全文获取类型
收费全文 | 128796篇 |
免费 | 17975篇 |
国内免费 | 10878篇 |
专业分类
化学 | 61483篇 |
晶体学 | 915篇 |
力学 | 5746篇 |
综合类 | 520篇 |
数学 | 10131篇 |
物理学 | 37256篇 |
综合类 | 41598篇 |
出版年
2024年 | 582篇 |
2023年 | 2636篇 |
2022年 | 4024篇 |
2021年 | 4362篇 |
2020年 | 4393篇 |
2019年 | 3680篇 |
2018年 | 3509篇 |
2017年 | 3266篇 |
2016年 | 5013篇 |
2015年 | 5134篇 |
2014年 | 6594篇 |
2013年 | 7915篇 |
2012年 | 9337篇 |
2011年 | 9570篇 |
2010年 | 6744篇 |
2009年 | 6796篇 |
2008年 | 7356篇 |
2007年 | 6651篇 |
2006年 | 6025篇 |
2005年 | 5194篇 |
2004年 | 3998篇 |
2003年 | 3172篇 |
2002年 | 3041篇 |
2001年 | 2826篇 |
2000年 | 2750篇 |
1999年 | 4063篇 |
1998年 | 3711篇 |
1997年 | 3694篇 |
1996年 | 3549篇 |
1995年 | 3091篇 |
1994年 | 2685篇 |
1993年 | 2320篇 |
1992年 | 2037篇 |
1991年 | 1843篇 |
1990年 | 1558篇 |
1989年 | 1321篇 |
1988年 | 1049篇 |
1987年 | 735篇 |
1986年 | 543篇 |
1985年 | 342篇 |
1984年 | 166篇 |
1983年 | 123篇 |
1982年 | 101篇 |
1981年 | 58篇 |
1980年 | 42篇 |
1979年 | 15篇 |
1976年 | 1篇 |
1974年 | 1篇 |
1957年 | 31篇 |
1922年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 11 毫秒
861.
[reaction: see text] A highly diastereoselective acetate aldol reaction that uses a tert-leucine-derived thiazolidinethione auxiliary and dichlorophenylborane has been developed. The reaction proceeds in excellent yields and with high diastereoselectivities (drs range from 9.5:1 to >100:1). 相似文献
862.
Zhang Z Blom DA Gai Z Thompson JR Shen J Dai S 《Journal of the American Chemical Society》2003,125(25):7528-7529
One-dimensional (1D) magnetic nanomaterials have attracted much attention recently because of their applications in magnetic recording and spintronics. Nevertheless, it remains a challenge to prepare free-standing magnetic nanowires in high yield. This Communication reports the successful high-yield synthesis of an interesting 1D ferromagnetic CoPt alloy by direct decomposition of platinum acetylacetonate and cobalt carbonyl compound in ethylenediamine solvent through a solvothermal reaction. The CoPt alloy nanowires obtained have a tunable diameter of 10-50 nm and a length along the longitudinal axis of up to several microns, depending on crystallization temperature and reaction time. A unique formation mechanism involving coarsening and ripening under solvothermal conditions was discovered. This research opens new opportunities in synthesizing nanomaterials through low-temperature solvothermal processes. 相似文献
863.
The tetraamide ligand, DOTA-tetra(glycine ethyl ester), forms complexes with the lanthanide(III) cations that exist in solution predominantly as the square antiprism structure with single, slowly exchanging inner-sphere water molecule. Variable-temperature 1H and 17O NMR studies revealed that the bound water lifetimes in these complexes were sharply dependent upon the ionic radius of Ln3+ cation. A novel lanthanide-induced shift technique was used to unmask the bound water 17O resonance of SmL3+ and YL3+ complexes from the bulk water resonance. The bound water lifetime (tauM298) was approximately 800 mus in the EuL3+ complex but became much shorter (several microseconds) for Ln3+ cations with larger and smaller ionic radii. This demonstrates that water exchange is exquisitely fine-tuned in this macrocyclic tetraamide system and that a variety of Ln3+ complexes meet with the exchange requirement, Deltaomega*tauM >/= 1, necessary for an efficient MT agent. 相似文献
864.
Analytical methodologies for aluminium speciation in environmental and biological samples--a review 总被引:1,自引:0,他引:1
Bi SP Yang XD Zhang FP Wang XL Zou GW 《Fresenius' Journal of Analytical Chemistry》2001,370(8):984-996
It is recognized that aluminium (Al) is a potential environmental hazard. Acidic deposition has been linked to increased Al concentrations in natural waters. Elevated levels of Al might have serious consequences for biological communities. Of particular interest is the speciation of Al in aquatic environments, because Al toxicity depends on its forms and concentrations. In this paper, advances in analytical methodologies for Al speciation in environmental and biological samples during the past five years are reviewed. Concerns about the specific problems of Al speciation and highlights of some important methods are elucidated in sections devoted to hybrid techniques (HPLC or FPLC coupled with ET-AAS, ICP-AES, or ICP-MS), flow-injection analysis (FIA), nuclear magnetic resonance (27Al NMR), electrochemical analysis, and computer simulation. More than 130 references are cited. 相似文献
865.
A tetrasubstituted derivative of 1,4,7,10-tetraazacyclododecane with amide coordinating groups and extended noncoordinating phosphonate groups forms a complex with gadolinium(III) (shown in the picture) which contains one slowly exchanging inner-sphere water molecule (tau(M)=21 μs). The 20-MHz water proton relaxivity of the complex was found to be highly pH dependent. Protonation of the noncoordinating phosphonate groups appears to catalyze prototropic exchange of the bound water protons, thereby providing a mechanism for enhanced water contrast below pH 7. 相似文献
866.
A series of sterically demanding diporphyrins H2(por)-X-(por)H2 ligands that contain spacers (X) with different degrees of flexibility were synthesized from the trimesitylporphyrin derivatives 5-(4-hydroxyphenyl)-10,15,20-trimesitylporphyrin (TMP-OH)H2 (1a) and 5-(2,6-dimethyl-4-hydroxyphenyl)-10,15,20-trimesityl-porphyrin, (DMTMP-OH)H2 (1b). The monomeric porphyrins 1a,b, which have steric demands similar to that of tetramesitylporphyrin, (TMP)H2, and carry a hydroxyl functional group at the para position of one of the mesophenyl substituents, were constructed from reaction of pyrrole with two aromatic aldehydes by a mixed aldehyde condensation approach. The diporphyrins with alkyl diether tethers were obtained stepwise from reactions of the hydroxy functionalized porphyrins 1a,b with dibromides Br(CH2)nBr. The diporphyrin which contains a more rigid m-xylylene spacer, was made directly from reaction of 1b with alpha,alpha'-dibromo-m-xylene. Rhodium was inserted into the porphyrins using Rh2(CO)2Cl2 and converted to dimethyl complexes Me-Rh(Por)-X-(Por)Rh-Me. The dirhodium(II) derivatives .Rh(por)-X-(por)Rh.) were generated by photolysis of the dimethyl complexes and observed to occur as stable bimetalloradicals because the ligand steric demands prohibit Rh(II)-Rh(II) bonding. EPR spectra of the dirhodium(II) derivatives, triphenyl phospine adducts, and dioxygen complexes are reported. The kinetic advantage of bimetalloradical complexes for substrate reactions that have two metal-centered radicals in the transition state is demonstrated by reactions of dihydrogen with dirhodium(II) bimetalloradical complexes. 相似文献
867.
Most magnetorheological materials, composed of magnetic microparticles in a liquid, require significant amounts of magnetic particles and a large magnetic field to achieve the desired effects. Here, we report on a new type of magnetorheological materials consisting of small amounts of magnetic nanoparticles (0.8 wt %) but exhibiting large rheological change (i.e., a gel-sol transition) upon the application of a small magnetic field. We use self-assembly to create hybrid nanofibers, which consist of supramolecular hydrogelators and magnetic nanoparticles, as the matrices of the hydrogel. Localized in the nanofibers at a distance of 1-2 nm, the magnetic nanoparticles occupy a small volume fraction of the hydrogel, significantly enhancing the magnetic dipole interactions between them, which results in the large magnetoresponse. This strategy generates a hierarchical nanostructure and eliminates several drawbacks of the simple mixture of polymers with nanoparticles, and thus provides a new methodology that uses magnetic force to control the nanostructures and properties of soft materials. 相似文献
868.
Jiang Hu Wei‐Dong Zhang Yun‐Heng Shen Chuan Zhang Run‐Hui Liu Xi‐Ke Xu Bin Wang 《Helvetica chimica acta》2007,90(4):720-722
Two novel alkaloids, 4,5‐dihydroxy‐1‐methyl‐3‐oxo‐2‐(trichloromethyl)‐3H‐indolium chloride ( 1 ) and 4‐(2‐methoxyethyl)‐N,N‐dimethylbenzenamine ( 2 ), were isolated from the EtOH extract of the roots of Zanthoxylum nitidum. Their structures were identified on the basis of spectroscopic and mass‐spectrometric analyses. 相似文献
869.
J. Bates Q. Zhang L. Spiccia B. O. West 《Journal of Sol-Gel Science and Technology》1994,2(1-3):29-34
Two lead titanium oxyalkoxides with composition Pb2Ti4O2(O2CCH3)2(OC2H5)14 and Pb2Ti2O2(O2CCH3)2(OCH(CH3)2)8 have been isolated and characterised by elemental analysis, IR, 207Pb NMR and molecular weight measurements. X-ray structural analysis of the 1:2 complex confirmed the presence of two Pb2Ti2O units which are linked by a common Pb···Pb edge and are held together by alkoxide and acetate bridges. The acetate groups have migrated from the Pb to the Ti centres during the reaction. Hydrolysis of the 1:1 Pb/Ti complex produced clear gels providing the H2O/complex ratio was less than 4. Heat treatment of the gel results in loss of residual organics below 400°C. The XRD pattern indicates the presence of the pyrochlore and perovskite phases after heating at 500°C but the sample is poorly crystalline. Complete conversion to the perovskite phase of lead titanate occurs on heating to 600°C for 1 hour. Thin films of lead titanate were deposited by dip-coating a solution of this complex in isopropanol. Analyses of the films, carried out using electron microprobe, Scanning Auger Spectroscopy and Rutherford Backscattering, indicated that they were of excellent quality, crystalline after heating at 600°C and with relatively sharp substrate-coating interface. 相似文献
870.