全文获取类型
收费全文 | 4544篇 |
免费 | 692篇 |
国内免费 | 639篇 |
专业分类
化学 | 3707篇 |
晶体学 | 35篇 |
力学 | 267篇 |
综合类 | 63篇 |
数学 | 607篇 |
物理学 | 1196篇 |
出版年
2024年 | 5篇 |
2023年 | 66篇 |
2022年 | 117篇 |
2021年 | 107篇 |
2020年 | 146篇 |
2019年 | 153篇 |
2018年 | 143篇 |
2017年 | 126篇 |
2016年 | 225篇 |
2015年 | 200篇 |
2014年 | 274篇 |
2013年 | 364篇 |
2012年 | 385篇 |
2011年 | 337篇 |
2010年 | 319篇 |
2009年 | 274篇 |
2008年 | 271篇 |
2007年 | 250篇 |
2006年 | 254篇 |
2005年 | 205篇 |
2004年 | 189篇 |
2003年 | 189篇 |
2002年 | 306篇 |
2001年 | 260篇 |
2000年 | 137篇 |
1999年 | 119篇 |
1998年 | 86篇 |
1997年 | 51篇 |
1996年 | 47篇 |
1995年 | 38篇 |
1994年 | 45篇 |
1993年 | 10篇 |
1992年 | 17篇 |
1991年 | 29篇 |
1990年 | 25篇 |
1989年 | 17篇 |
1988年 | 15篇 |
1987年 | 16篇 |
1986年 | 12篇 |
1985年 | 11篇 |
1984年 | 9篇 |
1982年 | 5篇 |
1981年 | 4篇 |
1980年 | 5篇 |
1979年 | 3篇 |
1977年 | 3篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1972年 | 2篇 |
1971年 | 1篇 |
排序方式: 共有5875条查询结果,搜索用时 0 毫秒
81.
JiaChengNING ShuMAO YeDiGUAN 《中国化学快报》2005,16(1):17-19
Eleven (S)-(-)-bishydrocarbyl-(l-alkanoylpyrrolidin-2_yl)_methanol derivatives of three types were synthesized from L-proline.asymmtncally selective alkylation products were obtained oy LDA treatment and alkylation using methyl 2-bromoethyl ether, and three types of chiral α-Substituted-γ-butyrolactones were obtained by hydrolyzing the alkylation products, with %e.e. beijing up to 89 percent. 相似文献
82.
生色冠醚研究.Ⅱ.2、6-二溴靛酚冠醚在甲醇溶液中与碱金属和碱土金属盐的变色作用 总被引:1,自引:0,他引:1
冠醚化酚(1a,1b)和酚型开链冠醚(2a,2b)在甲醇中氢氧化锂的作用下,与2、6—二溴醌氯亚胺反应,生成兰色的2、6—二溴靛酚冠醚(1c,1d,2c,2d)锂盐。在其甲醇溶液中加入其它碱金属和碱土金属盐时,产生颜色变化,其中以2c和2d表现出对Sr~(2+)和Ba~(2+)有较明显的选择性变色作用,其△λ_(max)(nm)分别为:2c:38(SrCl_2),37(BaCl_2);2d:64(SrCl_2),56(BaCl_2)。还考查了介质中含水量对变色作用的影响和锶盐的阴离子效应,探讨了选择性变色作用的机理。 相似文献
83.
Wang M Wang BM Shi L Tu YQ Fan CA Wang SH Hu XD Zhang SY 《Chemical communications (Cambridge, England)》2005,(44):5580-5582
A quinine/Selectfluor combination inducing rearrangement reaction of allylic alcohols was discovered, which involved a moderate yield with good enantioselective construction of alpha-quaternary carbon center and beta-fluoro aldehyde under base condition. 相似文献
84.
The electrocatalytic properties of the SiC particle‐modified glassy carbon electrode (MGC) for adrenaline oxidation were studied by cyclic voltammetry (CV), double‐potential step chronocoulometry (DPSCC), and electrochemical impedance spectroscopy (EIS) techniques in McIlvaine buffer solution. It was shown that the electrode modified with SiC particles markedly displayed an electrocatalytic effect on the process of the electrochemical reaction of adrenaline, i.e., the activity and the reversibility of the MGC electrode has been significantly improved. This was attributed to the adsorption effect of the electroactive adrenaline molecules on the MGC electrode surface. 相似文献
85.
Liu H Zhang S Nie S Zhao X Sun X Yang X Pan W 《Chemical & pharmaceutical bulletin》2005,53(6):631-633
Methylacrylic acid/styrene cross-linked with divinylbenzene is a novel pH-sensitive ion exchange resin. Microspheres of this resin were characterized by Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). The microspheres showed a pulsatile swelling behavior when the pH of the media changed. The pH-sensitive microspheres were loaded with salbutamol sulfate and the drug-release characteristics were studied under both simulated gastric and intestinal pH conditions. The results obtained showed that the drug release also depended on the pH of the release media. 相似文献
86.
The reactions of the cationic, diiron-bridging carbyne complexes [Fe(2)(mu-CAr)(CO)(4)(eta(8)-C(8)H(8))]BF(4) (1, Ar=C(6)H(5); 2, Ar=p-CH(3)C(6)H(4); 3, Ar=p-CF(3)C(6)H(4)) with LiN(C(6)H(5))(2) in THF at low temperature gave novel N-nucleophilic-addition products, namely, the neutral, diiron-bridging carbyne complexes [Fe(2)(mu-CAr)(CO)(4)(eta(7)-C(8)H(8)N(C(6)H(5))(2))] (4, Ar=C(6)H(5); 5, Ar=p-CH(3)C(6)H(4); 6, Ar=p-CF(3)C(6)H(4))). Cationic bridging carbyne complexes 1-3 react with (C(2)H(5))(2)NH, (iC(3)H(7))(2)NH, and (C(6)H(11))(2)NH under the same conditions with ring cleavage of the COT ligand to produce the novel diiron-bridging carbene inner salts [Fe(2)[mu-C(Ar)C(8)H(8)NR(2)](CO)(4)] (7, Ar=C(6)H(5), R=C(2)H(5); 8, Ar=p-CH(3)C(6)H(4), R=C(2)H(5); 9, Ar=p-CF(3)C(6)H(4), R=C(2)H(5); 10, Ar=C(6)H(5), R=iC(3)H(7); 11, Ar=p-CH(3)C(6)H(4), R=iC(3)H(7); 12, Ar=p-CF(3)C(6)H(4), R=iC(3)H(7); 13, Ar=C(6)H(5), R=C(6)H(11); 14, Ar=p-CH(3)C(6)H(4), R=C(6)H(11), 15, Ar=p-CF(3)C(6)H(4), R=C(6)H(11)). Piperidine reacts similarly with cationic carbyne complex 3 to afford the corresponding bridging carbene inner salt [Fe(2)[mu-C(Ar)C(8)H(8)N(CH(2))(5)](CO)(4)] (16). Compound 9 was transformed into a new diiron-bridging carbene inner salt 17, the trans isomer of 9, by heating in benzene. Unexpectedly, the reaction of C(6)H(5)NH(2) with 2 gave a novel COT iron-carbene complex [Fe(2)[=C(C(6)H(4)CH(3)-p)NHC(6)H(5)](mu-CO)(CO)(3)(eta(8)-C(8)H(8))] (18). However, the analogous reactions of 2-naphthylamine with 2 and of p-CF(3)C(6)H(4)NH(2) with 3 produce novel chelated iron-carbene complexes [Fe(2)[=C(C(6)H(4)CH(3)-p)NC(10)H(7)](CO)(4)(eta(2):eta(3):eta(2)-C(8)H(9))] (19) and [Fe(2)[=C(C(6)H(4)CF(3)-p)NC(6)H(4)CF(3)-p](CO)(4)(eta(2):eta(3):eta(2)-C(8)H(9))] (20), respectively. Compound 18 can also be transformed into the analogous chelated iron-carbene complex [Fe(2)[=C(C(6)H(4)CH(3)-p)NC(6)H(5)](CO)(4)(eta(2):eta(3):eta(2)-C(8)H(9))] (21). The structures of complexes 6, 9, 15, 17, 18, and 21 have been established by X-ray diffraction studies. 相似文献
87.
A new pyrenemethylamine substituted l-Boc-tyrosine derivative was synthesized and characterized. UV-vis, FL, CD, and light scattering experiments proved that the chiral molecules were able to self-assemble for formation of new aggregate structure. The SEM and AFM images indicated that the helical wires could be fabricated by π-π stacking interaction between adjacent pyrene molecules. 相似文献
88.
Ab initio molecular orbital theory and density functional theory have been used to study nine isomers of N7 ionic clusters with low spin at the HF/6-31G*, MP2/6-31G*, B3LYP/6-31G*, and B3LYP/6-311(+)G* levels of theory. All stationary
points are examined with harmonic vibrational frequency analyses. Four N7
+ isomers and five N7
− isomers are determined to be local minima or very close to the minima on their potential-energy hypersurfaces, respectively.
For N7
+ and N7
−, the energetically low lying isomers are open-chain structures (C
2
v
and C
2
v
or C2). The results are very similar to those of other known odd-number nitrogen ions, such as N5
+, N9
+, and N9
−, for which the open-chain structures are also the global minima. This research suggests that the N7 ionic clusters are likely to be stable and to be potential high-energy-density materials if they could be synthesized.
Received: 16 July 2001 / Accepted: 8 October 2001 / Published online: 21 January 2002 相似文献
89.
90.
ZuPeiLIANG YaQingFENG ShuXianMENG ZhiYanLIANG 《中国化学快报》2005,16(1):135-138
Urease was immobilized onto the glutaraldehyde cross-linked chitosan beads that were prepared under microwave irradiation. The activity and the yield of activity of immobilized urease was 10.83 U/g B and 47.7%, respectively. The conditions of urease immobilization were optimized. The properties of the immobilized urease were investigated and compared with that of the free enzyme. 相似文献