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981.
An operationally straightforward and efficient method for the alkylation of carbamate-protected guanidines with various alkyl halides and mesylates is described. This protocol proceeds via deprotonation of the acidic N-carbamate hydrogen of the guanidine under biphasic conditions using a catalytic amount of a tetrabutylammonium salt as a phase-transfer catalyst. In this manner, highly functionalized guanidines can be obtained. The reaction is tolerant of a wide range of functional groups on both the alkyl halide and guanidine component. In addition, the reaction is sufficiently mild such that simple aqueous workup and filtration through a short silica gel column yields the substituted guanidines in high purity. In conjunction with the EDCI-mediated guanylation of disubstituted thioureas with amines, phase-transfer catalyzed alkylation of guanidines via a one-pot, three-component synthesis of substituted guanidines was achieved. 相似文献
982.
The reaction of H2CO and H2NCH2CH2OH with the nickel(II) complex of 1,9-diamino-3,7-diazanonane (2,3,2-tet) in the presence of Et3N gives the nickel(II) complex of the macrocycle 3-hydroxyethyl-1,3,5,8,12-pentaazacyclotetradecane (L), which can be readily isolated as the perchlorate salt. The reaction of KCNS with the perchlorate salt in aqueous solution gives [NiL(NCS)2] and the crystal structure of this complex has been determined. The complex is octahedral and trans with the two N-bonded thiocyanates in the axial sites with Ni-NCS bond lengths of 2.106 and 2.145AÅ. The equatorial sites are occupied by N2, N5, N8 and N12 with Ni-N bond distances of 2.053 to 2.076AÅ, which are typical for octahedral nickel(II) complexes. The ligand has a trans III configuration of the sec-NH centres, leading to chair six-membered rings and gauche five-membered rings. The hydroxyethyl group on N3 is axial. There is no evidence for hydrogen-bonding interactions involving the hydroxyethyl group in the crystal lattice. 相似文献
983.
M. N. Ramsis Ch. A. Philip M. Abd El Khalik E. R. Souaya 《Journal of Thermal Analysis and Calorimetry》1996,46(6):1775-1788
CoO/Al2O3 catalysts containing amounts of cobalt ranging form 2 to 20% were prepared atpH 11 from neutral mesoporous alumina composed of γ-Al2O3 and poorly crystalline boehmite, and were then dried at 80?C. X-ray diffraction, DTA and TG techniques were used to study the structural changes produced upon thermal treatment up to 700?C. Soaking of the alumina in cobalt ammine complex solutions for a period of 10 days (the time required for equilibrium) resulted in a series of catalyst samples (I–V). Another sample (III-a) was soaked for a period of 5 days only in order to study the effect of the soaking time upon the equilibrium conditions. Cobalt aluminate (CoAl2O4) bands were characterized in all catalyst samples except III-a. They increased in intensity with increasing cobalt content. Surface species appeared in samples heated to 80?C, and others persisted at 150?C. Heating to temperatures above 200?C resulted in the formation of cobalt oxides, due to decomposition of the surface compounds. DTA and TG studies showed that this was more pronounced at higher concentrations of cobalt. Samples heated at 500?C and above did not undergo any further structural changes, except that the boehmite in the support was converted to γ-Al2O3. The variations in the surface parameters followed the same pattern as found previously [1], demonstrating that the catalyst samples are mesoporous, with retention of two ranges of pore size in most cases. 相似文献
984.
Maria A. A. F. de C. T. Carrondo Pedro M. Matias William Heggie Philip R. Page 《Structural chemistry》1994,5(2):73-77
The structure of 4(dimethylamino)-1, 4, 4a, 5, 5a, 6, 11, 12a-octahydro-3, 5, 10, 12, 12a-pentahydroxy-6-methylene-1, 11-dioxo-2-naphthacenecarboxamide hydrobromide salt was determined by an X-ray analysis. One methacycline cation and one bromide anion were found in the asymmetric unit of an orthorhombic cell, space group P212121,a 9.580(1),b 12.147(2),c 18.735(3) å,V2180.0(5) å3, Z4,D
c 1.59 g cm–3, (MoK) 19.15 cm–1. The structure was solved and refined toR(F) 0.062 andR
w(F) 0.064 by a full matrix least-squares procedure. The conformation of the methacycline cation is found to be similar to that reported for 6-demethyl-7-chlorotetracycline hydrochloride trihydrate. 相似文献
985.
986.
The salts (Ph(4)E)[M(SOCPh)(3)] (M = Zn, Cd, or Hg; E = P or As) are produced by the reaction of Zn(NO(3))(2).6 H(2)O, Cd(NO(3))(2).4H(2)O or HgCl(2) with Et(3)NH(+)PhCOS(-) and (Ph(4)E)X (E = P, X = Br; E = As, X = Cl) in aqueous MeOH in the ratios M(II):PhCOS(-):Ph(4)E(+) = 1:>/=3:>/=1. The crystal structures of (Ph(4)P)[Zn(SOCPh)(3)] (1), (Ph(4)As)[Cd(SOCPh)(3)] (2) and (Ph(4)P)[Hg(SOCPh)(3)] (3) have been determined by single-crystal X-ray diffraction experiments. Crystal data for 1: triclinic; space group P&onemacr;; Z = 2; a = 10.819(2) ?, b = 13.219(3) ?, c = 15.951(3) ?; alpha = 101.75(2) degrees, beta = 97.92(1) degrees, gamma = 109.18(2) degrees. Crystal data for 2: triclinic; space group P&onemacr;; Z= 2; a = 10.741(2) ?, b = 13.168(2) ?, c = 15.809(2) ?; alpha = 101.00(1) degrees, beta = 97.65(1) degrees, gamma = 109.88(1) degrees. Crystal data for 3: monoclinic; space group P2(1)/n; Z = 4; a = 13.302(2) ?, b = 14.276(2) ?, c = 21.108(2) ?; beta = 90.92(1) degrees. The compounds 1 and 2 are isomorphous and isostructural. In the anions [M(SOCPh)(3)](-) the metal atoms have trigonal planar coordination by three sulfur atoms. The metal atoms are further more weakly coordinated intramolecularly to one (M = Hg) or two (M = Zn, Cd) thiobenzoate oxygen atom(s). Using the Bond Valence approach it is found that the contribution of M.O bonding to the total bonding is in the order Cd > Zn > Hg. The metal ((113)Cd, (199)Hg) NMR signals of [M(SOCPh)(3)](-) (M = Cd, Hg) are more shielded than those found for MS(3) kernels in thiolate complexes, a difference attributed to the M(.)O bonding in the thiobenzoate complexes. The (113)Cd resonance of [Cd(SOCPh)(3)](-) in dilute solution is in the region anticipated from dilution data for [Na(Cd{SOCPh}(3))(2)](-). 相似文献
987.
Vernon C. Gibson Charlotte K.A. Gregson Catherine M. Halliwell Nicholas J. Long Philip J. Oxford Andrew J.P. White David J. Williams 《Journal of organometallic chemistry》2005,690(26):6271-6283
Treatment of aminoferrocene with substituted 2-hydroxybenzaldehydes yields the air- and moisture-stable ligands 1–4, which were then reacted to form the chromium dichloride complexes 5–7 and the nickel bis-chelate species 8 and 9. The metal compounds are very air-sensitive but the chromium compounds act as pre-catalysts for the polymerisation of ethylene. Reaction of 1,1′-bis(amino)ferrocene with similarly substituted 2-hydroxybenzaldehyes or simple benzaldehyde gives the ligands 10–12 and 17, respectively. The X-ray crystal structure of 11 shows the molecule to have non-crystallographic C2 symmetry and to be linked by C–Hπ interactions between the anthracene rings. Titanium-containing complexes 13–16 can be formed utilising ligands 10–12 and there is a change in geometry within the complexes dependent on the adjacent co-ligands, whilst ligand 17 can be reacted with PdClMe(COD) to form the chelate complex 18. Cyclic voltammetric studies have been carried out on 18 and its oxidised analogue 19, but both complexes are inactive towards ethylene polymerisation. 相似文献
988.
Alan J. Crowe Peter J. Smith Philip G. Harrison 《Journal of organometallic chemistry》1980,204(3):327-331
A series of cationic tributyltin complexes with a tetraphenylborate counter anion, [Bu3SnL2]+BPh4,?, where L = DMSO, Ph3PO, Ph3,AsO, pyO or DMF, and L2 = diphosO2, has been prepared and their 119mSn Mössbauer spectra investigated. These indicate that the triorganotin cation occupies a pentacoordinate trigonal bipyramidal geometry with equatorial organic groups when L = monodentate donor, whilst the bidentate diphosO2 ligand produces a mer-R3SnX2 stereochemistry about tin. 相似文献
989.
Prof. Dr. Antoaneta D. Stefanova Philip I. Iotov Dimcho I. Dimitrov 《Monatshefte für Chemie / Chemical Monthly》1975,106(3):723-728
The liquid phase oxidation of 1.2.4.5-tetramethylbenzene catalysed by cobaltous acetate and promoted by KBr in acetic acid was kinetically studied. In view of deriving the kinetic equation for the absorption of oxygen, a number of experiments were carried out. The values of the activation energy and of the preexponentA=1014 were determined as well. The resulting kinetic equation: $$ - \frac{{d\left[ {O_2 } \right]}}{{d\tau }} = 10^{14} \cdot \exp \left( { - \frac{{84,460 \times 10^3 }}{{RT}}} \right) \cdot C_{C_6 H_2 (CH_3 )_4 }^{0,5} \cdot C_{Co(OAc)_2 }^{0,5} \cdot C_{KBr}^{0,5} $$ is in accordance with the theoretically derived expression of this type. 相似文献
990.