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71.
Sílvia S. P. R. Almeida Joo J. R. Fraústo Da Silva Armando J. L. Pombeiro 《Journal of organometallic chemistry》1993,450(1-2)
Treatment of a THF solution of trans-[ReCl(N2)(dppe)2] (dppe = Ph2PCH2CH2PPh2) with a 1-alkyne HCCR (R =tBu, CO2Me, CO2Et, or C6H4Me-4), in the presence of Tl[BF4]/[NH4][BF4], under sunlight, affords the corresponding carbyne-fluoro complexes trans-[ReF(CCH2R)(dppe)2][BF4] in an unprecedented single-pot synthesis. Further reaction with [BU4N]OH leads to the vinylidenefluoro compounds trans-[ReF(=C=CHR)(dppe)2] (R = CO2Me, CO2Et, or C6H4Me-4). 相似文献
72.
Casas JS Castaño MV García-Tasende MS Rodríguez-Castellón E Sánchez A Sanjuán LM Sordo J 《Dalton transactions (Cambridge, England : 2003)》2004,(13):2019-2026
Zinc(II) and cadmium(II) acetates were reacted in methanol under various experimental conditions with thiosemicarbazones derived from beta-keto amides or beta-keto esters (HTSC). Some of these reactions afforded thiosemicarbazonate complexes [M(TSC)2] with IR and NMR spectra compatible with N,S-coordination, but most gave complexes [ML2], where HL is a substituted 2,5-dihydro-5-oxo-1H-pyrazole-1-carbothioamide resulting from cyclization of the HTSC. Some of these pyrazolonates and two of the HL ligands were studied by X-ray diffractometry, and their structures are discussed. Surprisingly, the reactions of zinc(II) acetate with HTSC in 1:1 mol ratio usually gave a third, previously unreported type of complex with a dideprotonated ligand, [Zn(L-H)], which was also formed when [ZnL2] and Zn(OAc)2 interacted at room temperature in 1:1 mol ratio. These L-H complexes are highly insoluble in all common solvents, which hinders their characterization but suggests that they are polymeric in nature. 相似文献
73.
Jiří Kohout Mária Kabešová Prof. Dipl.-Ing. Dr. Ján Gažo 《Monatshefte für Chemie / Chemical Monthly》1977,108(5):1011-1018
The infrared spectra of thiocyanato-copper(II) complexes of the type Cu(NCS)2
L
2 with all isomeric picolines and lutidines (L) as well as those of the type Cu(NCS)2
L
3 withL=3- and 4-picoline, 3,4- and 3,5-lutidine were measured. The behaviour of the (CN) stretching vibrations of the Cu(NCS)2
L
2 complexes led to conclusions on the different kind of coordination of the NCS groups in dependence on the ligandL. The mutually conditioned strength of the Cu–NCS and Cu–N(L) bonds in the equatorial plane, especially in the presence of ligandsL with the steric effect, was determined from the frequency shift of the Cu–NCS and Cu–N(L) stretching vibrations with regard to the vibrations for Cu(NCS)2(pyridine)2.
Mit 1 Abbildung 相似文献
Mit 1 Abbildung 相似文献
74.
Queiroz MJ Abreu AS Ferreira PM Oliveira MM Dubest R Aubard J Samat A 《Organic letters》2005,7(22):4811-4814
[structure: see text] A new photochromic thieno-2H-chromene alpha-amino acid derivative was prepared by C-N palladium-catalyzed cross-coupling of a bromothieno-2H-chromene with the aminated aromatic side chain of the methyl ester of a N,N-diprotected amino acid. Its good photochromic properties demonstrated by flash photolysis and continuous irradiation indicate a possible application in ophthalmic lenses. It may also be inserted into peptides to give photoinduced reversible structural changes. 相似文献
75.
Mathieu Allix Philip P.C. Frampton Rocío Ruiz-Bustos 《Journal of solid state chemistry》2006,179(3):775-792
Polycrystalline samples of bilayered brownmillerite-like Ca2.5Sr0.5GaCo0.15Mn1.85O8 and Ca2.5Sr0.5Ga1.2Mn1.8O8 have been prepared and characterised by magnetometry and neutron diffraction over a wide temperature range. The structural chemistry and magnetic properties are compared to those of Ca2.5Sr0.5GaMn2O8. Ga enrichment has a significant effect on the former but not on the latter, whereas changes in both occur when paramagnetic Co3+ cations enter the parent phase on the 4-coordinate sites. The coupling between the environment around the 4-coordinate cations and the transition to an antiferromagnetic ordered state that was observed in Ca2.5Sr0.5GaMn2O8 is not apparent in the cation-substituted compositions, although both show long-range antiferromagnetic order at low temperatures. 相似文献
76.
Martínez AG Vilar ET Barcina JO De La Moya Cerero S 《Journal of the American Chemical Society》2002,124(23):6676-6685
The effect of a bridgehead methyl group on the hydride ion affinity in the gas phase of bicyclo[1.1.1]pent-1-yl (1+), 1-norbornyl (3+), cubyl (5+), 1-adamantyl (7+), bicyclo[2.2.2]oct-1-yl (9+),and bicyclo[3.1.1]hept-1-yl (11+) cations has been studied using density functional theory and ab initio methods. It is concluded that the methyl group always increases the stability of the substituted cations. The effect of the solvent on the stability of methyl-substituted cations in relation to the unsubstituted cations has been studied using the polarizable continuum model of the self-consistent reaction field theory. In the case of rearranging cations, the nucleophilic assistance of the solvent is determined by means of the interaction energy of the corresponding water complexes. It is concluded that the solvent causes the relative stabilization of the parent cations. As a consequence, most of the methyl-substituted bridgehead derivatives show a lower solvolysis rate than the corresponding unsubstituted compounds. A nonqualitative explanation of the methyl effect on the relative stability of bridgehead cations in both gas phase and solution is given for the first time. The ratios of solvolysis products in the case of rearranging bridgehead cations have also been computed from the relative stability of the intermediate water complexes. 相似文献
77.
J. Kohout M. Quastlerová-Hvastijová J. Gažo 《Monatshefte für Chemie / Chemical Monthly》1973,104(3):779-783
Zusammenfassung Die Ligandenfeldspektren der Komplexe des Typs Cu(NCO)2
L
2 (L=Ligand der Chinolin- bzw. Isochinolingruppe) im festen Zustand wurden aufgenommen. Das Spektrum des Komplexes Cu(NCO)2(Chin)2 weist eine einzige Bande auf und deutet auf eine pseudooktaedrische Struktur. Die Spektren der übrigen Komplexe enthalten hingegen neben den Hauptbanden auch Schultern bzw. ist die anwesende Bande zusammengesetzt, so daß diese Spektren mit einer planaren Struktur im Einklang sind. Die annähernden Werte für den Parameter 10Dq wurden berechnet; sie liegen im Bereich von 7,1 bis 7,8 kK.
Mit 1 Abbildung
6. Mitt.:M. Quastlerová-Hvastijová, J. Kohout undJ. Gao, Z. anorg. allgem. Chem., im Druck. 相似文献
Ligand field spectra of some cyanato-copper(II) complexes with ligands from the quinoline- and isoquinoline group
The ligand field spectra of complexes of the type Cu(NCO)2 L 2 (L=ligand from the quinoline or isoquinoline group) in the solid state were recorded. Only the spectrum of Cu(NCO)2(Quin)2 exhibits a single band and indicates a pseudooctahedral structure, while the spectra of the remaining complexes also contain shoulders in addition to the main band, or this band is composite, thus being in accordance with a planar structure. The approximate values of the parameter 10Dq were calculated and found to be in the range of 7.1 to 7.8 kK.
Mit 1 Abbildung
6. Mitt.:M. Quastlerová-Hvastijová, J. Kohout undJ. Gao, Z. anorg. allgem. Chem., im Druck. 相似文献
78.
Silva Silvio S. Ribeiro JoÃo D. Felipe Maria G. A. Vitolo Michelle 《Applied biochemistry and biotechnology》1997,(1):557-564
Batch fermentations of sugar cane bagasse hemicellulosic hydrolysate treated for removing the inhibitors of the fermentation
were performed byCandida guilliermondii FTI20037 for xylitol production. The fermentative parameters agitation and aeration rate were studied aiming the maximization
of xylitol production from this agroindustrial residue. The maximal xylitol volumetric productivity (0.87 g/L h) and yield
(0.67 g/g) were attained at 400/min and 0.45 v.v.m. (KLa 27/h). According to the results, a suitable control of the oxygen input permitting the xylitol formation from sugar cane
bagasse hydrolysate is required for the development of an efficient fermentation process for large-scale applications. 相似文献
79.
80.
The paper discusses the investigation of crystallization of metals and alloys by differential thermal analysis (DTA). It was assumed that this method allows determination of the mechanism and kinetics of volumetric crystallization underiso conditions (e.g. anisothermal) on the basis of the parameters of the equation expressing an integral form of the DTA curve. From DTA, a course of eutectic transformation was determined for a technical Zn?Al alloy containing 4wt% Al. Investigations were carried out under continuous cooling at various rates and the kinetics parameters were determined with the KEKAM equation:-ln(1-x)=kl n 相似文献