篇 |
排序方式: 共有1415条查询结果,搜索用时 19 毫秒
1.
Tiago Augusto Donegatti Alnilan Lobato Luís Moreira Gonalves Elisabete Alves Pereira 《Electrophoresis》2019,40(22):2929-2935
Aldehydes are important compounds in a large number of samples, especially food and beverages. In this work, for the first time, cyclohexane‐1,3‐dione (CHD) was used as a derivatizing reagent aiming aldehyde (formaldehyde, acetaldehyde, propionaldehyde, and valeraldehyde) analysis by MEKC‐DAD. The optimized separation of the derivates was performed using a voltage program (+20 kV, 0–15 min.; +23 kV, 15–17 min.) at a temperature of 26°C, and using as the running buffer a mixture containing 100 mmol/L of sodium dodecyl sulfate and 29 mmol/L of sodium tetraborate at pH 9.2, with maximum absorbance at 260 nm. CHD was compared with two other derivatizing agents: 3‐methyl‐2‐benzothiazolinone hydrazone and phenylhydrazine‐4‐sulfonic acid. The CHD‐aldehyde derivatives were also characterized by LC‐MS. The calibration curves for all aldehydes had r2 above 0.999 and LODs ranged from 0.01 to 0.7 mg/L. The optimized methodology was applied in sugar cane brandy (cachaça) samples successfully. CHD showed to be an alternative derivatization reagent due to its stability, aqueous solubility, high selectivity and sensitivity, reduced impurities, and simple preparation steps. 相似文献
2.
Yangang Cheng Yan Liu Jinyan Tan Yanping Sun Wei Guan Yuan Liu Bingyou Yang Haixue Kuang 《Biomedical chromatography : BMC》2020,34(9):e4881
Our previous work demonstrated that total withanolides of Datura metel L. leaves (TWD) exhibited excellent therapeutic effects on psoriasis. However, current knowledge of its mechanisms is incomplete. In this study, integrated spleen and thymus untargeted metabolomics were used to analyze the changes in endogenous metabolites underlying the immunosuppressive activity of TWD on psoriasis animal models induced by imiquimod. The results suggested that TWD treatment markedly attenuated imiquimod-induced psoriasis and showed significant immunosuppressive activity as evidenced by decreased elevation index of spleen and thymus. Meanwhile, TWD significantly reversed the elevation of immunoregulatory factors, including IL-10, IL-17, IL-22 and IL-23. Multivariate trajectory analysis revealed that TWD treatment could restore the psoriasis-disturbed spleen and thymus metabolite profiles towards the normal metabolic status. A total of 25 and 27 metabolites associated with the immunomodulatory effects for which levels changed markedly upon treatment have been identified in spleen and thymus, respectively. These differential metabolites were mainly involved in amino acid metabolism, nucleotide metabolism, fatty acid metabolism and lipid metabolism. Our investigation provided a holistic view of TWD for intervention in psoriasis through immunoregulation and provided further scientific information in vivo about a clinical value of TWD for psoriasis. 相似文献
3.
Karen Beatriz Méndez-Rodríguez Nicté Figueroa-Vega César Arturo Ilizaliturri-Hernandez Mónica Cardona-Alvarado Jaime Antonio Borjas-García Carlos Kornhauser Juan Manuel Malacara Rogelio Flores-Ramírez Francisco Javier Pérez-Vázquez 《Biomedical chromatography : BMC》2020,34(12):e4956
Metabolomics is a potential tool for the discovery of new biomarkers in the early diagnosis of diseases. An ultra-fast gas chromatography system equipped to an electronic nose detector (FGC eNose) was used to identify the metabolomic profile of Volatile Organic Compounds (VOCs) in type 2 diabetes (T2D) urine from Mexican population. A cross-sectional, comparative, and clinical study with translational approach was performed. We recruited twenty T2D patients and twenty-one healthy subjects. Urine samples were taken and analyzed by FGC eNose. Eighty-eight compounds were identified through Kovats's indexes. A natural variation of 30% between the metabolites, expressed by study groups, was observed in Principal Component 1 and 2 with a significant difference (p < 0.001). The model, performed through a Canonical Analysis of Principal coordinated (CAP), allowed a correct classification of 84.6% between healthy and T2D patients, with a 15.4% error. The metabolites 2-propenal, 2-propanol, butane- 2,3-dione and 2-methylpropanal, were increased in patients with T2D, and they were strongly correlated with discrimination between clinically healthy people and T2D patients. This study identified metabolites in urine through FGC eNose that can be used as biomarkers in the identification of T2D patients. However, more studies are needed for its implementation in clinical practice. 相似文献
4.
Yalda Liaghati Mobarhan Ronald Soong Daniel Lane Andre J. Simpson 《Magnetic resonance in chemistry : MRC》2020,58(5):427-444
Traditionally, due to different hardware requirements, nuclear magnetic resonance (NMR) has developed as two separate fields: one dealing with solids, and one with solutions. Comprehensive multiphase (CMP) NMR combines all electronics and hardware (magic angle spinning [MAS], gradients, high power Radio Frequency (RF) handling, lock, susceptibility matching) into a universal probe that permits a comprehensive study of all phases (i.e., liquid, gel-like, semisolid, and solid), in intact samples. When applied in vivo, it provides unique insight into the wide array of bonds in a living system from the most mobile liquids (blood, fluids) through gels (muscle, tissues) to the most rigid (exoskeleton, shell). In this tutorial, the practical aspects of in vivo CMP NMR are discussed including: handling the organisms, rotor preparation, sample spinning, water suppression, editing experiments, and finishes with a brief look at the potential of other heteronuclei (2H, 15N, 19F, 31P) for in vivo research. The tutorial is aimed as a general resource for researchers interested in developing and applying MAS-based approaches to living organisms. Although the focus here is CMP NMR, many of the approaches can be adapted (or directly applied) using conventional high-resolution magic angle spinning, and in some cases, even standard solid-state NMR probes. 相似文献
5.
Determination of nitrofuran and chloramphenicol residues by high resolution mass spectrometry versus tandem quadrupole mass spectrometry 总被引:1,自引:0,他引:1
An ultra-high performance liquid chromatography based method, coupled to high resolution mass spectrometry (UHPLC–HRMS), was developed to permit the detection and quantification of various nitrofuran and chloramphenicol residues in a number of animal based food products. This method is based on the hydrolysis of covalently bound metabolites and derivatization with 2-nitrobenzaldehyde. Clean-up is achieved by a liquid/liquid and a reversed phase/solid phase extraction. Not only are the four conventional nitrofurans (nitrofurantoin, furazolidone, nitrofurazone and furaltadone) detected, but also nifursol, nitrovin and nifuroxazide. Furthermore, an underivatizable nitrofuran (nifurpirinol) and another banned drug (chloramphenicol) can be quantified as well. The compounds are detected in the form of their precursor ions, [M + H]+ and [M − H]−, respectively. The mass resolving power of 70,000 FWHM, and the applied mass window ensure sufficient selectivity and sensitivity. Confirmation is obtained by monitoring the HRMS resolved product ions which were derived from the unit-mass resolved precursor ions. The multiplexing capability of the utilized Orbitrap instrument provides not only highly selective, but also sensitive confirmatory signals. This method has been validated according to the CD 2002/657/EC for the following matrices: muscle, liver, kidney, fish, honey, eggs and milk. 相似文献
6.
Li‐Ming Sun Bo Zhang Yu‐Chen Wang Hao‐Ke He Xiao‐Guang Chen Su‐Juan Wang 《Biomedical chromatography : BMC》2019,33(2)
Alum‐processing is a traditional method to attenuate the toxicity of Pinelliae Rhizoma (tubers of Pinellia ternate, PT). The present study aimed at investigating the chemical and cytotoxic changes during alum processing. Metabolomic profiles of raw and alum‐processed PT were studied based on ultra‐performance liquid chromatography coupled with Orbitrap mass spectrometry. More than 80 chemicals in positive MS mode and 40 chemicals in negative MS mode, such as organic acids, amino acids, glucosides and nucleosides, were identified after multivariate statistical analysis, including principal component analysis and orthogonal partial least‐square discriminant analysis. Almost all of the identified chemical markers were significantly decreased ~10‐ to 100‐fold after alum processing. Meanwhile, the correlations between the chemical markers were assimilated to a positive coefficient from disorderly distribution during the processing. Raw PT extracts could inhibit the proliferation of human carcinoma cells (HCT‐116, HepG2, and A549) at the rate of 40.5, 24.8 and 31.6% more strongly than processed PT. It was concluded that the alum processing of PT could decrease the number of actively water‐soluble principles at the same time as decreasing toxicity. Given the water‐insoluble property of toxic calcium oxalate raphides in PT, we suggest that a more scientific processing method should be sought. 相似文献
7.
Durgesh Dubey Smriti Chaurasia Anupam Guleria Sandeep Kumar Dinesh Raj Modi Ramnath Misra Dinesh Kumar 《Magnetic resonance in chemistry : MRC》2019,57(1):30-43
Currently, there are no reliable biomarkers available that can aid early differential diagnosis of reactive arthritis (ReA) from other inflammatory joint diseases. Metabolic profiling of synovial fluid (SF)—obtained from joints affected in ReA—holds great promise in this regard and will further aid monitoring treatment and improving our understanding about disease mechanism. As a first step in this direction, we report here the metabolite specific assignment of 1H and 13C resonances detected in the NMR spectra of SF samples extracted from human patients with established ReA. The metabolite characterization has been carried out on both normal and ultrafiltered (deproteinized) SF samples of eight ReA patients (n = 8) using high-resolution (800 MHz) 1H and 1H─13C NMR spectroscopy methods such as one-dimensional 1H CPMG and two-dimensional J-resolved1H NMR and homonuclear 1H─1H TOCSY and heteronuclear1H─13C HSQC correlation spectra. Compared with normal SF samples, several distinctive 1H NMR signals were identified and assigned to metabolites in the 1H NMR spectra of ultrafiltered SF samples. Overall, we assigned 53 metabolites in normal filtered SF and 64 metabolites in filtered pooled SF sample compared with nonfiltered SF samples for which only 48 metabolites (including lipid/membrane metabolites as well) have been identified. The established NMR characterization of SF metabolites will serve to guide future metabolomics studies aiming to identify/evaluate the SF-based metabolic biomarkers of diagnostic/prognostic potential or seeking biochemical insights into disease mechanisms in a clinical perspective. 相似文献
8.
食源性致病微生物导致的食源性疾病已成为全球化的公共卫生问题。快速、有效地检测食源性致病微生物是实现食源性疾病预防与控制的关键环节,也是保障食品安全的技术关键。表面增强拉曼光谱(SERS)具有简单、快速、灵敏度高等优点,在食品安全、生物医学、环境监控等领域展现出良好的应用前景。介绍了近年来SERS在食源性致病微生物检测中的应用研究进展。对SERS技术概况、SERS增强理论及SERS增强基底进行了简要介绍,重点回顾了SERS在食源性致病微生物检测中的应用和发展现状。在食品安全分析方面,利用SERS与模式识别方法相结合对食品中常见食源性致病微生物能实现快速、有效鉴别,部分研究已应用于不同食品样品的分析,体现了SERS作为“指纹图谱”的分析优势;在医学诊断方面,SERS可对病理样品(如血液、尿液等)中食源性致病微生物进行快速检测,缩短了样本分析时间,使食源性疾病的快速诊断成为可能;随着微流控技术的发展,微流控平台结合SERS技术被称为“芯片实验室”应用于食源性致病微生物的检测,可提高分析的可控性,稳定性,特异性和灵敏度。通过对比分析,发现不同研究可采用不同分离方法、不同基底、不同目标捕获方式等实现了食源性致病微生物的检测,展示了不同方法间的差异性。已有研究表明了SERS在食源性致病微生物检测中应用可克服传统方法耗时等缺点,实现灵敏快速分析,为食品安全实时监控,食源性疾病即时诊断提供了有效的分析工具。同时,指出了SERS技术应用于食源性致病微生物分析依然面临很大挑战,(1)大多数研究并没有聚焦于实际样品,而标准培养液和实际样品的SERS检测存在较大差异,实际样品组分会对SERS响应产生干扰;(2)不同方法结果有较大差异,主要是由于纳米增强基底差异,吸附方式原理的差异,稳定性的差异等,因此需要更多深入研究进一步优化条件;(3)期望建立标准化的SERS方法替代传统技术,充分展示SERS作为新兴分析工具快速、灵敏、简捷的优势应用于食品安全,医学诊断等领域。将来,随着研究的深入及相关学科的发展,SERS作为极具潜力的快速分析工具,将在食品安全,生物医学等领域具有更广阔的应用前景。 相似文献
9.
Dr. Jun Zeng Dr. Zhichao Wang Dr. Xin Huang Dr. Sabine S. Eckstein Prof. Dr. Xiaohui Lin Prof. Dr. Hailong Piao Prof. Dr. Cora Weigert Dr. Peiyuan Yin Prof. Dr. Rainer Lehmann Prof. Dr. Guowang Xu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(21):5427-5432
Mass spectrometry (MS) driven metabolomics is a frequently used tool in various areas of life sciences; however, the analysis of polar metabolites is less commonly included. In general, metabolomic analyses lead to the detection of the total amount of all covered metabolites. This is currently a major limitation with respect to metabolites showing high turnover rates, but no changes in their concentration. Such metabolites and pathways could be crucial metabolic nodes (e.g., potential drug targets in cancer metabolism). A stable-isotope tracing capillary electrophoresis–mass spectrometry (CE-MS) metabolomic approach was developed to cover both polar metabolites and isotopologues in a non-targeted way. An in-house developed software enables high throughput processing of complex multidimensional data. The practicability is demonstrated analyzing [U-13C]-glucose exposed prostate cancer and non-cancer cells. This CE-MS-driven analytical strategy complements polar metabolite profiles through isotopologue labeling patterns, thereby improving not only the metabolomic coverage, but also the understanding of metabolism. 相似文献
10.
The global epidemic owing to COVID-19 has generated awareness to ensuring best practices for avoiding the microorganism spread. Indeed, because of the increase in infections caused by bacteria and viruses such as SARS-CoV-2, the global demand for antimicrobial materials is growing. New technologies by using polymeric systems are of great interest. Virus transmission by contaminated surfaces leads to the spread of infectious diseases, so antimicrobial coatings are significant in this regard. Moreover, antimicrobial food packaging is beneficial to prevent the spread of microorganisms during food processing and transportation. Furthermore, antimicrobial textiles show an effective role. We aim to provide a review of prepared antimicrobial polymeric materials for use in coating, food packaging, and textile during the COVID-19 pandemic and after pandemic. 相似文献