全文获取类型
收费全文 | 2460篇 |
免费 | 278篇 |
国内免费 | 167篇 |
专业分类
化学 | 978篇 |
晶体学 | 5篇 |
力学 | 536篇 |
综合类 | 52篇 |
数学 | 567篇 |
物理学 | 767篇 |
出版年
2024年 | 13篇 |
2023年 | 47篇 |
2022年 | 118篇 |
2021年 | 94篇 |
2020年 | 69篇 |
2019年 | 65篇 |
2018年 | 86篇 |
2017年 | 118篇 |
2016年 | 126篇 |
2015年 | 93篇 |
2014年 | 121篇 |
2013年 | 180篇 |
2012年 | 174篇 |
2011年 | 156篇 |
2010年 | 126篇 |
2009年 | 155篇 |
2008年 | 158篇 |
2007年 | 133篇 |
2006年 | 93篇 |
2005年 | 92篇 |
2004年 | 104篇 |
2003年 | 75篇 |
2002年 | 63篇 |
2001年 | 53篇 |
2000年 | 53篇 |
1999年 | 44篇 |
1998年 | 43篇 |
1997年 | 29篇 |
1996年 | 25篇 |
1995年 | 26篇 |
1994年 | 23篇 |
1993年 | 23篇 |
1992年 | 21篇 |
1991年 | 18篇 |
1990年 | 17篇 |
1989年 | 10篇 |
1988年 | 8篇 |
1987年 | 9篇 |
1986年 | 9篇 |
1985年 | 5篇 |
1984年 | 9篇 |
1982年 | 4篇 |
1981年 | 5篇 |
1980年 | 2篇 |
1979年 | 3篇 |
1978年 | 1篇 |
1977年 | 3篇 |
1974年 | 1篇 |
1970年 | 1篇 |
1967年 | 1篇 |
排序方式: 共有2905条查询结果,搜索用时 15 毫秒
141.
A New Technique of Synthesizing 10—Hydroxy—5—methyl—5,10—dihydrophenophosphazine 10—Oxide 总被引:1,自引:0,他引:1
ZhiGangYIN DeFengZHAO 《中国化学快报》2003,14(4):347-350
10-Hydroxy-5-methyl-5,10-dihydrophenophosphazine 10-oxide(1)was prepared by a new technique of treating 10-methoxy-5,10-dihydrophenophosphazine 10-oxide(2)with an equivalent of NaH in anhydrous DMF,and then at 120℃ for 3-4h,which not only avoided poisonous and expensive methyl iodide used in literature,but made the consumption of NaH greatly decrease as well.The possible reaction mechanism was also described.The chemical structure of 1 was confiremed by IR,NMR,and mass spectroscopy. 相似文献
142.
Affinity enrichment of plasma membrane for proteomics analysis 总被引:6,自引:0,他引:6
Proteomics analysis of plasma membranes from cells exposed to different extracellular environments is potentially a powerful approach for the identification of membrane-associated proteins responding to these environments. Preparation of high concentration plasma membrane fractions with low contamination from cellular organelles is essential for such studies. Here, we describe an affinity enrichment method, which combines cell surface biotinylation with affinity enrichment by immobilized streptavidin beads, for the isolation of plasma membranes. This method results in a 400-fold enrichment of plasma membrane relative to endoplasmic reticulum, a major contaminant in standard plasma membrane preparations, and dramatically reduces contamination from other cellular organelles. The biotinylation reaction did not interfere with ligand-dependent activation of receptor tyrosine kinases or G-protein coupled receptors, suggesting cell-surface signal transduction machinery remains functional. Membrane fractions prepared by this method should provide excellent starting materials for membrane proteomics analysis such as studies of dynamic trafficking and regulation of signaling molecules or identification of disease-specific membrane markers. 相似文献
143.
Ultra‐performance liquid chromatography coupled with electrospray ionization/quadrupole time‐of‐flight mass spectrometry for the rapid analysis of constituents in the traditional Chinese medical formula Danggui San 下载免费PDF全文
In this work, ultra‐performance LC with ESI quadrupole TOF‐MS (UPLC–ESI‐Q‐TOF‐MS) and automated MetaboLynx analysis was used to rapidly separate and identify the chemical constituents of Danggui San, a traditional Chinese medical formula. The analysis was performed on a Waters UPLC BEH C18 column using a gradient elution system. A hyphenated ESI and Q‐TOF analyzer was used for the determination of the accurate mass of the protonated or deprotonated molecule and fragment ions in both positive and negative modes. Based on retention times, accurate mass, and the mass spectrometric fragmentation characteristics, a total of 47 compounds distributed over the chemical groups of phthalides, flavonoids, monoterpene glycosides, sesquiterpenoids, phenolics, and alkaloids, were simultaneously separated within 18 min and identified or tentatively elucidated in Danggui San for the first time. UPLC–ESI‐Q‐TOF‐MS analysis revealed the complexity of the chemical composition of this formula. The method developed is rapid, accurate, reliable, and highly sensitive to characterize the chemical constituents of Danggui San. 相似文献
144.
Probing the Anticancer Mechanism of (−)‐Ainsliatrimer A through Diverted Total Synthesis and Bioorthogonal Ligation 下载免费PDF全文
Dr. Chao Li Ting Dong Qiang Li Prof. Dr. Xiaoguang Lei 《Angewandte Chemie (International ed. in English)》2014,53(45):12111-12115
Herein, we report an efficient approach for exploring the novel anticancer mechanism of (?)‐ainsliatrimer A, a structurally complex and unique trimeric sesquiterpenoid, through a combined strategy of diverted total synthesis (DTS) and bioorthogonal ligation (TQ ligation), which allowed us to visualize the subcellular localization of this natural product in live cells. Further biochemical studies facilitated by pretarget imaging revealed that PPARγ, a nucleus receptor, was a functional cellular target of ainsliatrimer A. We also confirmed that the anticancer activity of ainsliatrimer A was caused by the activation of PPARγ. 相似文献
145.
Serum pharmacochemistry combined with multiple data processing approach to screen the bioactive components and their metabolites in Mutan Cortex by ultra‐performance liquid chromatography tandem mass spectrometry 下载免费PDF全文
Jian‐hua Liu Hui Sun Ai‐hua Zhang Guang‐li Yan Ying Han Chang‐song Xue Xiao‐hang Zhou Hui Shi Xi‐jun Wang 《Biomedical chromatography : BMC》2014,28(4):500-510
Root cortex of Paeonia suffruticosa Andrews (Paeoniaceae), known as Moutan Cortex (MC), is known to have anti‐allergic and anti‐inflammatory properties. However, the constituents absorbed into blood after oral administration of MC remain unknown. A sensitive and rapid method by ultra‐high‐pressure liquid chromatography–electrospray ionization–quadrupole‐time‐of‐flight mass spectrometry (UPLC‐ESI‐Q‐TOF‐MS) technology and the MetaboLynxTM software combined with multiple data processing approach (Mdpa) was established to investigate the absorbed constituents in rats after oral administration of MC, providing unique high‐throughput capabilities for drug metabolism study. A hyphenated electrospray ionization and quadrupole‐time‐of‐flight analyzer was used for the determination of accurate mass of the fragment ion in negative mode, with excellent MS mass accuracy and enhanced data acquisition. This rapid automated analysis method was successfully applied for screening and identification of the constituents absorbed and metabolized studies of MC after oral administration to rats. A total of 46 peaks were obtained from MC, 41 of which were tentatively characterized. In the VIP‐plot of orthogonal partial least‐squares discriminant analysis, 23 interesting ions in serum samples were extracted, and 16 parent components and seven metabolites were detected in vivo. The integrative serum pharmacochemistry technique, UPLC‐ESI‐Q‐TOF‐MS, and Mdpa method were successfully applied for rapid discovery of multiple components from MC. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
146.
Ultra‐performance liquid chromatography tandem mass spectrometry combined with automated MetaboLynx analysis approach to screen the bioactive components and their metabolites in Wen‐Xin‐Formula 下载免费PDF全文
147.
基于液相色谱-质谱联用的代谢组学技术因其高效分离能力和高灵敏检测能力已成为生命科学研究的重要手段,但由于缺乏有效的通用标准谱图库,检测到的大量代谢物的结构难以鉴定。这制约了代谢组学覆盖度的提高和生物标志物的发现,造成化学和生物信息的严重丢失,成为代谢组学发展的主要技术瓶颈。随着质谱仪器及计算机技术的进步,基于大气压电离质谱(API-MS)的代谢物结构鉴定技术飞速发展,本文从质谱仪器、代谢物分子结构式判别、数据库及谱图检索以及计算机辅助谱图解析等方面,对代谢物结构鉴定的最新进展进行了综述。 相似文献
148.
Yan‐Xue Chen Kang‐Kang Tang Xin Wang Bing‐Yi Chen Guo‐Qiang Qin Jin‐Hui Yang 《无机化学与普通化学杂志》2014,640(11):2292-2295
The zinc(II) coordination polymer [Zn3(BPT)2(μ2‐H2O)2(H2O)2]n · n(DMA) ( 1 ) (H3BPT = biphenyl‐3,4′,5‐tricarboxylic acid, DMA = N,N′‐dimethylactamide) was obtained by the solvothermal reaction of H3BPT with Zn(NO3)2 in DMA/H2O mixed solvent. Single crystal X‐ray analysis reveals that compound 1 has a complicated 3D framework containing linear trinuclear [Zn3(COO)4(μ2‐H2O)2] clusters as building subunits, which can be simplified into a (3,6)‐connected rtl topological network with the Schläfli symbol {4.62}2{42.610.83}. The calculated results of total and partial density of states (DOS) indicate that the luminescence of 1 mainly originates from intraligand charge transfer. 相似文献
149.
Patients are usually exposed to multiple drugs, and metabolite profiling of each drug in complex biological matrices is a big challenge. This study presented a new application of an improved high resolution mass spectrometry (HRMS)-based data-mining tools in tandem to fast and comprehensive metabolite identification of combination drugs in human. The model drug combination was metronidazole-pantoprazole-clarithromycin (MET-PAN-CLAR), which is widely used in clinic to treat ulcers caused by Helicobacter pylori. First, mass defect filter (MDF), as a targeted data processing tool, was able to recover all relevant metabolites of MET-PAN-CLAR in human plasma and urine from the full-scan MS dataset when appropriate MDF templates for each drug were defined. Second, the accurate mass-based background subtraction (BS), as an untargeted data-mining tool, worked effectively except for several trace metabolites, which were buried in the remaining background signals. Third, an integrated strategy, i.e., untargeted BS followed by improved MDF, was effective for metabolite identification of MET-PAN-CLAR. Most metabolites except for trace ones were found in the first step of BS-processed datasets, and the results led to the setup of appropriate metabolite MDF template for the subsequent MDF data processing. Trace metabolites were further recovered by MDF, which used both common MDF templates and the novel metabolite-based MDF templates. As a result, a total of 44 metabolites or related components were found for MET-PAN-CLAR in human plasma and urine using the integrated strategy. New metabolic pathways such as N-glucuronidation of PAN and dehydrogenation of CLAR were found. This study demonstrated that the combination of accurate mass-based multiple data-mining techniques in tandem, i.e., untargeted background subtraction followed by targeted mass defect filtering, can be a valuable tool for rapid metabolite profiling of combination drugs in vivo. 相似文献
150.
Jun‐Seok Lee Jae Wook Lee Namyoung Kang Hyung‐Ho Ha Young‐Tae Chang 《Chemical record (New York, N.Y.)》2015,15(2):495-510
Synthetic molecules that modulate and probe biological events are critical tools in chemical biology. Utilizing combinatorial and diversity‐oriented synthetic strategies, access to large numbers of small molecules is becoming more and more feasible, and research groups in this field can take advantage of the power of chemical diversity. Since the majority of early studies were focused on the discovery of compounds that perturb protein functions, diversity‐based approaches are often considered as therapeutic lead discovery tactics. However, the diversity‐oriented approach can also be applied to advance distinct aims, such as target protein identification, or the development of imaging probes and sensors. This review provides a personal perspective of the chemical‐diversity‐based approach and how this principle can be adapted to various chemical biology studies. 相似文献