首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   646篇
  免费   76篇
  国内免费   90篇
化学   507篇
晶体学   13篇
力学   24篇
综合类   6篇
数学   80篇
物理学   182篇
  2024年   4篇
  2023年   10篇
  2022年   24篇
  2021年   30篇
  2020年   29篇
  2019年   28篇
  2018年   20篇
  2017年   18篇
  2016年   31篇
  2015年   41篇
  2014年   35篇
  2013年   52篇
  2012年   55篇
  2011年   41篇
  2010年   38篇
  2009年   30篇
  2008年   22篇
  2007年   30篇
  2006年   32篇
  2005年   27篇
  2004年   16篇
  2003年   10篇
  2002年   17篇
  2001年   14篇
  2000年   12篇
  1999年   24篇
  1998年   17篇
  1997年   9篇
  1996年   15篇
  1995年   15篇
  1994年   4篇
  1993年   14篇
  1992年   7篇
  1991年   10篇
  1990年   12篇
  1989年   7篇
  1988年   5篇
  1987年   2篇
  1986年   2篇
  1985年   3篇
排序方式: 共有812条查询结果,搜索用时 15 毫秒
71.
In order to investigate the effect of the organic ligands on the structures of coordination polymers, two new cadmium(II) coordination polymers based on the different dicarboxylate ligands, namely [Cd2(bpdc)2(DPNDI)2] · 3H2O · NMF ( 1 ) and [Cd(obb)(DPNDI)] ( 2 ) [H2bpdc = biphenyl‐4,4′‐dicarboxylate, H2obb = 4,4′‐oxybis(benzoic acid), DPNDI = N,N′‐bis(4‐pyridyl)‐1,4,5,8‐naphthalene tetracarboxydiimide, and NMF = N‐methylformamide), were synthesized under solvothermal condition and further characterized. Complex 1 shows a twofold interpenetrated pcu topology. Complex 2 possesses a two‐dimensional (2D) layer structure with –ABCD– stacking sequence. Furthermore, the luminescent properties of complexes 1 and 2 are investigated.  相似文献   
72.
A C2‐symmetric Schiff‐base ligand, derived from tridentate‐Schiff‐base, was developed and successfully applied to the asymmetric Michael addition of nitroalkanes to 2‐enoyl‐pyridine N‐oxides. With this newly catalytic system, an unprecedented diastereoselectivity was obtained in the asymmetric Michael addition of nitroalkanes to 2‐enoyl‐pyridine N‐oxides. In addition, a switch in enantioselectivity was achieved by using this newly catalytic system and our previous catalyst. After a facile reduction, the optically active adduct was converted to a biologically active dihydro2H‐pyrrol 4 a . Furthermore, a connection of two tridentate‐Schiff‐base subunits proved to be an effective strategy in ligand design.  相似文献   
73.
激光雷达以其高垂直空间分辨率和高时间分辨率的优势在大气气溶胶监测中具有重要作用。在利用Fernald法反演气溶胶消光系数和光学厚度的过程中,雷达比是反演结果的主要误差源。在目前的应用中雷达比普遍都是取固定值,这就必然给雷达反演带来误差。通过对污染物以及气象数据与雷达比的逐步回归分析,建立了雷达比估算模型,从而实现雷达比的动态估算。研究表明:雷达比的变化与空气中PM2.5质量浓度、相对湿度、SO2和NO2质量浓度等具有明显相关性。相比于固定值,利用动态雷达比反演的气溶胶消光系数和光学厚度精度明显提高。  相似文献   
74.
As the physicochemical characteristics of solid lipid nanoparticles (SLNs) play a critical role in their success, it is important to understand how the materials and process used in their preparation affect these properties. In this study, two stearyl alcohol-based formulations were prepared using nanotemplate engineering technology and characterized. Both formulations were of a small particle size (<100 nm), ellipsoidal shape, and low polydispersity. (1)H NMR spectroscopy confirmed that the SLNs have the expected solid core structure and PEGylated surface. Analysis of the bulk materials indicated that a number of complex interactions are present among the SLN components, including a eutectic between stearyl alcohol and Brij 78. The decreased crystallinity resulting from these interactions may allow for enhanced drug loading. Physiological stability was identified and confirmed as a potential problem due to the low melting point of the eutectic. However, it is expected that with appropriate formulation modifications nanotemplate engineered SLNs will possess the properties necessary for a successful drug delivery system.  相似文献   
75.
76.
Li J  Li X  Guo Z  Yu L  Zou L  Liang X 《The Analyst》2011,136(19):4075-4082
Desalting peptides before mass spectrometry analysis is important because salts lead to adduct formation, increased chemical noise and ion suppression effect. A high concentration of salt can clog nanoelectrospray ionization (ESI) emitters. The reverse phase C18 material is commonly used to desalt peptides because of its high binding capacity. However, peptides with high hydrophilicity, such as glycopeptides, are not retained well on this material, resulting in the loss of peptide information. To improve the efficiency of glycopeptide desalting, we introduced a hydrophilic interaction chromatography (HILIC)-based material named click maltose. Four glycoproteins, horseradish peroxidase (HRP), human serum immunoglobulin G (IgG), bovine ribonuclease B (RNase B), and α-1 acid glycoprotein (AGP) were chosen as models and their glycopeptides were desalted with click maltose, AQ C18, Empore C18 and ZipTip C18. Click maltose as a HILIC material exhibited better performance than the other three C18 materials for both number of targeted glycopeptides and their corresponding intensities. In addition, accurate glycopeptide profiling was achieved with click maltose desalting regardless of peptide lengths and glycan types.  相似文献   
77.
This work demonstrated the feasibility of detecting hydrocortisone in cosmetics using a novel CdSe/CdS quantum dots‐based competitive fluoroimmunoassay with magnetic core/shell Fe3O4/Au nanoparticles (MCFN) as solid carriers. Hydrocortisone antigen was labeled with the synthesized core/shell CdSe/CdS quantum dots (QDs) to form the antigen‐QDs conjugate. Meanwhile, hydrocortisone antibody was incubated with MCFN and the immobilized antibody was obtained. The immobilized antibody was then mixed sequentially with hydrocortisone and a slightly excess amount of the QDs‐labeled hydrocortisone antigen, allowing their competition for binding with the antibody immobilized on MCFN. The bound hydrocortisone and the antigen‐QDs conjugates on MCFN were removed subsequently after the mixture was applied to a magnetic force. The analyte concentration was obtained by measuring the fluorescence intensity of the unbound hydrocortisone antigen‐QDs conjugates. The proposed method was characterized by simplicity, rapidity, and high sensitivity with a wide linear working range of 0.5 to 15000 pg·mL?1 and a low detection limit of 0.5 pg·mL?1. The proposed method was successfully applied to the determination of hydrocortisone in cosmetics with satisfactory results.  相似文献   
78.
Selective enrichment of glycopeptides is of great importance for protein glycosylation analysis using mass spectrometry since the signals of glycopeptides could be severely suppressed by the coexisting non-glycosylated peptides in the protein digest. In the present work, a strategy for N-linked glycopeptide enrichment through reversed-phase depletion coupled with hydrophilic affinity enrichment by applying the customized matrix named Click OEG-CD is developed. Compared with single hydrophilic interaction liquid chromatography (HILIC) mode, the strategy exhibited remarkably higher selectivity for N-linked glycopeptides. As many as 22, 18, and eight glycopeptides were detected in the glycopeptide fraction enriched with the strategy from the digests of human immunoglobulin G, horseradish peroxidase and bovine ribonuclease B, respectively. In addition, the strategy also showed high glycosylation microheterogeneity coverage for the enrichment of human α1-acid glycoprotein glycopeptides. More than 170 glycopeptides covering all the glycosylation sites were detected in the enriched fraction. The revered-phase liquid chromatography depletion coupled with HILIC enrichment strategy by using Click OEG-CD matrix is expected to show more potential in further applications in glycosylation analysis.  相似文献   
79.
当前疫情线上教学重心正逐渐转移为如何优化线上课程。针对化学实验线上课程短于实验过程控制环节,而线下课程在时空、科教融合和课堂互动等存在一定的局限性的两难现状,我们以有机化学实验线上课程为例,介绍如何通过重建教案和重整课件、视频、虚拟仿真实验和MOOC等资源,对实验预习、直播课堂、实验过程控制和实验拓展等重要教学环节进行再设计,提高学生主动学习成效和促进科教融合的协同培养。  相似文献   
80.
It is reported for the first time the growth of urotropine (HMT) crystals by a semiopen physical vapour transport (SOPVT) technique. HMT crystals, approximately 1 cm3 in volume, are grown on a glass pedestal from solution-grown seeds. The final habit of the crystals is limited by rhomboedrical {110} faces which develop on an otherwise hemispherical shape. Preliminary X-ray diffraction investigations (rocking curves and topographs) point to a still non-homogeneous crystal structure, which very likely originates at the seed-crystal interface. However, in comparison with solution-grown samples, the best structural quality was observed in a SOPVT-grown sample.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号