全文获取类型
收费全文 | 7755篇 |
免费 | 391篇 |
国内免费 | 66篇 |
专业分类
化学 | 5766篇 |
晶体学 | 72篇 |
力学 | 225篇 |
综合类 | 1篇 |
数学 | 644篇 |
物理学 | 1504篇 |
出版年
2023年 | 30篇 |
2022年 | 39篇 |
2021年 | 136篇 |
2020年 | 141篇 |
2019年 | 159篇 |
2018年 | 87篇 |
2017年 | 89篇 |
2016年 | 220篇 |
2015年 | 205篇 |
2014年 | 287篇 |
2013年 | 475篇 |
2012年 | 568篇 |
2011年 | 681篇 |
2010年 | 434篇 |
2009年 | 378篇 |
2008年 | 536篇 |
2007年 | 410篇 |
2006年 | 397篇 |
2005年 | 390篇 |
2004年 | 346篇 |
2003年 | 279篇 |
2002年 | 306篇 |
2001年 | 179篇 |
2000年 | 187篇 |
1999年 | 110篇 |
1998年 | 95篇 |
1997年 | 68篇 |
1996年 | 89篇 |
1995年 | 72篇 |
1994年 | 68篇 |
1993年 | 64篇 |
1992年 | 38篇 |
1991年 | 49篇 |
1990年 | 45篇 |
1989年 | 45篇 |
1988年 | 31篇 |
1987年 | 31篇 |
1986年 | 33篇 |
1985年 | 49篇 |
1984年 | 36篇 |
1983年 | 39篇 |
1982年 | 26篇 |
1981年 | 35篇 |
1980年 | 19篇 |
1979年 | 22篇 |
1978年 | 20篇 |
1977年 | 28篇 |
1976年 | 29篇 |
1975年 | 22篇 |
1974年 | 16篇 |
排序方式: 共有8212条查询结果,搜索用时 15 毫秒
91.
Hyoung Sik Kim Min Kang Min Woo Song Jin Won Park Byoung Ryul Min 《Reaction Kinetics and Catalysis Letters》2004,81(2):251-257
Pt-Pd bimetallic catalysts were prepared in order to develop and investigate catalysts having excellent activity and stability
for benzene destruction. The effect of Pt addition to Pd catalysts is studied by XPS analysis.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
92.
Reaction of 1,6-enynes with a hydrosilane in the presence of immobilized cobalt/rhodium bimetallic nanoparticles gives 2-methyl-1-silylmethylidene-2-cyclopentanes in the absence of carbon monoxide and 2-formylmethyl-1-silylmethylidene-2-cyclopentanes under 1 atm of carbon monoxide, respectively. [reaction: see text] 相似文献
93.
A new approach to indolizines has been developed using a 5-endo-trig iodocyclization of allylic esters followed by isomerization and dehydroiodination facilitated by triethylamine at rt. This mild procedure enabled us to synthesize a number of highly substituted indolizines in good yields. 相似文献
94.
Jae Hyung Park Yong Woo Cho Yoen Ju Son Kwangmeyung Kim Hesson Chung Seo Young Jeong Kuiwon Choi Chong Rae Park Rang-Woon Park In-San Kim Ick Chan Kwon 《Colloid and polymer science》2006,284(7):763-770
An anthracycline drug, adriamycin, was chemically conjugated onto the backbone of glycol chitosan via an acid-labile cis-aconityl linkage. The physicochemical characteristics of the glycol chitosan–adriamycin (GC–ADR) conjugates were investigated by dynamic light scattering, atomic force microscopy, and fluorescence spectroscopy. The GC–ADR conjugates were capable of forming nano-sized self-aggregates in an aqueous medium, when the adriamycin content in the conjugate was in the range of 2.0–5.0 wt.%. The self-aggregates were spherical in shape, and had mean diameters of 238–304 nm, depending on the adriamycin content. The critical aggregation concentrations of the conjugates, estimated by the fluorescence quenching method, were as low as 1.0–2.5×10−2 mg/ml. The size of self-aggregates was not affected by the polymer concentration in the range from 50 to 2,000 μg/ml, and was maintained up to 8 days in phosphate-buffered saline (pH 7.4), indicating high colloidal stability. The release of adriamycin from self-aggregates was significantly dependent on the pH of the medium due to the cis-aconityl linkage; e.g., the amount of adriamycin released for 4 days was 7.3±0.3% at pH 7, whereas it was 29.3±1.9% at pH 4. The cell viability results demonstrated that free adriamycin shows more potent cytotoxicity than the conjugates, primarily attributed to the sustained release of adriamycin from self-aggregates. In conclusion, the self-aggregates, formed by GC–ADR conjugates, might be useful for the site-specific delivery of adriamycin in a sustained manner. 相似文献
95.
G. J. De Jong U. A. Th. Brinkman 《Journal of Radioanalytical and Nuclear Chemistry》1977,35(1):223-232
For the system liquid anion-exchanger—Cr(III)−NCS−, an investigation has been made of the dependence of the percentage extraction of Cr(III) on parameters such as standing
time of the Cr(III)−NCS− solution, temperature, pH and type of exchanger. Quantitative extraction of e.g. 4·10−4 M Cr(III) by 0.1M Aliquat in CCl4 is easily achieved at room temperature, using 4.75M KNCS−0.05N HCl as aqueous phase. At high Cr(III) concentrations, the
complex anion present in the organic phase is Cr(NCS)
6
3−
; when working with dilute metal ion solutions, the species extracted is Cr(NCS)4 (H2O)
2
−
. Separations of mixtures containing 10−2−10−4 M Co(II), Ni(II) and Cr(III) have successfully been accomplished. 相似文献
96.
Tae?Shin?Chung Young?Mee?Na Shin?Won?Kang Ok-Sang?JungEmail author Young-A?Lee 《Transition Metal Chemistry》2005,30(5):541-545
Hydrogen peroxide oxidation of platinum(II) compounds containing labile groups such as Cl, OH, and alkene moieties has been carried out and the products characterized. The reactions of [PtII (X)2 (N–N)] (X = Cl, OH, X2 = isopropylidenemalorate (ipm); N–N 2,2-dimethyl-1,3-propanediamine [(dmpda), N-isopropyl-1,3-propanediamine (ippda)] with hydrogen peroxide in an appropriate solvent at room temperature affords [PtIV (OH)(Y)(X)2(N–N)] (Y = OH, OCH3). The crystal structures of [PtIV(OH)(OCH3)(Cl)2(dmpda)]·2H2O (P-1 bar, a = 6.339(2) Å , b = 9.861(1) Å, c = 11.561(1) Å, a = 92.078(9)°, β = 104.78(1)°, γ=100.54(1)°, V = 684.3(2) Å3, Z = 2R = 0.0503) and [PtIV(OH)2(ipm)(ippda)]·3H2O (C 2/c, a = 27.275(6) Å, b=6.954(2) Å, c = 22.331(4) Å, β = 118.30(2)°, V = 3729(2) Å3, Z = 8, R = 0.0345) have been solved and refined. The local geometry around the platinum(IV) atom approximates to a typical octahedral arrangement with two added groups (OH and OCH3; OH and OH) in a transposition. The platinum(IV) compounds with potential labile moieties may be important intermediate species for further reactions. 相似文献
97.
Young-Gu Cho Dae-Kwang Park Dae-Won Park Hee-Chul Woo Jong-Shik Chung 《Research on Chemical Intermediates》2002,28(5):419-431
The selective oxidation of hydrogen sulfide containing excess water and ammonia was studied over vanadium-bismuth mixed oxide catalysts. The investigation was focused on understanding the complex reaction steps and the roles of each metal oxide. Therefore, supported V2O5/TiO2, V-Bi-O/TiO2 catalysts and a mechanical mixture of V2O5 + Bi2O3 were tested in the reaction. Ammonia reacted either with H2S or SO2, produced from the oxidation of H2S. Water vapor promoted the reaction of ammonia and SO2. Strong synergistic phenomena in catalytic activity were observed for the mechanically mixed catalyst of V2O5 and Bi2O3. V-Bi-O/TiO2 catalyst showed very high H2S conversion without any considerable emission of SO2. Temperature-programmed studies (TPR and TPO), XRD and Raman analyses revealed that the high catalytic performance of V-BiO/TiO2 catalyst originated from the high redox capacity of the bismuth vanadate phase. 相似文献
98.
Shyh‐Jong Chen Cheng Chen Yaw‐Shun Hong 《International journal of quantum chemistry》2005,103(2):198-214
This investigation conducted reaction channels of weakly bound complexes CO2…HF, CO2…HF…NH3, CO2…HF…NH2CH3, CO2…HF…NH(CH3)2, and CO2…HF…N(CH3)3 systems, using the Gaussian 98 package at the B3LYP/6‐311++G(3df,2pd) level. The syn‐fluoroformic acid or syn‐fluoroformic acid plus NH3 or amine conformers are more stable than the related anti‐fluoroformic acid or anti‐fluoroformic acid plus NH3 or amine conformers. However, the above‐mentioned weakly bound complexes are more stable than both the related syn‐ and anti‐type fluoroformic acid or acid plus NH3 or amine conformers and their related decomposed into CO2 + HF or CO2 + NHR3F (R?H, CH3) combined molecular systems. Five reaction channels of the weakly bound complexes exist. Each channel includes weakly bound complexes and their related above‐mentioned systems. Moreover, each reaction channel contains two transition states. The transition state between the weakly bound complex and anti‐fluoroformic acid type structure (T13) is significantly higher than that of internal rotation (T23) between syn‐ and anti‐FCO2H (or FCO2H…NR3) structures. However, the above‐mentioned T13 can significantly decrease its energy by adding the third molecule NH3 or NR3 (R?H or CH3). The more CH3 that is substituted in NR3 of the reaction channel, the lower the activation energy of the transition state in the system is affected. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
99.
Klapars A Waldman JH Campos KR Jensen MS McLaughlin M Chung JY Cvetovich RJ Chen CY 《The Journal of organic chemistry》2005,70(24):10186-10189
[reaction: see text] A mild and transition-metal-free method for the alpha-arylation of aliphatic nitriles with activated heteroaryl halides was developed using NaHMDS or KHMDS as base at ambient temperature. The key to the success of this method is generation of the nitrile anion in the presence of the heteroaryl halide. The method is applicable to both primary and secondary carbonitriles and a wide range of heteroaryl halides. Selective monoarylation was observed with primary carbonitriles. The operational simplicity and the mild reaction conditions add to the value of this method as a practical alternative to the preparation of alpha-heteroaryl carbonitriles. 相似文献
100.
Quantitative investigation of the shape selectivity for the competitive intercalation reaction of isomeric mixtures in the interlayer of LDH was achieved by analyzing the solid phases synthesized by the reaction of [LiAl(2)(OH)(6)]Cl.yH(2)O with various compositional mixtures of (E,E)- and (Z,Z)-muconates. The apparent partition constant K' for the anion-exchange reaction between (E,E)- and (Z,Z)-muconates was quite dependent on the mole fraction of muconates in solution. The only single phase saturated with [LiAl(2)(OH)(6)](2)[(E,E)-C(6)H(4)O(4)].zH(2)O could be obtained in the range of the initial mole fraction of (E,E)-muconate larger than 0.6 in the starting solution, while mixed phases intercalated with (E,E)- and (Z,Z)-muconates could be obtained at lower mole fractions of (E,E)-muconate. The shape selectivity for the competitive reaction of two muconates on the [LiAl(2)(OH)(6)](+) lattice could be ascribed to thermodynamic processes, and the conditions under which that pure (E,E)-muconate was efficiently separated from isomeric mixtures of two muconates were successfully evaluated. 相似文献