全文获取类型
收费全文 | 4896篇 |
免费 | 853篇 |
国内免费 | 745篇 |
专业分类
化学 | 3181篇 |
晶体学 | 127篇 |
力学 | 277篇 |
综合类 | 78篇 |
数学 | 822篇 |
物理学 | 2009篇 |
出版年
2024年 | 11篇 |
2023年 | 79篇 |
2022年 | 105篇 |
2021年 | 154篇 |
2020年 | 207篇 |
2019年 | 187篇 |
2018年 | 186篇 |
2017年 | 210篇 |
2016年 | 235篇 |
2015年 | 236篇 |
2014年 | 256篇 |
2013年 | 364篇 |
2012年 | 449篇 |
2011年 | 444篇 |
2010年 | 361篇 |
2009年 | 374篇 |
2008年 | 402篇 |
2007年 | 334篇 |
2006年 | 298篇 |
2005年 | 248篇 |
2004年 | 178篇 |
2003年 | 161篇 |
2002年 | 197篇 |
2001年 | 175篇 |
2000年 | 125篇 |
1999年 | 87篇 |
1998年 | 52篇 |
1997年 | 37篇 |
1996年 | 47篇 |
1995年 | 31篇 |
1994年 | 38篇 |
1993年 | 30篇 |
1992年 | 27篇 |
1991年 | 29篇 |
1990年 | 26篇 |
1989年 | 11篇 |
1988年 | 13篇 |
1987年 | 9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6494条查询结果,搜索用时 93 毫秒
141.
用CoMFA和HQSAR两种QSAR方法研究了50个乙内酰脲类分子的定量构效关系.本研究从构象搜索所得的低能结构出发构建化合物分子的构象, 建立CoMFA模型,并进行了全空间搜索. HQSAR本质上是一种二维的QSAR方法,与CoMFA方法相比,该方法在数据处理方面,比CoMFA方法快捷,并且可重复性好.两种方法均得到了较好分析结果, CoMFA的交叉验证相关系数q2 值为0.815, HQSAR的q2值为0.893.这些方程有力地说明了该类分子在(R,R)-N-3,5-dinitrobenzoyl-1,2-diamine型手性固定相上拆分过程中的影响因素,对今后类似拆分的实验研究提供了理论支持. 相似文献
142.
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
143.
144.
145.
纳秒强激光场中苯电离产生高价离子的研究 总被引:2,自引:0,他引:2
用25 ns脉冲Nd-YAG 532 nm的激光,在1010~1011 W•cm-2的光场强度下,利用飞行时间质谱对He、 N2、Ar载气条件下苯的激光电离过程进行了研究.发现当利用氩作为载气时,除观察到C2+、C2H2+、C3H3+、C6H6+离子外,还观察到很强的Cq+(q=1~3)高价离子.这些离子都有很高的平动能, C2+的最可几平动能为12.9 eV, C3+为37.5 eV.通过改变载气种类和压力及在不同光场强度条件下的实验,可以认为这些高价离子来源于含苯团簇的库仑爆炸过程. 相似文献
146.
Caignan GA Deshmukh R Wilks A Zeng Y Huang HW Moënne-Loccoz P Bunce RA Eastman MA Rivera M 《Journal of the American Chemical Society》2002,124(50):14879-14892
The origin of the unusual regioselectivity of heme oxygenation, i.e. the oxidation of heme to delta-biliverdin (70%) and beta-biliverdin (30%), that is exhibited by heme oxygenase from Pseudomonas aeruginosa (pa-HO) has been studied by (1)H NMR, (13)C NMR, and resonance Raman spectroscopies. Whereas resonance Raman indicates that the heme-iron ligation in pa-HO is homologous to that observed in previously studied alpha-hydroxylating heme oxygenases, the NMR spectroscopic studies suggest that the heme in this enzyme is seated in a manner that is distinct from that observed for all other alpha-hydroxylating heme oxygenase enzymes for which a structure is known. In pa-HO, the heme is rotated in-plane approximately 110 degrees, so the delta-meso-carbon of the major orientational isomer is located within the HO-fold in the place where the alpha-hydroxylating enzymes typically place the alpha-meso-carbon. The unusual heme seating displayed by pa-HO places the heme propionates so that these groups point in the direction of the solvent-exposed heme edge and appears to originate in large part from the absence of stabilizing interactions between the polypeptide and the heme propionates, which are typically found in alpha-hydroxylating heme oxygenase enzymes. These interactions typically involve Lys-16 and Tyr-112, in Neisseriae meningitidis HO, and Lys-16 and Tyr-134, in human and rat HO-1. The corresponding residues in pa-HO are Asn-19 and Phe-117, respectively. In agreement with this hypothesis, we found that the Asn-19 Lys/Phe-117 Tyr double mutant of pa-HO exists as a mixture of molecules exhibiting two distinct heme seatings; one seating is identical to that exhibited by wild-type pa-HO, whereas the alternative seating is very similar to that typical of alpha-hydroxylating heme oxygenase enzymes and is related to the wild-type seating by approximately 110 degrees in-plane rotation of the heme. Furthermore, each of these heme seatings in the pa-HO double mutant gives rise to a subset of two heme isomeric orientations that are related to each other by 180 degrees rotation about the alpha-gamma-meso-axis. The coexistence of these molecules in solution, in the proportions suggested by the corresponding area under the peaks in the (1)H NMR spectrum, explains the unusual regioselectivity of heme oxygenation observed with the double mutant, which we found produces alpha- (55%), delta- (35%), and beta-biliverdin (10%). Alpha-biliverdin is obtained by oxidation of the heme seated similar to that of alpha-hydroxylating enzymes, whereas beta- and delta-biliverdin are formed from the oxidation of heme seated as in wild-type pa-HO. 相似文献
147.
148.
Ke Jian Liu Jin Jie Jiang Li Li Ji Xianglin Shi Harold M. Swartz 《Research on Chemical Intermediates》1996,22(5):499-509
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
149.
本文研究了十七种2-芳基吲哚(1a-1q)在甲醇-乙酸介质中的亚甲基蓝(MB)敏化光氧化反应, 发现有十五种吲哚(1a-1o)以85%-95%的产率给出2,2'-二芳基-[2,3'-联-1H-吲哚]-3(2H)-酮(2a-2o), 而2-(4-硝基苯基]吲哚(1p)和2-联苯基吲哚(1q)则分别生成2-甲氧基-2-(4-硝基苯基)-1,2-二氢-3H-吲哚-3-酮(7p)和2-联苯基-4H-3,1-苯并恶嗪-4-酮(11q), 其中7p在分离过程中失去甲醇分子给出2-(4-硝基苯基)-3H-吲哚-3-酮(10p)。 相似文献
150.
磺化丁基橡胶离聚体在混合溶剂中的聚集行为 总被引:1,自引:0,他引:1
用顺磁共振(ESR)谱和粘度法考察了磺化丁基橡胶离聚体在二甲苯/正己醇混合溶剂中的聚集行为.ESR谱表明离聚体的离子基团发生聚集,其聚集程度受极性共溶剂(正己醇)的影响.粘度考察表明,在不同的浓度时离子基团有不同的聚集形式,低浓度时以分子内聚集为主,高浓度时以分子间聚集为主.离聚体的聚集度(DA)与浓度(c)的关系可用经验式DA=Aexp(kc2)表示,其中A、k为常数.k值反映聚集度受浓度影响的程度,醇含量增大时k值减小,这是因为醇对离子的溶剂化作用导致离子聚集的倾向减小. 相似文献