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71.
A. K. Shukla S. Saini P. Kumar J. S. P. Rai A. K. Srivastava 《Journal of polymer science. Part A, Polymer chemistry》1989,27(3):807-815
Polymerization of vinyl acetate initiated by β-picolinium p-chlorophenacylide was carried out at 30, 35, and 40°C, using conventional dilatometric technique. The initiator and the monomer exponent values were 0.80 ± 0.15 and unity, respectively. The polymerization was inhibited in the presence of hydroquinone, but was favored by nonpolar solvent and polymerization temperature. The energy of activation was 90.3 KJ mol?1. An average value of k/kt for the present system was found to be 0.37 × 10?2. The results are explained in terms of a radical mode of polymerization with degradative initiator transfer; the principal mode of termination, however, was bimolecular. 相似文献
72.
In search for a cheaper anode catalyst for the oxidation of ethanol for development of direct alcohol fuel cells, Pd has been
considered here as an interesting substitute for Pt in Pt Ru binary electrodeposite. The binary catalyst when co-deposited
on nickel support has been found to increase the current density and decrease the anodic overvoltage significantly with respect
to pure Pt, Pd and Ni. Its electrocatalytic capability is also comparable with that of the Pt-Ru binary electrocatalyst on
Ni-support, when studied in 1 M EtOH containing 1 M NaOH solution. The effect of loading of Pd Ru electrocatalyst on Ni support has also been tested. The electrocatalytic activity
of the electrodes for oxidation of ethanol has been explained by studies of cyclic voltammetry, chronopotentiometry, steady-state
polarization, and conjugated scanning electron microscopy–energy dispersion X-ray spectroscopy. It has been found that electrode
containing the higher amount of deposit are less affected by carbonaceous poisons. 相似文献
73.
S. Chandrasekhar G. Pavan Kumar Reddy Ch. Nagesh Ch. Raji Reddy 《Tetrahedron letters》2007,48(7):1269-1271
The first deaminative homologation of amines (-CH2NH2) to esters (-CH2CH2COOEt) in one-pot is reported. The reaction proceeds through, formation of an aldehyde from an amine in the presence of Pd/C as catalyst followed by Wittig reaction and catalytic hydrogenation using poly(ethylene glycol) as the solvent in one-pot. 相似文献
74.
Adarsh Kumar A. K. Bose Prof. S. P. Mushran 《Monatshefte für Chemie / Chemical Monthly》1975,106(4):863-869
The oxidation kinetics of cycloheptanone by chloramine-T in alkaline media has been investigated. A mechanism involving the formation of an intermediate by the interaction between the enolic anion of cycloheptanone and chloramine-T in a slow step followed by its interaction with another molecule of chloramine-T in a fast step leading to products has been proposed. The scheme satisfactorily accords with the observed stoichiometry, negligible influence of ionic strength and a positive dielectric effect. Various rate parameters have been computed and 1.2-cycloheptanedione identified as the end product.With 2 Figures 相似文献
75.
Density functional calculations have been carried out on a series of linearly annelated acenes and their BN analogues. Even though borazine shows aromatic and reactivity behavior parallel with that of benzene, its condensed derivatives show patterns different from those of their hydrocarbon analogues. Nucleus independent chemical shift (NICS) values in acenes suggest that the aromaticity of the inner rings is more than that of benzene, whereas in BN-acenes there is no substantial change in the aromaticity of the individual rings. Molecular electrostatic potential (MESP) is employed to obtain further insights into the bonding and reactivity trends for these systems. The MESP topography patterns of acenes and BN-acenes are substantially different, with BN-acenes showing more localized pi electron features compared to those of acenes. The MESP values at the critical points (CPs) indicate overall lowering of aromaticity in these annelated systems. However, this change is gradual among the BN-acenes. 相似文献
76.
Synthesis of phthalide derivatives using nickel-catalyzed cyclization of o-haloesters with aldehydes
Rayabarapu DK Chang HT Cheng CH 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(12):2991-2996
The reaction of o-bromobenzoate (1 b) with benzaldehyde (2 a) in the presence of [NiBr(2)(dppe)] (dppe=1,2-bis(diphenylphosphino)ethane) and zinc powder in THF (24 hours, reflux temperature), afforded 3-phenyl-3H-isobenzofuran-1-one (3 a) in an 86 % yield. Similarly, o-iodobenzoate reacts with 2 a to give 3 a, but in a lower yield (50 %). A series of substituted aromatic and aliphatic aldehydes (2 b, 4-MeC(6)H(4)CHO; 2 c, 4-MeOC(6)H(4)CHO; 2 d, 3-MeOC(6)H(4)CHO; 2 e, 2-MeOC(6)H(4)CHO; 2 f, 4-CNC(6)H(4)CHO; 2 g, 4-(Me)(3)CC(6)H(4)CHO; 2 h, 4-C(6)H(5)C(6)H(4)CHO; 2 i, 4-ClC(6)H(4)CHO; 2 j, 4-CF(3)C(6)H(4)CHO; 2 k, CH(3)(CH(2))(5)CHO; 2 l, CH(3)(CH(2))(2)CHO) also underwent cyclization with o-bromobenzoate (1 b) producing the corresponding phthalide derivatives in moderate to excellent yields and with high chemoselectivity. Like 1 b, methyl 2-bromo-4,5-dimethoxybenzoate (1 c) reacts with tolualdehyde (2 b) to give the corresponding substituted phthalide 3 m in a 71 % yield. The methodology can be further applied to the synthesis of six-membered lactones. The reaction of methyl 2-(2-bromophenyl)acetate (1 d) with benzaldehyde under similar reaction conditions afforded six-membered lactone 3 o in a 68 % yield. A possible catalytic mechanism for this cyclization is also proposed. 相似文献
77.
Chloride1), borohydrides2) and hydrides3) of dicyclopentadienyl thallium (III) and diindenyl thallium (III) have already been reported. The present communication deals with a study on the preparation and characterization of difluorenyl thallium (III) chloride, -hydride and -borohydride. 相似文献
78.
Akhilesh K. Verma Rupesh Kumar Amit Saxena Subho Mozumdar 《Tetrahedron letters》2005,46(31):5229-5232
A novel method for effecting the aza-Michael reactions of N-alkyl- and N-arylpiperazines with acrylonitrile using Cu-nanoparticles is described. The method features the use of 10 mol % Cu (14-17 nm) nanoparticles under mild reaction conditions to afford the addition products in good to excellent yields. The Cu-nanoparticles selectively catalysed the aza-Michael reaction of N-alkyl- and N-arylpiperazines in the presence of aromatic amino or aliphatic hydroxy groups. 相似文献
79.
An efficient and mild method for the reduction of aromatic nitro and azido groups on solid support using Al/NiCl2·6H2O and Al/NH4Cl is described. This solid phase reduction technique has been applied towards the synthesis of DNA binding pyrrolo[2,1-c][1,4]benzodiazepine antitumour antibiotics. 相似文献
80.
The spin transitions in two new cationic complexes of iron, i. e., iron bipyridine formate, [Fe/bipy/3]/HCOO/2. 5/HCOOH/ and iron bipyridine tetrafluoro borate, [Fe/bipy/3]/BF4/2. 2H2O have been studied by using Mössbauer spectroscopy. From quadrupole splitting values, at different temperatures, it has been established that both the complexes show the coexistence of both the high spin state and the low spin state at 300 K while complete transformation to low spin state occurs at 77 K. Both compounds were prepared by electrochemical technique. 相似文献