全文获取类型
收费全文 | 49473篇 |
免费 | 11985篇 |
国内免费 | 1477篇 |
专业分类
化学 | 45548篇 |
晶体学 | 385篇 |
力学 | 711篇 |
数学 | 2810篇 |
物理学 | 4059篇 |
无线电 | 9422篇 |
出版年
2023年 | 96篇 |
2022年 | 142篇 |
2021年 | 381篇 |
2020年 | 1905篇 |
2019年 | 3305篇 |
2018年 | 1561篇 |
2017年 | 1135篇 |
2016年 | 4136篇 |
2015年 | 4245篇 |
2014年 | 4246篇 |
2013年 | 5003篇 |
2012年 | 3884篇 |
2011年 | 3175篇 |
2010年 | 3541篇 |
2009年 | 3505篇 |
2008年 | 3253篇 |
2007年 | 2517篇 |
2006年 | 2160篇 |
2005年 | 2295篇 |
2004年 | 1997篇 |
2003年 | 1798篇 |
2002年 | 2420篇 |
2001年 | 1653篇 |
2000年 | 1568篇 |
1999年 | 563篇 |
1998年 | 220篇 |
1997年 | 180篇 |
1996年 | 178篇 |
1995年 | 147篇 |
1994年 | 140篇 |
1993年 | 140篇 |
1992年 | 110篇 |
1991年 | 113篇 |
1990年 | 98篇 |
1989年 | 95篇 |
1988年 | 83篇 |
1987年 | 53篇 |
1986年 | 40篇 |
1985年 | 81篇 |
1984年 | 70篇 |
1983年 | 62篇 |
1982年 | 60篇 |
1981年 | 46篇 |
1980年 | 44篇 |
1979年 | 53篇 |
1978年 | 40篇 |
1977年 | 49篇 |
1976年 | 37篇 |
1975年 | 28篇 |
1973年 | 37篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
981.
Moon Jeong Park Jongnam Park Taeghwan Hyeon Kookheon Char 《Journal of polymer science. Part A, Polymer chemistry》2006,44(24):3571-3579
We investigated the effect of hard additives, that is, magnetic nanoparticles (NPs) and metal NPs, on the ordered morphology of block copolymers by varying the NP concentration. To characterize the structural changes of a block copolymer associated with different NP loadings, small-angle X-ray scattering and transmission electron microscopy were performed. Monodisperse maghemite (γ-Fe2O3) NPs (7 nm in diameter) and silver (Ag) NPs (6 nm in diameter) with surfaces modified with oleic acids were synthesized, and a cylinder-forming poly(styrene-block-isoprene) diblock copolymer was used as a structure-directing matrix for the NPs. As the NP concentration increased, domains of NP aggregates were observed for both magnetic and metal NPs. In the case of mixtures of cylinder-forming poly(styrene-block-isoprene) and Ag NPs with weak particle–particle interactions, random aggregates of Ag NPs were observed, and the ordered morphology of the block copolymer lost its long-range order with an increase in the NP concentration. However, regular, latticelike aggregates obtained with γ-Fe2O3 NPs, because of the strong interparticle interactions, induced an intriguing morphological transformation from hexagonal cylinders to body-centered-cubic spheres via undulated cylinders, whereas the neat block copolymer did not show such a morphological transition over a wide range of temperatures. The interplay between magnetic NPs and the block copolymer was also tested with magnetic NPs of different sizes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3571–3579, 2006 相似文献
982.
Theoretical study of the unimolecular decomposition mechanisms of energetic TNAD and TNAZ explosives
Min‐Hsien Liu Cheng Chen Yaw‐Shun Hong 《International journal of quantum chemistry》2005,102(4):398-408
Calculation methods based on hybrid Density Functional Theory (DFT) with the basis sets of the B3LYP/6‐31+G(d)//B3LYP/4‐31G(d) method and the differential overlap (INDO) program were used to derive reasonable decomposition mechanisms of 1,4,5,8‐tetranitro‐1,4,5,8‐tetraazadecalin (TNAD) and 1,3,3‐trinitroazetidine (TNAZ) explosives. All possible decomposition species and transition states, including intermediates and products, were identified and their corresponding enthalpy of formation and Gibbs free energy of formation were obtained using polyparametric modification equations. INDO bond energy calculation results reveal the weakest bonding site for reference and determine where cleavage can occur easily. This work is concerned mainly with eliminating HONO (cis or trans form). The activation energy for trans‐form HONO elimination is lower than that of cis‐form HONO elimination in the initial steps of both TNAD and TNAZ decomposition, being 18.5 kJ/mol and 33.3 kJ/mol, respectively. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
983.
The cerium‐containing MCM‐41 (Ce‐MCM‐41) has been synthesized by direct hydrothermal method. The low‐angle XRD patterns revealed the typical five major peaks of MCM‐41 type hexagonal structures. The interplanar spacing d100 = 38.4 Å was obtained that can be indexed on a hexagonal unit cell parameter with ao = 44.3 Å which was larger than that of pure siliceous MCM‐41 (Si‐MCM‐41). Transmission electron micrograph shows the regular hexagonal array of uniform channel characteristics of MCM‐41. The BET surface area of Ce‐MCM‐41 was 840 m2/g, which is much reduced as compared to that of Si‐MCM‐41, with the pore size of 26.9 Å and mesopore volume of 0.78 cm3/g were measured by nitrogen adsorption‐desorption isotherm at 77 K. Along with the results, the synthesized Ce‐MCM‐41 exhibited a well‐ordered MCM‐41‐type mesoporous structure with the incorporation of cerium. Using Ce‐MCM‐41 as a support, the Rh (0.5 wt%) catalyst exhibited very high activity for the NO/CO reactions. 相似文献
984.
985.
Sheng‐Xiong Huang Xun Liao Quan‐Jiang Nie Li‐Sheng Ding Shu‐Lin Peng 《Helvetica chimica acta》2004,87(3):598-604
Three new phenyl glycosides, scrophenoside A ( 1 ), B ( 2 ), and C ( 3 ), and two new phenylethyl glycosides, scroside D ( 4 ) and scroside E ( 5 ), were isolated from the stem of Picrorhiza scrophulariiflora Pennell (Scrophularlaceae), besides five known compounds. On the basis of spectroscopic evidence, the structures of the new compounds were elucidated as 4‐acetyl‐2‐methoxyphenyl 6‐O‐[4‐(β‐D ‐glucopyranosyloxy)vanilloyl]‐β‐D ‐glucopyranoside ( 1 ), 4‐acetylphenyl 6‐O‐[(E)‐p‐coumaroyl]‐β‐D ‐glucopyranoside ( 2 ), 4‐[(1R)‐ and (1S)‐1‐hydroxyethyl]‐2‐methoxyphenyl β‐D ‐glucopyranoside ( 3a and 3b , resp.), 2‐(3,4‐dihydroxyphenyl)ethyl O‐β‐D ‐glucopyranosyl‐(1→3)‐4‐O‐[(E)‐feruloyl]‐β‐D ‐glucopyranoside ( 4 ), and 2‐(3,4‐dihydroxyphenyl)ethyl O‐β‐D ‐glucopyranosyl‐(1→3)‐6‐O‐[(E)‐feruloyl]‐β‐D ‐glucopyranoside ( 5 ). 相似文献
986.
Sarah Almazroa Mohamed H. Elnagdi Abdellatif M. Salah El‐Din 《Journal of heterocyclic chemistry》2004,41(2):267-272
The enaminones 1b,d,f react with 4‐phenyl‐3‐methyl‐5‐pyrazoleamine 3a to yield the pyrazole derivatives 4a‐c that cyclised readily on reflux in pyridine solution in presence of hydrochloric acid to yield the pyrazolo[1,5‐a]pyrimidines 5a‐c. Similarly 3(5)‐amino‐1H‐triazole (3b) reacted with 1b,d,f to yield the triazolo[1,5‐a]pyrimidines 5d‐f. In contrast attempted condensation of the 5‐tetrazoloamine (3c) with 1a,d,e resulted in its trimerisation and only triaroylbenzene 8a,d,e was isolated. The reaction of 1a,b,d with anthranilonitrile 9a and the reaction of 1a‐c with the 2‐aminocyclohexene thiophene‐3‐nitrile 10a afforded the cis enaminones 11a‐c and 12a‐c. Similarly, reaction of 1a‐c with the methylanthranilate 9b and reaction of 1b,e with ethyl 2‐aminocyclohexene thiophene‐3‐carboxylate 10b afforded the cis enaminones 11d‐f and 12d,e respectively. Attempted cyclization of 11a‐c into quinoline failed. Successful cyclization of 11d into the quinolinone 13 could be affected, on heating for five minutes in a domestic microwave oven at full power. The reaction of 1a‐c,f with piperidine afforded the trans enaminones 14a‐d. Similarly, trans 14e was formed from the reaction of 1b with morpholine. The coupling reaction of 1b with excess of benzene diazonium chloride afforded the formazane 16. The enaminone 2 reacted with heterocyclic amines to yield the pyridones 17,18. 相似文献
987.
Zhen‐Yu Li Ping Chen Hong‐Gui Xu Shu‐Ying Peng Yi‐Ming Yang Zhong‐Zhen Zhao Yue‐Wei Guo 《Helvetica chimica acta》2007,90(7):1353-1359
Five new polycyclic Daphniphyllum alkaloids, macropodumines F ( 1 ) and G ( 2 ), 17‐oxoyuzurimine ( 3 ), and macropodumines H ( 4 ) and I ( 5 ), were isolated from the leaves of D. macropodum Miq ., collected in Sichuan Province, China. The structures and relative configurations of the new compounds – as well as of four known, related alkaloids – were elucidated on the basis of in‐depth spectroscopic and mass‐spectrometric analyses, by chemical derivatization, and by comparison of spectroscopic data with those of known compounds. 相似文献
988.
Wang‐Ting Wu Feng‐Ying Chen Shui‐Yang He Huai‐Ming Hu Meng‐Lin Yang Yao‐Yu Wang 《中国化学》2006,24(5):711-713
The binuclear praseodymium(III) complex with N‐(1‐carboxyethylidene)‐salicylhydrazide (C10H10N2O4, H2L) was prepared in H2O‐C2H5OH mixed solution, and the crystal structure of [Pr2L2(HL)2(H2O)4]·3H2O·C6H6 was determined by X‐ray single crystal diffraction. The crystal complex crystallizes in the triclinic system with space group P‐1, and in the structure each Pr atom is 9‐coordinated by carboxyl O and acyl O and azomethine N atoms of two tridentate ligands to form two stable five‐membered rings sharing one side in keto‐mode and two water molecules. The coordination polyhedron around Pr3+ was described as a monocapped square antiprism geometry. In an individual molecule, four tridentate ligands were coordinated by two negative univalent (HL) and two bivalent forms (L) respectively. Two negative univalent ligands were coordinated via μ2‐bridging mode. 相似文献
989.
Guo‐Fu Chen Chang‐Heng Tan Zhu‐Lian Li Shan‐Hao Jiang Da‐Yuan Zhu 《Helvetica chimica acta》2003,86(3):787-792
Pseudolarolides O ( 1 ) and P ( 2 ), two novel triterpenoids with a cycloartane‐type framework, were isolated from the seeds of Pseudolarix kaempferi Gord. (Pinaceae). Their structures were elucidated as (16R,23S,25R)‐16,23‐epoxy‐3,4 : 9,10‐disecocycloartan‐1(10),9(11)‐diene‐3(4),26(23)‐diolide ( 1 ), and (9S,16R,23S,25R)‐1,9 : 16,23‐diepoxy‐8,9 : 9,10‐disecocycloartan‐1(29),5(6),10(19)‐triene‐3(4),26(23)‐diolide ( 2 ), respectively, on the basis of spectroscopic techniques and X‐ray‐diffraction studies. 相似文献
990.
IntroductionReversiblecolorchangesuponexternalorinternalstimulationshavebeenattractingmuchattentionduetotheirutilityasfunctionalmaterials .Forexample ,pho tochromismdescribesthecolorchangesinducedbypho toirradiationandcanbeusedasphoto recordingmateri als… 相似文献