全文获取类型
收费全文 | 13295篇 |
免费 | 913篇 |
国内免费 | 1443篇 |
专业分类
化学 | 9309篇 |
晶体学 | 26篇 |
力学 | 692篇 |
综合类 | 224篇 |
数学 | 3242篇 |
物理学 | 2158篇 |
出版年
2024年 | 28篇 |
2023年 | 124篇 |
2022年 | 285篇 |
2021年 | 282篇 |
2020年 | 326篇 |
2019年 | 292篇 |
2018年 | 279篇 |
2017年 | 337篇 |
2016年 | 378篇 |
2015年 | 378篇 |
2014年 | 474篇 |
2013年 | 688篇 |
2012年 | 830篇 |
2011年 | 549篇 |
2010年 | 532篇 |
2009年 | 647篇 |
2008年 | 742篇 |
2007年 | 799篇 |
2006年 | 729篇 |
2005年 | 680篇 |
2004年 | 591篇 |
2003年 | 543篇 |
2002年 | 684篇 |
2001年 | 489篇 |
2000年 | 453篇 |
1999年 | 439篇 |
1998年 | 444篇 |
1997年 | 351篇 |
1996年 | 375篇 |
1995年 | 311篇 |
1994年 | 242篇 |
1993年 | 235篇 |
1992年 | 204篇 |
1991年 | 145篇 |
1990年 | 119篇 |
1989年 | 117篇 |
1988年 | 80篇 |
1987年 | 61篇 |
1986年 | 64篇 |
1985年 | 54篇 |
1984年 | 41篇 |
1983年 | 25篇 |
1982年 | 44篇 |
1981年 | 47篇 |
1980年 | 28篇 |
1979年 | 29篇 |
1978年 | 20篇 |
1977年 | 6篇 |
1976年 | 11篇 |
1973年 | 6篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
91.
92.
M. A. Massiah V. Saraswat H. F. Azurmendi A. S. Mildvan 《Journal of Molecular Structure》2004,700(1-3):247-254
The MutT pyrophosphohydrolase from E. coli (129 residues) catalyzes the hydrolysis of nucleoside triphosphates (NTP), including 8-oxo-dGTP, by substitution at Pβ, to yield NMP and pyrophosphate. The product, 8-oxo-dGMP is an unusually tight binding, slowly exchanging inhibitor with a KD=52 nM, (ΔG°=−9.8 kcal/mol) which is 6.1 kcal/mol tighter than the binding of dGMP (ΔG°=−3.7 kcal/mol). The higher affinity for 8-oxo-dGMP results from a more favorable ΔHbinding (−32 kcal/mol) despite an unfavorable −TΔS°binding (+22 kcal/mol). The solution structure of the MutT–Mg2+-8-oxo-dGMP complex shows a narrowed, hydrophobic nucleotide-binding cleft with Asn-119 and Arg-78 among the few polar residues. The N119A, N119D, R78K and R78A single mutations, and the R78K+N119A double mutant all showed largely intact active sites, on the basis of small changes in the kinetic parameters of dGTP hydrolysis and in 1H–15N HSQC spectra. However, the N119A mutation profoundly weakened the active site binding of 8-oxo-dGMP by 4.3 kcal/mol (1650-fold). The N119D mutation also weakened 8-oxo-dGMP binding but only by 2.1 kcal/mol (37-fold), suggesting that Asn-119 functioned both as a hydrogen bond donor to C8=O, and a hydrogen bond acceptor from N7H of 8-oxo-dGMP, while aspartate at position −119 functioned as an acceptor of a single hydrogen bond. Much smaller weakening effects (0.3–0.4 kcal/mol) on the binding of dGMP and dAMP were found, indicating specific hydrogen bonding of Asn-119 to 8-oxo-dGMP. While formation of the wild type MutT–Mg2+-8-oxo-dGMP complex slowed the backbone NH exchange rates of 45 residues distributed throughout the protein, the same complex of the N119A mutant slowed the exchange rates of only 11 residues at or near the active site, indicating an increase in conformational flexibility of the N119A mutant. The R78K and R78A mutations weakened the binding of 8-oxo-dGMP by 1.7 and 1.1 kcal/mol, respectively, indicating a lesser role of Arg-78 than of Asn-119 in the selective binding of 8-oxo-dGMP, likely donating a single hydrogen bond to its C6=O. The R78K+N119A double mutant weakened the binding of 8-oxo-dGMP (KIslope=3.1 mM) by 6.5±0.2 kcal/mol which overlaps, within error with the sum of the effects of the two single mutants (6.0±0.3 kcal/mol). Such additive effects of the two single mutants in the double mutant are most simply explained by the independent functioning of Asn-119 and Arg-78 in the binding of 8-oxo-dGMP. Independent functioning of these two residues in nucleotide binding is consistent with their locations in the MutT–Mg2+-8-oxo-dGMP complex, on opposite sides of the active site cleft, with a distance of 8.4±0.5 Å between their side chain nitrogens. 相似文献
93.
比光谱-导数吸光光度法及其应用与进展 总被引:1,自引:1,他引:1
综述了比光谱-导数吸光光度法的基本原理、主要试验条件的选择及其在多组分混合物同时测定中的应用与进展。全文共引用了参考文献50篇。 相似文献
94.
95.
二安替比林(3,4—二甲氧基)苯基甲烷光度法测定茶叶中锰 总被引:8,自引:0,他引:8
在碱性介质中,加热时空气氧化Mn为Mn,Mn与二安替比林苯基甲烷反应生成橙色产物,吐温20和乳酸起到协同增敏作用,λmax=460nm,ε=7.8×10^4L.mol^-1.cm^-1,锰量在0-12μg/25ml范围内符合比尔定律。 相似文献
96.
用统计模拟分光光度法测定复方消咳新片4个组分含量。按均匀设计表制备合成样品,绘制溶液的UV-VIS吸收曲线,获得有限但足够的实验数据,用逐步回归法构造反映该复方制剂组分在灵敏波长的吸光度-组分含量经验关系的“最优”数学模型,用改进单纯形法寻优,求出未知样品的各组分含量。磺胺甲基异恶唑、甲氧苄胺嘧啶、盐酸溴已新、枸橼酸维静宁的回收率分别为1003%、1004%、999%、990%,标准差分别为091%、14%、12%、39%。 相似文献
97.
Two greener procedures for flow-injection spectrophotometric determination of nitrite in natural waters were developed and critically compared. Replacement of toxic reagents, waste minimization and treatment were exploited to attend the standards of clean chemistry. The flow system was designed with solenoid micro-pumps in order to minimize reagent consumption and waste generation. The first procedure is based on the Griess diazo-coupling reaction with sulfanilamide and N-(1-naphthyl)ethylenediamine (NED) yielding an azo dye, followed by photodegradation of the low amount of waste generated based on the photo-Fenton reaction. The second procedure is based on the formation of iodine from nitrite and iodide in acid medium in order to avoid the use of toxic reagents. For Griess method, linear response was achieved up to 1.0 mg L− 1, described by the equation A = − 0.007 + 0.460C (mg L− 1), r = 0.999. The detection limit was estimated as 8 μg L− 1 at the 99.7% confidence level and the coefficient of variation was 0.8% (n = 20). The sampling rate was estimated as 108 determinations per hour. The consumption of the most toxic reagent (NED) is reduced 55-fold and 20-fold in comparison to batch method and flow injection with continuous reagent addition, respectively. A colorless residue was obtained by in-line photodegradation with reduction of 87% of the total organic carbon content. The results obtained for natural water samples were in agreement with those achieved by the reference method at the 95% confidence level. For the nitrite–iodide method, linear response was observed up to 2.0 mg L− 1, described by the equation A = − 0.024 + 0.148C (mg L− 1), r = 0.999. The detection limit was estimated as 25 μg L− 1 at the 99.7% confidence level and the coefficient of variation was 0.6% (n = 20). The sampling rate was estimated as 44 determinations per hour. Despite avoiding the use of toxic reagents, the nitrite–iodide method presented worst performance in terms of selectivity and sensitivity. 相似文献
98.
双波长分光光度法同时测定岩石矿物中的微量金和钯 总被引:2,自引:0,他引:2
本文提出以硫代米蚩酮为显色剂,用双波长分光光度法同时测定岩石矿物中的微量金和钯的方法,消除了测定金钯的相互干扰,该方法简便,快速,选择性好,用于矿石样品中金和钯的测定,结果满意。 相似文献
99.
过氧化物模拟酶在介体型生物传感器方面应用初探 总被引:2,自引:0,他引:2
meso-四(4-磺基苯)卟啉锰(Ⅲ)作为过氧化物模拟酶可催化H_2O_2与K_4Fe(CN)_6反应。电流响应与H_2O_2浓度在3.0×10~(-4)~1.0×10~(-3)mol/L范围内呈线性关系。重现性和回收率良好。抗坏血酸和DL-半胱氨酸干扰严重。 相似文献
100.
动力学分光光度法测定痕量硫氰酸根的研究 总被引:11,自引:1,他引:11
利用SCN~-对溴酸钾氧化罗丹明B反应的抑制作用。建立了动力学光度法测定痕量SCN~-的新方法。检出限为0.30ng SCN~-/ml,测定范围为0.30~8.3ngSCN~-/ml.应用于吸烟者与不吸烟者尿中SCN~-的测定。结果较为满意。 相似文献