全文获取类型
收费全文 | 58536篇 |
免费 | 13701篇 |
国内免费 | 4528篇 |
专业分类
化学 | 56786篇 |
晶体学 | 600篇 |
力学 | 2429篇 |
综合类 | 282篇 |
数学 | 4729篇 |
物理学 | 11939篇 |
出版年
2024年 | 69篇 |
2023年 | 508篇 |
2022年 | 827篇 |
2021年 | 1088篇 |
2020年 | 2226篇 |
2019年 | 3475篇 |
2018年 | 1810篇 |
2017年 | 1418篇 |
2016年 | 4433篇 |
2015年 | 4654篇 |
2014年 | 4739篇 |
2013年 | 5764篇 |
2012年 | 5053篇 |
2011年 | 4475篇 |
2010年 | 4312篇 |
2009年 | 4237篇 |
2008年 | 3750篇 |
2007年 | 3022篇 |
2006年 | 2705篇 |
2005年 | 2637篇 |
2004年 | 2354篇 |
2003年 | 2012篇 |
2002年 | 2667篇 |
2001年 | 1976篇 |
2000年 | 1819篇 |
1999年 | 885篇 |
1998年 | 506篇 |
1997年 | 427篇 |
1996年 | 428篇 |
1995年 | 373篇 |
1994年 | 363篇 |
1993年 | 267篇 |
1992年 | 274篇 |
1991年 | 231篇 |
1990年 | 201篇 |
1989年 | 167篇 |
1988年 | 105篇 |
1987年 | 95篇 |
1986年 | 89篇 |
1985年 | 85篇 |
1984年 | 45篇 |
1983年 | 51篇 |
1982年 | 45篇 |
1981年 | 24篇 |
1980年 | 17篇 |
1979年 | 8篇 |
1977年 | 5篇 |
1975年 | 7篇 |
1969年 | 4篇 |
1957年 | 8篇 |
排序方式: 共有10000条查询结果,搜索用时 46 毫秒
991.
镧的植物防病效果及其生物学效应 总被引:4,自引:1,他引:4
通过灭菌土接种Rhizoctonia solani以及混合接菌Rhizoctonia solani和Fusarium solani进行盆栽试验,分别研究了镧浸种处理对高羊茅及板蓝根出苗、生长发育的影响。结果表明,镧浸种能明显地减少病原菌的侵染,对由其所造成的种腐、芽腐及根腐等有显著的防治效果,提高了板蓝根和高羊茅种子的出苗率。同时,镧浸种在适当的浓度范围内,还能显著地促进植物的生长发育,生物量明显增加。利用盆栽水稻试验研究了稀土镧对水稻纹枯菌(Rhizoctonia solani)的毒力,测定结果表明,镧喷施于水稻植株上对水稻纹枯病有明显的防治效果,且在活体条件下,喷施镧后1和7 d对水稻纹枯菌(Rhizoctonia solani)的有效中浓度分别为128.7和128.1 mg.L-1,均明显低于离体条件下的有效中浓度(171.9 mg.L-1)。 相似文献
992.
Hu J Chekmenev EY Gan Z Gor'kov PL Saha S Brey WW Cross TA 《Journal of the American Chemical Society》2005,127(34):11922-11923
Recently available ultrahigh magnetic fields offer new opportunities for studies of quadrupole nuclei in biological solids because of the dramatic enhancement in sensitivity and resolution associated with the reduction of second-order quadrupole interactions. Here, we present a new approach for understanding the function and energetics of ion solvation in channels using solid-state 17O NMR spectroscopy of single-site 17O-labeled gramicidin A. The chemical shift and quadrupole coupling parameters obtained in powder samples of lyophilized material are similar to those shown in the literature for carbonyl oxygens. In lipid bilayers, it is found that the carbonyl 17O anisotropic chemical shift of Leu10, one of the three carbonyl oxygens contributing to the ion binding site in gramicidin A, is altered by 40 ppm when K+ ion binds to the channel, demonstrating a high sensitivity to such interactions. Moreover, considering the large breadth of the carbonyl 17O chemical shift (>500 ppm), the recording of anisotropic 17O chemical shifts in bilayers aligned with respect to magnetic field B0 offers high-quality structural restraints similar to 15N and 13C anisotropic chemical shifts. 相似文献
993.
原位氧化还原沉淀水热合成法制备LixMn2O4尖晶石 总被引:3,自引:0,他引:3
Li xMn2O4尖晶石是新一代的锂离子二次电池正极材料 [1], 其合成方法对材料的电化学性质影响很大[2].常规合成大多采用高温固相反应法, 此法具有反应温度高, 反应时间长, 容易产生缺陷和产物不纯净等缺点, 导致所合成的锂离子二次电池正极材料的性能较差. 目前用水热合成法制备电池正极材料Li xMn2O4尖晶石尚未见文献报道. 本文在常规水热合成法的基础上采用原位氧化还原沉淀水热合成法 [3]制备前驱物, 该法合成条件更温和, 而且使材料的综合性能得到了改善和提高. 相似文献
994.
Cai H Chen T Wang X Schultz AJ Koetzle TF Xue Z 《Chemical communications (Cambridge, England)》2002,(3):230-231
Reactions of Ta(NMe2)5 with D2SiR'Ph (R' = Me, Ph) were found to give a dideuteride eta 2-imine complex (Me2N)3Ta(mu-D)2(mu-N-eta 2-N,C-CH2NMe)Ta(NMe2)3(1-d2) through C-H activation of an amide ligand via beta-H abstraction, and the structure of 1 was confirmed by single crystal neutron and X-ray diffraction. 相似文献
995.
The chiral phosphine‐oxazoline ligands 3 and 4 bearing 4‐alkoxymethyl substituents on the oxazoline ring with (R)‐configuration were prepared from L‐serine methyl ester in 66% and 33% yields, respectively. Along this synthetic pathway, the β‐hydroxylamides derived from L‐serine methyl ester and 2‐halobenzoyl chlorides were expediently converted to the corresponding oxazolines by using diethylaminosulfur trifluoride as the activation agent. Potassium diphenylphosphide was the reagent of choice for replacing the bromine atom on the phenyl ring, giving the desired oxazoline‐phosphine ligands 3 and 4 . Together with [Pd(η3‐allyl)Cl]2, ligands 3 and 4 induced an enantioselective allylic substitution reaction of 1,3‐diphenyl‐2‐pro‐penyl acetate by dimethyl malonate. Although ligands 3 and 4 exhibit the (R)‐configuration, differing from the (S)‐configuration of Pfaltz‐Helmchen‐Williams phosphine‐oxazoline ligands, all these ligands led to the same enantiotopic preference in the allylic substitution reaction. To facilitate the recovery and reuse of the phosphine‐oxazoline ligand, immobilization on Merrifield resin was attempted, albeit in low loading. 相似文献
996.
Xiufang Xu Yumei Xing Xia Yang Guichang Wang Zunsheng Cai Zhenfeng Shang Yinming Pan Xuezhuang Zhao 《International journal of quantum chemistry》2005,101(2):160-168
A total of eight possible isomers of C50O, an oxide of fullerene C50 (D5h), have been investigated by B3LYP/3‐21G calculations. The isomer, which has an annulene‐like structure with oxygen bridging across a [5,6] type C? C bond at the site between the pole and the equatorial belt, is found being the ground state of C50O. Four isomers are relatively more stable and the energy differences between them are not large. This result indicates that more than one C50O isomer will coexist once C50O is synthesized. The relative stabilities of the C50O isomers may be determined mainly by the strain release and by the formation of the cyclic phenylene substructure at the equatorial belt of the cage. The calculated nucleus independent chemical shifts (NICS) of the C50O isomers will be useful because from them one can expect outstanding NMR properties that can lead to their identification and characterization. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
997.
Yong‐Min Lee Yoon‐Bo Shim Seung Jae Lee Sung Kwon Kang Sung‐Nak Choi 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(12):o733-o734
The structure of the title compound, C15H27N2+·ClO4?, consists of a monoprotonated sparteinium cation and a perchlorate anion. The two tertiary N atoms of the cation, one perchlorate O atom and a H atom form a bifurcated hydrogen bond, the four hydrogen‐bonding atoms being nearly in the same plane. 相似文献
998.
在非质子极性溶剂-二甲基乙酰胺中,室温下用碘乙烷与C_1—C_6脂肪酸及乳酸的四甲基铵盐反应制备各酸相应的乙酯。乙酯在15%的邻苯二甲酸二壬酯与6%的土温-80混合固定液填充柱上获得满意分离。用本法测定饮料酒中的低沸点有机酸含量,简便、快速、准确。 相似文献
999.
1000.
应用等离子体发射光谱法(ICP-AES)对精神分裂症急性期男病人48例,女病人30例和慢性期男病人50例,女病人30例,检测头发中Zn、Fe、Cu、Ca、Mn5种元素,并与158名男女正常人作对照,发现无论是急性期还是慢性期,男女病人的Cu、Mn两元素的含量,均显著低于正常人(P<0.05~0.001). 相似文献