全文获取类型
收费全文 | 4912篇 |
免费 | 81篇 |
国内免费 | 12篇 |
专业分类
化学 | 2474篇 |
晶体学 | 131篇 |
力学 | 225篇 |
数学 | 667篇 |
物理学 | 1508篇 |
出版年
2022年 | 64篇 |
2021年 | 72篇 |
2020年 | 77篇 |
2019年 | 88篇 |
2018年 | 64篇 |
2017年 | 83篇 |
2016年 | 124篇 |
2015年 | 102篇 |
2014年 | 128篇 |
2013年 | 346篇 |
2012年 | 236篇 |
2011年 | 261篇 |
2010年 | 166篇 |
2009年 | 156篇 |
2008年 | 198篇 |
2007年 | 215篇 |
2006年 | 165篇 |
2005年 | 170篇 |
2004年 | 136篇 |
2003年 | 94篇 |
2002年 | 90篇 |
2001年 | 64篇 |
2000年 | 51篇 |
1999年 | 52篇 |
1998年 | 50篇 |
1997年 | 31篇 |
1996年 | 53篇 |
1995年 | 48篇 |
1994年 | 56篇 |
1993年 | 71篇 |
1992年 | 63篇 |
1991年 | 48篇 |
1990年 | 58篇 |
1989年 | 52篇 |
1988年 | 62篇 |
1987年 | 51篇 |
1985年 | 73篇 |
1984年 | 95篇 |
1983年 | 57篇 |
1982年 | 63篇 |
1981年 | 70篇 |
1980年 | 71篇 |
1979年 | 72篇 |
1978年 | 68篇 |
1977年 | 62篇 |
1976年 | 57篇 |
1975年 | 44篇 |
1974年 | 47篇 |
1973年 | 55篇 |
1972年 | 34篇 |
排序方式: 共有5005条查询结果,搜索用时 15 毫秒
151.
152.
Shipra Mital Gupta 《High Energy Chemistry》2013,47(3):130-134
Nanoparticles of lead sulphide have been stabilized in the presence of excess Pb2+ in aqueous basic medium by a simple chemical route of synthesis. These PbS nanoparticles were synthesized very conveniently at room temperature using hexametaphosphate as stabilizer. These nanoparticles have an absorption extending into the NIR region. A significant quantum confinement effect made the bandgap of lead sulphide nanoparticles produce a blue shift from 0.41 eV to about 1.5 eV. The size and morphology of the particles were studied by TEM. Particles were relatively small sized (about 6 nm) having narrow size distribution. XRD data analysis indicate that the product is a mixture of PbS, PbO and Pb(OH)2. Both XRD pattern and HRTEM images confirm the crystalline structure of lead sulphide crystals. IR spectroscopy indicates the formation of PbS. PbS nanoparticles were fairly stable and could be stored for about three weeks at room temperature and for about two months at 5°C without agglomeration. These particles were photoactive and sensitized the reaction of aniline by light leading to the formation of azobenzene. 相似文献
153.
S. C. Tripathi K. K. Gupta M. Bindu P. M. Gandhi 《Journal of Radioanalytical and Nuclear Chemistry》2013,295(1):657-661
Present investigation describes our study on photochemical generation of uranous ions and consequent degradation of solvent in the uranium loaded 30 % Tributyl phosphate-n-dodecane-nitric acid system. Samples of 30 % TBP-n-dodecane loaded with uranium were subjected to UV photolysis at 254, 300 and 350 nm respectively. Wavelength dependent formation of U(IV) has been determined spectrophotometrically by measuring absorbance at 656 nm. Additionally, photochemical yield of U(IV) has also been estimated semi quantitatively as a function of time of photolysis. The changes in the solvent composition under different photochemical conditions have been studied by examination of comparative gas chromatographic profiles of the solvent before and after photolysis. Among the wavelength of photo irradiation studied, the yield of U(IV) was found to be optimum at 300 nm with least degradation of PUREX solvent. 相似文献
154.
The heterostructured Ag nanoparticles decorated Fe3O4 Glutathione (Fe3O4‐Glu‐Ag) nanoparticles (NPs) were synthesized by sonicating glutathione (Glu) with magnetite and further surface immobilization of silver NPs on it. The ensuing magnetic nano catalyst is well characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), powder X‐ray diffraction (PXRD), thermogravimetric analysis (TGA). The prepared Fe3O4‐Glu‐Ag nanoparticles have proved to be an efficient and recyclable nanocatalyst with low catalyst loading for the reduction of nitroarenes and heteronitroarenes to respective amines in the presence of NaBH4 using water as a green solvent which could be easily separated at the end of a reaction using an external magnet and can be recycled up to 5 runs without any significant loss in catalytic activity. Gram scale study for the reduction of 4‐NP has also being carried out successfully and it has been observed that this method can serve as an efficient protocol for reduction of nitroarenes on industrial level. 相似文献
155.
Dr. Manivannan Ethirajan Dr. Ping Chen Dr. Tymish Y. Ohulchanskyy Dr. Lalit N. Goswami Dr. Anurag Gupta Dr. Avinash Srivatsan Dr. Mahabeer P. Dobhal Joseph R. Missert Prof. Paras N. Prasad Prof. Karl M. Kadish Prof. Ravindra K. Pandey 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(21):6670-6684
We report herein a simple and efficient approach to the synthesis of a variety of meso‐substituted purpurinimides. The reaction of meso ‐ substituted purpurinimide with N‐bromosuccinimide regioselectively introduced a bromo functionality at the 20‐position, which on further reaction with a variety of boronic acids under Suzuki reaction conditions yielded the corresponding meso‐substituted analogues. Interestingly, the free base and the metalated analogues showed remarkable differences in photosensitizing efficacy (PDT) and tumor‐imaging ability. For example, the free‐base conjugate showed significant in vitro PDT efficacy, but limited tumor avidity in mice bearing tumors, whereas the corresponding NiII derivative did not produce any cell kill, but showed excellent tumor‐imaging ability at a dose of 0.3 μmol kg?1 at 24, 48, and 72 h post‐injection. The limited PDT efficacy of the NiII analogue could be due to its inability to produce singlet oxygen, a key cytotoxic agent required for cell kill in PDT. Based on electrochemical and spectroelectrochemical data in DMSO, the first one‐electron oxidation (0.52 V vs. SCE) and the first one‐electron reduction (?0.57–0.67 V vs. SCE) of both the free base and the corresponding NiII conjugates are centered on the cyanine dye, whereas the second one‐electron reduction (?0.81 V vs. SCE) of the two conjugates is assigned to the purpurinimide part of the molecule. Reduction of the cyanine dye unit is facile and occurs prior to reduction of the purpurinimide group, which suggests that the cyanine dye unit as an oxidant could be the driving force for quenching of the excited triplet state of the molecules. An interaction between the cyanine dye and the purpurinimide group is clearly observed in the free‐base conjugate, which compares with a negligible interaction between the two functional groups in the NiII conjugate. As a result, the larger HOMO–LUMO gap of the free‐base conjugate and the corresponding smaller quenching constant is a reason to decrease the intramolecular quenching process and increase the production of singlet oxygen to some degree. 相似文献
156.
Chetan R. Singh Gaurav Gupta Ruth Lohwasser Sebastian Engmann Jens Balko Mukundan Thelakkat Thomas Thurn‐Albrecht Harald Hoppe 《Journal of Polymer Science.Polymer Physics》2013,51(12):943-951
A series of well‐defined poly(3‐hexylthiophene)s (P3HT) of different molecular weight (MW) and high regioregularity was investigated for charge transport properties in as‐cast and melt‐crystallized films. The semicrystalline structure of the P3HT was characterized by X‐ray scattering and Atomic force microscopy. Crystallization by cooling from the melt led to a substantial increase in crystallinity and a stronger alignment of the crystals in comparison to as‐cast films. The increase in crystallinity went along with an increase in hole mobility of up to an order of magnitude as measured by the space charge limited current method. Additionally, the hole mobility depended on the long period of P3HT lamellae and consequently on the MW. In compliance with the long period, the charge carrier mobility first increased with the MW before decreasing again at the onset of chain folding. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 943–951 相似文献
157.
Trichloroisocyanuric acid–KF afforded dialkylfluorophosphates from dialkylphosphites at room temperature through a facile electrophilic–nucleophilic metathesis. 相似文献
158.
In green chemistry, biocatalysis using microwaves is a very attractive tool for various regioselective syntheses. L-Ascorbyl fatty acid esters were synthesized by an immobilized lipase from Bulkholderia multivorans using microwaves, with a dynamically enhanced rate of reaction and appreciable yield of around 80%. Microwave radiation had no effect on enzymic inactivation, however, synergism between microwaves and biocatalyst was observed. 相似文献
159.
Photochemical cyclization of 3 afforded 5, 4 and 8.5 on LAH reduction furnished (±)-glaucine (6) and on treatment with ethanolic HCl afforded (±)-norglaucine (7). 10 obtained by the photocyclization of 9 was converted into 7 and 11 via 12. 相似文献
160.
One of the key steps in the synthesis of ABT-431 is the diastereoselective cyclization of thieny alcohol 1 to trans amide 2. We report a detailed study of the influence of acids, solvents and temperature over the ratio of cis and trans diastereomers. 相似文献