全文获取类型
收费全文 | 856篇 |
免费 | 19篇 |
国内免费 | 2篇 |
专业分类
化学 | 407篇 |
晶体学 | 25篇 |
力学 | 30篇 |
数学 | 96篇 |
物理学 | 319篇 |
出版年
2023年 | 5篇 |
2022年 | 6篇 |
2021年 | 5篇 |
2020年 | 20篇 |
2019年 | 17篇 |
2018年 | 11篇 |
2017年 | 17篇 |
2016年 | 28篇 |
2015年 | 14篇 |
2014年 | 28篇 |
2013年 | 43篇 |
2012年 | 63篇 |
2011年 | 60篇 |
2010年 | 42篇 |
2009年 | 31篇 |
2008年 | 35篇 |
2007年 | 37篇 |
2006年 | 28篇 |
2005年 | 33篇 |
2004年 | 40篇 |
2003年 | 35篇 |
2002年 | 20篇 |
2001年 | 12篇 |
2000年 | 13篇 |
1999年 | 14篇 |
1998年 | 7篇 |
1997年 | 7篇 |
1996年 | 12篇 |
1995年 | 15篇 |
1994年 | 15篇 |
1993年 | 15篇 |
1992年 | 6篇 |
1991年 | 12篇 |
1990年 | 5篇 |
1989年 | 7篇 |
1988年 | 11篇 |
1987年 | 5篇 |
1986年 | 8篇 |
1985年 | 8篇 |
1984年 | 10篇 |
1983年 | 3篇 |
1982年 | 7篇 |
1981年 | 7篇 |
1980年 | 9篇 |
1979年 | 8篇 |
1978年 | 11篇 |
1977年 | 6篇 |
1976年 | 5篇 |
1975年 | 6篇 |
1973年 | 4篇 |
排序方式: 共有877条查询结果,搜索用时 15 毫秒
101.
Pandey R Ghosh S Mukhopadhyay S Ramasesha S Das PK 《The Journal of chemical physics》2011,134(4):044533
We report large quadratic nonlinearity in a series of 1:1 molecular complexes between methyl substituted benzene donors and quinone acceptors in solution. The first hyperpolarizability, β(HRS), which is very small for the individual components, becomes large by intermolecular charge transfer (CT) interaction between the donor and the acceptor in the complex. In addition, we have investigated the geometry of these CT complexes in solution using polarization resolved hyper-Rayleigh scattering (HRS). Using linearly (electric field vector along X direction) and circularly polarized incident light, respectively, we have measured two macroscopic depolarization ratios D=I(2ω,X,X)/I(2ω,Z,X) and D(')=I(2ω,X,C)/I(2ω,Z,C) in the laboratory fixed XYZ frame by detecting the second harmonic scattered light in a polarization resolved fashion. The experimentally obtained first hyperpolarizability, β(HRS), and the value of macroscopic depolarization ratios, D and D('), are then matched with the theoretically deduced values from single and double configuration interaction calculations performed using the Zerner's intermediate neglect of differential overlap self-consistent reaction field technique. In solution, since several geometries are possible, we have carried out calculations by rotating the acceptor moiety around three different axes keeping the donor molecule fixed at an optimized geometry. These rotations give us the theoretical β(HRS), D and D(') values as a function of the geometry of the complex. The calculated β(HRS), D, and D(') values that closely match with the experimental values, give the dominant equilibrium geometry in solution. All the CT complexes between methyl benzenes and chloranil or 1,2-dichloro-4,5-dicyano-p-benzoquinone investigated here are found to have a slipped parallel stacking of the donors and the acceptors. Furthermore, the geometries are staggered and in some pairs, a twist angle as high as 30° is observed. Thus, we have demonstrated in this paper that the polarization resolved HRS technique along with theoretical calculations can unravel the geometry of CT complexes in solution. 相似文献
102.
Chakraborty M Singh NJ Mandal PC Das S Mukhopadhyay S 《The journal of physical chemistry. A》2011,115(19):4882-4893
Described in this work is the kinetics of oxidation of ascorbic acid and hydroquinone by a tetranuclear Mn(IV) oxidant, [Mn(4)(μ-O)(6)(bipy)(6)](4+) (1(4+), bipy =2,2(/)-bipyridine), in aqueous solution over a wide pH range 1.5-6.0. In particular, below pH 3.0, protonation on the oxo-bridge of 1(4+) results in the formation of [Mn(4)(μ-O)(5)(μ-OH)(bipy)(6)](5+) (1H(5+)) as an additional oxidant over 1(4+). Both ascorbic acid and ascorbate whereas only hydroquinone and none of its protolytic species were found to be reactive reducing agents in these reactions. Analysis of the rate data clearly established that the oxo-bridge protonated oxidant 1H(5+) is kinetically far more superior to 1(4+) in oxidizing ascorbic acid and hydroquinone. Rates of these reactions are substantially lowered in D(2)O-enriched media in comparison to that in H(2)O media. An initial one electron one proton transfer electroprotic rate step could be mechanistically conceived. DFT studies established that among the two sets of terminal and central Mn(IV) atoms in the tetranuclear oxidant, one of the two terminal Mn(IV) is reduced to Mn(III) at the rate step that we can intuitively predict considering the probable positive charge distribution on the Mn(IV) atoms. 相似文献
103.
Sukul PK Asthana D Mukhopadhyay P Summa D Muccioli L Zannoni C Beljonne D Rowan AE Malik S 《Chemical communications (Cambridge, England)》2011,47(43):11858-11860
We report unique and spontaneous formation of hydrogels of perylene derivatives with melamine. The luminescent gel network is formed by H-type aggregation of the perylene core, supramolecularly cross-linked by melamine units. As a result of controlled aggregation in the extended nanofibers, strong exciton fluorescence emission is observed. 相似文献
104.
Bharti U. N. Verma Kingsuk Mukhopadhyay 《Journal of Thermal Analysis and Calorimetry》2011,104(3):1071-1075
The ligand [2-(1,2,3,4-thiatriazole-5-yliminomethyl)-phenol] (L) is a schiff base derived from condensation reaction of 1,2,3,4-thiatriazole-5-ylamine
and Salicylaldehyde. Synthesis of the ligand (L) and the complex [Cu(II)(L)2]·2H2O have been studied in our previous work (Bharti et al., Asian J Chem 23(2):773–776, 2011). Thermal decomposition behavior
of synthesized Cu(II) complex has been investigated by thermo gravimetric (TG) analysis at heating rate of 10 °C min−1 under nitrogen atmosphere. The mechanism of decomposition of Cu(II) complex has been established from TG data. Kinetic parameters
such as order of reaction (n), activation energy (E
a), frequency factor (Z) and entropy of activation (∆S
≠) were calculated by using Freeman and Carroll (J Phys Chem 62:394–397, 1958) as well as Doyle’s methods as modified by Zsako
(J Phys Chem 72(7):2406–2411, 1968). 相似文献
105.
Nidhi Joshi Anindita Mukhopadhyay Sujit Basak Goutam De Krishnananda Chattopadhyay 《Particle & Particle Systems Characterization》2013,30(8):683-694
The presence of magnetic nanoparticles (NPs) in physiological systems induces toxicity through its effects on mitochondrial function and reactive oxygen species (ROS) imbalance. Magnetic NP induced cytotoxicity has been elaborately evaluated for impending threats, however, a detailed investigation is lacking. It is shown that the interaction of Fe3O4 NPs with cytochrome c can lead to different events based on the NPs to protein ratio, the solution conditions, and the type of surface protection. At low NPs concentration, rapid binding and subsequent electron transfer are the preferred events while at higher concentration slow oxidative modification of the protein is initiated. The slow event of protein modification yields conformational disorientation, loss of stability, and formation of amyloid‐like structures with cytochrome c. The possibility that the NP induced oxidative stress and age can work in concert to compromise different aspects of cellular quality control processes is discussed. Suitable surface modifications of the NPs inhibit their direct binding to the protein molecules and minimize NP induced toxicity. 相似文献
106.
Neha Munot Ujjwala Kandekar Chaitali Rikame Abhinandan Patil Poulomi Sengupta Shabana Urooj Anusha Bilal 《Molecules (Basel, Switzerland)》2022,27(20)
Thiolation of polymers is one of the most appropriate approaches to impart higher mechanical strength and mucoadhesion. Thiol modification of gum karaya and gum acacia was carried out by esterification with 80% thioglycolic acid. FTIR, DSC and XRD confirmed the completion of thiolation reaction. Anticancer potential of developed thiomer was studied on cervical cancer cell lines (HeLa) and more than 60% of human cervical cell lines (HeLa) were inhibited at concentration of 5 µg/100 µL. Immobilized thiol groups were found to be 0.8511 mmol/g as determined by Ellman’s method. Cytotoxicity studies on L929 fibroblast cell lines indicated thiomers were biocompatible. Bilayered tablets were prepared using Ivabradine hydrochloride as the model drug and synthesized thiolated gums as mucoadhesive polymer. Tablets prepared using thiolated polymers in combination showed more swelling, mucoadhesion and residence time as compared to unmodified gums. Thiol modification controlled the release of the drug for 24 h and enhanced permeation of the drug up to 3 fold through porcine buccal mucosa as compared to tablets with unmodified gums. Thiolated polymer showed increased mucoadhesion and permeation, anticancer potential, controlled release and thus can be utilized as a novel excipient in formulation development. 相似文献
107.
B. K. Mukhopadhyay K. K. Ahlquist V. Gruenman A. Lutz I. I. Kovalevski B. Schulze E. Rieger A. Noll W. Nagel J. Grant A. Abrams P. W. Codwise W. Staedel und J. D. Piper 《Fresenius' Journal of Analytical Chemistry》1936,105(5-6):212-222
Ohne Zusammenfassung 相似文献
108.
The compound 4 propyl paraethoxy phenyl cyclohexyl carboxylate (code name D302) is a member of a homologous series and exhibits liquid crystalline (nematic) behavior in the temperature range 48°C to 78°C. An experiment has been set up for conducting X-ray studies of liquid crystal samples at various temperatures. From X-ray studies conducted at different temperatures on D302, the apparent molecular length and inter-molecular distance and their temperature dependence have been determined. The variation of the orientational-order parameter <P2>xray has been determined from the intensities of the scanned X-ray photographs taken at different temperatures. The results have been compared with the<P2>opt values obtained by us from birefringence studies. 相似文献
109.
Benzophenone (BP) in low concentrations (<0.001 mol 1?1) produces a rate enhancing effect in the H2O2-induced bulk photopolymerization of MMA. Rp is proportional to [H2O2]0.4 and [BP]0.4, and at 30° is 1.00 × 10?2 1.mol?1 sec?1. In diluted systems, different solvents produce different kinetic effects, reaction order with respect to monomer being negative for IPA and THF as solvent, positive but <1.0 for benzene and chloroform, 1.2 for acetonitrile, CCl4 and t-butanol and 1.8 for DMA. The variable solvent effect is attributed to modification of the initiation process by the various solvents to different extents. Kinetic analysis of data for bulk photopolymerization gives evidence for primary radical termination and degradative initiator transfer. 相似文献
110.