全文获取类型
收费全文 | 74054篇 |
免费 | 6669篇 |
国内免费 | 5941篇 |
专业分类
化学 | 11022篇 |
晶体学 | 963篇 |
力学 | 9760篇 |
综合类 | 567篇 |
数学 | 14732篇 |
物理学 | 13476篇 |
综合类 | 36144篇 |
出版年
2024年 | 203篇 |
2023年 | 706篇 |
2022年 | 1197篇 |
2021年 | 1339篇 |
2020年 | 1624篇 |
2019年 | 1433篇 |
2018年 | 1475篇 |
2017年 | 1995篇 |
2016年 | 2225篇 |
2015年 | 2196篇 |
2014年 | 3617篇 |
2013年 | 4121篇 |
2012年 | 4410篇 |
2011年 | 4866篇 |
2010年 | 3917篇 |
2009年 | 4445篇 |
2008年 | 4192篇 |
2007年 | 4917篇 |
2006年 | 4270篇 |
2005年 | 4050篇 |
2004年 | 3577篇 |
2003年 | 3276篇 |
2002年 | 2895篇 |
2001年 | 2443篇 |
2000年 | 2205篇 |
1999年 | 2026篇 |
1998年 | 1789篇 |
1997年 | 1621篇 |
1996年 | 1430篇 |
1995年 | 1217篇 |
1994年 | 1116篇 |
1993年 | 994篇 |
1992年 | 939篇 |
1991年 | 792篇 |
1990年 | 740篇 |
1989年 | 622篇 |
1988年 | 548篇 |
1987年 | 387篇 |
1986年 | 208篇 |
1985年 | 145篇 |
1984年 | 118篇 |
1983年 | 53篇 |
1982年 | 70篇 |
1981年 | 50篇 |
1980年 | 27篇 |
1979年 | 43篇 |
1978年 | 31篇 |
1977年 | 37篇 |
1976年 | 13篇 |
1957年 | 11篇 |
排序方式: 共有10000条查询结果,搜索用时 57 毫秒
991.
A new catalytic kinetic spectrophotometric method has been developed for the determination of trace amount of manganese (II) in nonionic microemulsion medium. The method is based on the catalytic effect of manganese (II) on the oxidation of dahlia violet by potassium periodate with nitrilotriacetic acid as an activitor in the presence of nonionic microemulsion. Under the optimum conditions, the calibration graph is linear in the range of 0.0004-0.0056 μg ml−1 of manganese (II) at 580 nm. The detection limit achieved is 3.75×10−5 μg ml−1. Manganese (II) in foodstuff samples was determined with satisfactory results. 相似文献
992.
以99.995% Ce(NO3)3和强碱性阴离子交换树脂为原料,采用离子交换-双氧水氧化法合成制备出纳米CeO2晶体。并就离子交换反应中的Ce3+浓度、树脂加入速度和离子交换温度及H2O2加入速度等条件对CeO2粒径的影响进行了探讨,得出了离子交换-双氧水氧化法制备纳米CeO2晶体的最佳工艺条件。FTIR、TEM分析表明,离子交换法无需对合成的Ce(OH)3溶胶进行洗涤即可去除NO3-、CO32-等阴离子杂质,并用H2O2将该溶胶氧化,经真空干燥可制得粒径分布均匀,平均晶粒尺寸约3 nm,高纯度的CeO2粉体。 相似文献
993.
L. Leite D. Jansone M. Fleisher H. Kazhoka J. Popelis N. Veretennikova I. Shestakova I. Domracheva E. Lukevics 《Chemistry of Heterocyclic Compounds》2004,40(6):715-724
The respective 4-(arylvinyl)lactones and compounds of the Michael adduct type were synthesized by the condensation of substituted benzaldehydes with 3-cyano-4,6,6-trimethyl-5,6-dihydro-2-pyranone in the presence of catalytic amounts of sodium hydroxide. It was shown by the semiempirical AM1 method that the indicated products can be formed through one and the same intermediate compound. Some of the synthesized phenylvinyl-5,6-dihydro-2-pyranones have a cytotoxic effect, and this corresponds to the prognosis of the OREX expert system. 相似文献
994.
在干燥氮气气氛下,以无水乙醇为溶剂,制备了低水合氯化钕与二乙氨基荒酸二乙铵(D-DDC)配合物,确定其组成为Et2NH2[Nd(S2CNEt2)4].单晶结构分析表明,配合物中4个二乙氨基荒酸根各通过2个硫原子与钕离子成键形成八配位十二面体阴离子,并与二乙铵阳离子形成缔合型分子.晶体属单斜晶系,空间群P21/n,a=1.37517(14)nm,b=2.1146(2)nm,c=1.44641(15)nm,β=102.028(2)°,Z=4.用微量热法测定了298.15K下水合氯化钕和D-DDC在无水乙醇中的溶解焓及二乙氨基荒酸钕液相生成反应焓变分别为(-17.89±0.096),(50.280±0.151)和(-10.116±0.065)kJ/mol,求得固相生成反应焓变. 相似文献
995.
Usachev N. Ya. Belanova E. P. Krukovsky I. M. Kanaev S. A. Atal"yan O. K. Kazakov A. V. 《Russian Chemical Bulletin》2003,52(9):1940-1949
Thermal transformations in systems formed by interaction of Zn and Na nitrates with Y, X, and A zeolites were studied by TG—DTA technique. Temperature regions of existence of adsorbed water, water of crystallization, and decomposition of NO3
– anion were determined. These intervals depend on the composition, structure, method of preparation, and pre-treatment conditions of zeolite systems. The extent of NO3
– decomposition depends not only on the zinc and sodium content but also on the presence of ammonia involved in NO3
– reduction. The zeolite matrix strongly stabilizes the occluded NO3
– anions. A portion of zinc oxide formed by zinc nitrate decomposition is probably localized inside the zeolite cavities as the [Zn—O—(ZnO)
n
—Zn]2+ particles. The latter compensate charges of the isolated [AlO4]– tetrahedra. 相似文献
996.
The bimolecular single collision reaction potential energy surface of an isocyanate NCO radical with a ketene CH2CO molecule was investigated by means of B3LYP and QCISD(T) methods. The computed results indicate that two possible reaction channels exist on the surface. One is an addition-elimination reaction process, in which the CH2CO molecule is attacked by the nitrogen atom at its methylene carbon atom to lead to the formation of the intermediate OCNCH2CO followed by a C-C rupture channel to the products CH2NCO+CO. The other is a direct hydrogen abstraction channel from CHzCO by the NCO radical to afford the products HCCO+HNCO. Because of a higher barrier in the hydrogen abstraction reaction than in the addition-elimination reaction, the direct hydrogen abstraction pathway can only be considered as a secondary reaction channel in the reaction kinetics of NCO+ CH2CO. The predicted results are in good agreement with previous experimental and theoretical investigations. 相似文献
997.
采用XRD表征了水蒸气和磷联合改性的HZSM-5沸石分子筛的结构.通过NH3-TPD和N2吸附脱附研究了样品的酸性和比表面.采用正庚烷的裂化反应研究了样品的裂化活性,研究结果表明,磷改性样品与母体样品相比,经过水蒸气处理后显示出较高的酸量和正庚烷裂化活性.上述结果首次用模型簇和计算量子化学方法进行了解释.采用Gaussian94软件包和PM3半经验量子化学方法对模型簇进行了全优化和频率分析.计算结果显示磷改性后样品的脱铝补硅反应热大于母体样品脱铝补硅反应热,从而显示出磷对骨架的稳定化作用. 相似文献
998.
2-(8-羟基喹啉-5-磺酸-7-偶氮)-1,8-二羟基-3,6-萘二磺酸与牛血清白蛋白的相互作用 总被引:5,自引:0,他引:5
用平衡透析法和分光光度法研究了 2 (8 羟基喹啉 5 磺酸 7 偶氮 ) 1,8 二羟基 3,6 萘二磺酸与牛血清白蛋白 (BSA)在酸性溶液中的结合反应 ,认为 8Q5SAC与BSA之间的结合力是以静电引力为主的非共键作用力 ,并探讨了其结合模型。在 2 98K下 ,测得这一反应的最大结合数为 35~ 40 ,结合常数为 6 .1× 10 5L mol。还研究了溶液基本条件如酸度和离子强度等对 8Q5SAC与牛血清白蛋白分子复合物形成的影响 ,在pH =3.34条件下 ,标准工作曲线的线性范围为 0 .2 0~ 46 .90mg L。 相似文献
999.
The static polarizabilities and the second-order hyperpolarizabilities of a series of tri-nuclear metal cluster models MS4(M′PPh3)2(M′PPh3)(M=Mo,W;M′=Cu,Ag,Au)have been calculated within the first-principle theoretical framework. The model clusters have two fragments of rhombic units and it is the charge ransfer from one of these moieties to the other that is responsible for nonlinear optical property. This kind of electronic delocaization, differentiated from that of planar π-system, is very interesting and is worthy for further investigation. 相似文献
1000.
The approximate expressions have been obtained to calculate the electrical double layer energy and force between two spherical colloidal particles based on the improved Derjaguin approximation. Results for identical spheres interacting under constant surface potential, constant surface charge are given. Comparison of present results with numerical results calculated by Carnie and Chan is made. The expressions are found to work quite well for the constant surface potential case, and for the constant charge case, we make correction for the expressions. The results given are satisfactory providedkh0.4. 相似文献