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   4459篇
  免费   768篇
  国内免费   714篇
化学   3032篇
晶体学   104篇
力学   224篇
综合类   65篇
数学   691篇
物理学   1825篇
  2024年   17篇
  2023年   81篇
  2022年   132篇
  2021年   164篇
  2020年   206篇
  2019年   179篇
  2018年   180篇
  2017年   181篇
  2016年   226篇
  2015年   210篇
  2014年   224篇
  2013年   325篇
  2012年   422篇
  2011年   407篇
  2010年   322篇
  2009年   322篇
  2008年   337篇
  2007年   288篇
  2006年   252篇
  2005年   211篇
  2004年   140篇
  2003年   146篇
  2002年   190篇
  2001年   153篇
  2000年   105篇
  1999年   85篇
  1998年   51篇
  1997年   37篇
  1996年   47篇
  1995年   34篇
  1994年   37篇
  1993年   30篇
  1992年   27篇
  1991年   28篇
  1990年   27篇
  1989年   9篇
  1988年   15篇
  1987年   13篇
  1986年   13篇
  1985年   8篇
  1984年   10篇
  1983年   9篇
  1982年   9篇
  1980年   2篇
  1977年   5篇
  1975年   2篇
  1974年   3篇
  1973年   5篇
  1972年   4篇
  1971年   4篇
排序方式: 共有5941条查询结果,搜索用时 15 毫秒
61.
Enol and keto tautomers of methyl 3-oxo pentanoate could be separated on a HP-5 capillary column. The chromatographic peaks were identified by examining characteristic mass ions arose from the corresponding enol and keto molecular ions. The study showed that the area percentage of enol tautomer is a function of temperature of the column. Treating the column as a reactor, the energy of activation for the on-column tautomerization could be extracted (35.1 kJ mol−1) by monitoring the loss of the enol tautomer, because the reaction is found to obey pseudo first-order kinetics. The enthalpy and the entropy changes (ΔH = −3.98 kJ mol−1, ΔS = −7.89 J K−1mol−1) for the enol-to-keto reaction in the stationary phase were also obtained.  相似文献   
62.
Application of the spin trapping technique in intact animals requires an understanding of the stability and distribution of the spin traps and their spin adducts in vivo. We studied the stability of DMPO in vivo in mice using HPLC and the stability of spin adducts of DMPO by EPR in plasma, whole blood, peritoneal fluid, and homogenized heart tissue of the rat. At 15 minutes after intraperitoneal injection DMPO had similar concentrations in the liver, heart, and blood of the mice and 40% remained in the organs 2 hours after the injection. In contrast, the spin adduct DMPO-OH was short lived, with a half-life of 3.0 minutes in plasma, and was not detectable 1 minute after formation in whole blood and homogenized heart tissue. The carbon centered spin adduct DMPO-CH(OH)CH3 was more stable, having half-lives of 16, 11, 3.6, and 0.79 minutes in plasma, peritoneal fluid, whole blood, and homogenized heart tissue, respectively. The spin adduct DMPO-SO3 was sufficiently stable for the adduct to be observed directly from living mice.  相似文献   
63.
Recent advances on the deoximation reactions are reviewed in this review. It was shown that catalytic deoximation with molecular oxygen as the mild oxidant should be the developing trend of the reaction.  相似文献   
64.
Zhong H  Li N  Zhao F  Li KA 《Talanta》2004,62(1):37-42
A new protein determination method by enhanced Rayleigh light scattering (RLS) technique has been developed. In acid condition (pH=3.60), RLS of 1,2-dihydroxyanthraquinone-3-sulfonate (Alizarin Red S) can be greatly enhanced by addition of proteins, resulting in two characteristic peaks, 360 and 505 nm, respectively. The new protein assay is based on the RLS enhancement and spectrum change. The optimum condition for the reaction was investigated. The linear range is 0.20-24.9 μg ml−1 for BSA and 0.20-15.5 μg ml−1 for HSA. The detection limits (S/N=3) are 9.59 ng ml−1 for BSA and 9.51 ng ml−1 for HSA. The results of determination for human serum samples were comparable to those obtained by Bradford method. The binding stoichiometry was determined.  相似文献   
65.
Mesoporous titanium dioxide nanosized powder with high specific surface area and anatase wall was synthesized via hydrothermal process by using cetyltrimethylammonium bromide (CTAB) as surfactant-directing agent and pore-forming agent. The resulting materials were characterized by XRD, nitrogen adsorption, FESEM, TEM, and FT-IR spectroscopy. The as-synthesized mesoporous TiO2 nanoparticles have mean diameter of 17.6 nm with mean pore size of 2.1 nm. The specific surface area of the as-synthesized mesoporous nanosized TiO2 exceeded 430 m2/g and that of the samples after calcination at 600 degrees C still have 221.9 m2/g. The mesoporous TiO2 nanoparticles show significant activities on the oxidation of Rhodamine B (RB). The large surface area, small crystalline size, and well-crystallized anatase mesostructure can explain the high photocatalytic activity of mesoporous TiO2 nanoparticles calcined at 400 degrees C.  相似文献   
66.
A quantitative analysis method for penicillins including ampicillin (AmP), benzyl penicillin (BP), oxacillin (OA) and amoxycillin (AmO) is proposed that makes use of the totally internally reflected resonance light scattering (TIR-RLS) signal from the penicillin at the H2O/CCl4 interface in the presence of cetyltrimethylammonium bromide (CTMAB), and enables the pharmacokinetics of penicillin taken orally and excreted through urine to be monitored. Penicillin is coadsorbed with CTMAB at the H2O/CCl4 interface in neutral solution, resulting in the formation of ion associates that display greatly enhanced TIR-RLS signals (maximum at 368–372 nm). This enhanced TIR-RLS intensity was found to be proportional to the penicillin concentration over the range 0.2×10–6 to 2.2×10–6 mol L–1, with limits of determination (3) of 5.0×10–8 to 7.0×10–8 mol L–1. Pharmacokinetics studies performed using the present method show that the excretion of orally-taken ampicillin through urine has a half-time of 1.05 h and an excremental quantum over 8 h of 49.3%, respectively.  相似文献   
67.
具无限时滞的非自治捕食者-食饵系统的持久性   总被引:16,自引:0,他引:16  
王克 《数学学报》1997,40(3):321-332
本文采用新的方法研究了具无限时滞的非自治、非卷积的捕食者-食饵系统的持久性问题,得到了新的、有趣的结果。本文的结果包含已知的结果作为特例.  相似文献   
68.
硫酸酯化反应以分子结构中的羟基为反应位点,向有机分子中引入硫酸酯基,是一种有效改善天然产物水溶性的结构修饰途径[1]。有些药物因水溶性差,致使其在临床应用中存在一些问题,如生物利用度不高,服用量大,制成的片剂或胶囊体内吸收缓慢等。这类化合物经硫酸酯化后不但可以增加  相似文献   
69.
Advanced glycation end products (AGEs) are the compounds produced by non-enzymatic glycation of proteins, which are involved in diabetic-related complications. To investigate the potential anti-glycation activity of Myriocin (Myr), a fungal metabolite of Cordyceps, the effect of Myr on the formation of AGEs resulted from the glycation of bovine serum albumin (BSA) and the interaction between Myr and BSA were studied by multiple spectroscopic techniques and computational simulations. We found that Myr inhibited the formation of AGEs at the end stage of glycation reaction and exhibited strong anti-fibrillation activity. Spectroscopic analysis revealed that Myr quenched the fluorescence of BSA in a static process, with the possible formation of a complex (approximate molar ratio of 1:1). The binding between BSA and Myr mainly depended on van der Waals interaction, hydrophobic interactions and hydrogen bond. The synchronous fluorescence and UV-visible (UV-vis) spectra results indicated that the conformation of BSA altered in the presence of Myr. The fluorescent probe displacement experiments and molecular docking suggested that Myr primarily bound to binding site 1 (subdomain IIA) of BSA. These findings demonstrate that Myr is a potential anti-glycation agent and provide a theoretical basis for the further functional research of Myr in the prevention and treatment of AGEs-related diseases.  相似文献   
70.
The clinical application of gentamicin may lead to acute kidney injury (AKI), and the nephrotoxicity of gentamicin is related to the pathological mechanism of several oxidative and inflammatory cytokines. Plant-derived essential oils have good anti-inflammatory and antioxidant properties. This study aimed to clarify the protective effect of Amomum tsao-ko essential oils (AOs) on gentamicin-induced AKI in rats and its possible mechanism. The rat AKI model was induced by intraperitoneal injection of gentamicin. After 14 days of oral AO treatment, the renal function and pathological changes of the kidney tissues were evaluated, and the level of kidney tissue oxidative stress was detected. The content of inflammatory cytokines was measured by ELISA. The expression of ERK1/2, JNK1/2, p38, NF-κB, caspase-3, and Bax/Bcl-2 proteins were estimated by Western blot analysis. The results showed that taking AO reduced the contents of serum urea and creatinine in AKI rats and improve the pathological changes and oxidative stress of the kidney tissue in rats. At the same time, AO reduced inflammation and apoptosis during AKI by regulating the MAPK pathway. The data show that AO has a protective effect on the kidneys and may be a potential drug for treating kidney injury.  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