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51.
Prathima N Harini M Rai N Chandrashekara RH Ayappa KG Sampath S Biswas SK 《Langmuir : the ACS journal of surfaces and colloids》2005,21(6):2364-2374
The thermal stability of short alkanethiol CH(3)(CH(2))(7)SH (C(8)) and long C(18) self-assembled monolayers (SAMs) is investigated using grazing angle reflection-absorption infrared spectroscopy, cyclic voltammetry, and molecular dynamics simulation. We track the disordering of SAM by untilting and gauche defect accumulation with increasing temperature in the 300-440 K range, a range of interest to tribology. Molecular dynamics simulation with both fully covered and partially covered C(6), C(8), and C(18) monolayers brings out the morphological changes in the SAM, which may be associated with the observed thermal stability characteristics. The molecular dynamics simulations reveal that short-chain C(6) and C(8) alkanethiols are more defective at lower temperature than the long-chain C(18) alkanethiol. With increasing temperature disorder in the SAM, as reflected in both untilting and gauche defect accumulation, tends to saturate at temperatures below 360 K for short-chain SAMs such that any further increase in temperature, until desorption, does not lead to any significant change in conformational order. In contrast the disorder in the long-chain C(18) SAM increases monotonically with temperature beyond 360 K. Thus, in a practical range of temperature, the ability of a SAM to retain order with increasing thermal perturbations is governed by the state of disorder prior to heat treatment. This deduction derived from molecular dynamics simulation helps to rationalize the significant difference we have observed experimentally between the thermal response of short- and long-chain thiol molecules. 相似文献
52.
Subhendu?Biswas Kamala?Mitra Bibhutosh?AdhikaryEmail author C.?Robert.?Lucas 《Transition Metal Chemistry》2005,30(5):586-592
Synthesis of six hydroxo-bridged binuclear manganese(III) complexes of formulae [MnL-X-MnL](ClO4) [X = OH (1–6)] along with a mononuclear manganese(III) complex (7) [Mn(L)(L′)(MeOH)2] [HL′ = 2-(2-hydroxy-phen-yl)benzimidazole] and two carboxylate-bridged binuclear manganese(III) complexes (8) and (9) are described. The complexes have been characterized by the combination of i.r., u.v.-vis spectroscopy, magnetic moments and by their redox properties. The electronic spectra of all the complexes exhibit almost identical features consisting of two d–d bands at ca. 550 and 600 nm, one MLCT band at ca.400 nm, together with two π–π* intra-ligand transitions at ca. 250 nm and ca.300 nm. Room temperature magnetic data range from μ = 2.7–3.0 BM indicates some super-exchange between the binuclear metal centers via bridging hydroxo/carboxylato groups. The X-ray crystal structure of the binuclear complex (5) revealed that it has a symmetric MnIIIN2O2 core bridged by a hydroxyl group. The X-ray analysis of the mononuclear complex (7) showed that the manganese-center possesses a distorted octahedral geometry. Electrochemical properties of hydroxo-bridged manganese(III) complexes (1–6) show identical features consisting of an irreversible and a quasi-reversible reduction corresponding to the Mn2III → MnIIMnIII → MnIIMnII couples in the voltammogram. It was found that electron withdrawing substituents on the ligand result in easier reduction. Complex (7) displays an irreversible reduction at 0.08 V and a reversible oxidation at 0.45V assignable to the MnIII → MnII reduction and MnIII → MnIV oxidation, respectively. The carboxylate-bridged compound (8) exhibits two irreversible oxidations at 0.4 and 0.6 V, probably due to Mn2III → MnIIIMnIV → MnIVMnIV oxidations and shows a quasi-reversible reductive wave at −0.85 V, tentatively assigned to Mn2III → MnIIMnIII reduction. 相似文献
53.
An efficient construction of a 24-membered macrocyclic hexaoxazole derivative pertinent to the synthesis of analogues of the important natural product telomestatin was developed, which featured a convergent union of two trisoxazole units. 相似文献
54.
Premamoy Ghosh Samir Biswas Utpal Niyogi 《Journal of polymer science. Part A, Polymer chemistry》1986,24(5):1053-1063
Photopolymerization of methyl methacrylate (MMA) in visible light was studied at 40°C using Rhodamine 6G—Benzoyl peroxide combination as photoinitiator. The photopolymerization proceeds by a free radical mechanism and the radical generation process occurs by an initial complexation reaction between the initiator components. Kinetic data indicated a lower-order dependence of Rp on initiator concentrations (initiator exponent < 0.5). Initiator-dependent chain termination was significant along with the bimolecular mode of chain termination. 相似文献
55.
Virendra Singh Anita Rampal S. N. Biswas K. Datta 《Letters in Mathematical Physics》1980,4(2):131-134
The solution of a difference equation in the form of an infinite continued fraction is used to obtain a class of exact solutions for the eigenfunctions and eigenvalues of doubly anharmonic oscillators described by potentials of the type (1/2)2x2+(1/4)x4+(1/6)x6, n>0, provided certain constraints on the couplings are satisfied. The class is denumerably infinite but not complete. 相似文献
56.
The polymerization of N-vinylcarbazole (NVC) initiated by PhMgBr in benzene was studied at 32°C. Rp is second order with respect to PhMgBr concentration but increases with NVC concentration (up to 0.06 M) and falls thereafter. Rp and P n are depressed by the addition of thiophene and water. Modifiers such as benzaldehyde, butanone, and ethylene glycol practically inhibit the polymerization. Carbon tetrachloride and carbon dioxide, when passed through the NVC solution first, enhance the Rp and P n increases with increasing PhMgBr and NVC concentrations, respectively. Rp increases with temperature, but P n shows a maxium at a certain temperature. A cationic mechanism has been proposed where the polymerization is initiated by RMg+ cations produced from the ionization of PhMgBr by the Ashby and Smith mechanism. 相似文献
57.
Njardarson JT Biswas K Danishefsky SJ 《Chemical communications (Cambridge, England)》2002,(23):2759-2761
A total synthesis of Epothilone 490 and a synthesis of 11-hydroxy dEpoB utilizing a vinyl-boronate cross-metathesis followed by a Suzuki macrocyclization. A mild route to reach aldehydes from terminal olefins, anticipating Nozaki-Kishi macrocyclization is described. 相似文献
58.
A Sarkar N Biswas S Kapoor H S Mahal C K K Nair T Mukherjee 《Research on Chemical Intermediates》2005,31(9):857-866
The oxidation of flavonoids is of great interest because of their action as antioxidants with the ability to scavenge radicals
by means of electron-transfer processes. The redox reactions of the flavonoid derivative troxerutin, (2-[3,4-bis-(2-hydroxyethoxy)
phenyl]-3[[6-deoxy-α-L-manno-pyranosyl)-β-(D-glucopyranosyl]-oxy]-5-hydroxy-7-(2-hydroxyethoxy)-4H-1-benzo-pyran-4-one), were investigated over a wide range of conditions,
using pulse radiolysis and cyclic voltammetry. The oxidation mechanism proceeds in sequential steps. One-electron redox potentials
for troxerutin were found to be +1.196, +0.846 and −0.634 V vs. NHE. 相似文献
59.
Hussain SA Deb S Biswas S Bhattacharjee D 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(11-12):2448-2454
This communication reports the surface pressure (pi) versus area per molecule (A) isotherm characteristics of the mixed films of 9-phenyl anthracene (PA) in stearic acid (SA) and polymethyl methacrylate (PMMA) matrices, at the air-water interface. The mixed Langmuir films at the air-water interface have been observed to be easily transferred onto solid substrates to form uniform Langmuir-Blodgett films. By changing various parameters, namely molefraction, surface pressure of lifting and number of layers, the mixed Langmuir-Blodgett (LB) films of various types have been fabricated successfully and their spectroscopic characteristics have been reported. From the isotherm characteristics and the area per molecule versus molefraction plot, it is evident that the PA molecules are successfully incorporated into mixed Langmuir-Blodgett films. UV-vis absorption spectroscopic study of the mixed LB films at various molefractions of PA in two different matrices reveal that formation of I-type aggregate in PMMA matrix whereas both I- and H-type aggregates are playing their dominant role in SA matrix. Moreover, fluorescence spectroscopic study reveals reabsorption effect. Molecular movement persists in the freshly prepared LB films, as is evident from the time dependent changes in both UV-vis absorption and fluorescence spectra of the mixed LB films in both matrices. From our observation it is evident that about 200 h is required to get the LB films in a stable condition. Dimers and higher order n-mers are formed at a higher surface pressure of 30 mNm(-1). 相似文献
60.
Sarmiento M Mooney P Bishop JM Biswas N Cason NM Dauwe L Godfrey J Kenney VP Pemper R Rojek E Ruchti RC Shephard WD Edelstein RM Forsyth CP Gamarnik K Ginther G Kreymer AE Lipton R McQuade JM Potter DM Russ JS Spiegel L Johnson DE Buchholz D Cremaldi L Delchamps SW Mao HS Rosen JL Sakumoto W Schluter RA Sontz SB Winter C 《Physical review D: Particles and fields》1992,45(7):2244-2248