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271.
Donia A. M. El-Boraey H. A. El-Samalehy M. F. 《Journal of Thermal Analysis and Calorimetry》2003,73(3):987-1000
Manganese and iron complexes of Schiff bases derived from 6-formylkhellin were prepared and characterized. Complexes of o-phenylenediamine derivative (ligand (I)) are monomeric or dimeric whereas those of p-phenylenediamine derivative (ligand (II)) are polymeric. The complexes obtained are characterized by a lower magnetic moment
values. The complexes also have different solvent of crystallization with different nature of interaction. The thermal behaviour
of the ligands and their metal complexes was investigated by means of DTA, TG, IR and X-ray diffraction spectroscopy. Ligand
(I) shows different thermal behaviour from that of ligands (II) and (III). The complexes of ligand (II) give abnormal oxides
as a final product during their thermal decomposition.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
272.
Ni-B和Ni-Ce-B超细非晶态合金的退火晶化及其催化性能 总被引:2,自引:0,他引:2
采用XAFS,XRD和DTA方法研究了Ni-B和Ni-Ce-B超细非晶态合金在退火过程中的结构变化及其结构与催化性能的关系.活性结果表明,在退火温度为623K时,Ni-B和Ni-Ce-B样品的苯加氢催化反应转化率最高,分别为63%和81%,0.3%Ce的掺入提高了Ni-Ce-B的催化活性.DTA结果表明,Ni-B超细非晶态合金在598和653K有两个晶化峰,而Ni-Ce-B样品有548,603,696和801K四个晶化峰.XAFS和XRD结果进一步说明,在573K退火时,Ni-B样品晶化生成晶态Ni3B和纳米晶Ni,此时Ni-Ce-B仅有少量晶态Ni3B生成.在673K退火时,Ni-B样品中的Ni3B开始分解生成晶态Ni,同时纳米晶Ni聚集并形成大颗粒晶态Ni,而Ni-Ce-B样品晶化生成晶态Ni3B和纳米晶Ni.在773K和更高的温度退火处理后,Ni-B样品中Ni的局域环境结构与金属Ni箔基本一致,但Ni-Ce-B样品晶化生成的Ni晶格有较大畸变,同时Ni3B并未分解.说明0.3%的Ce对提高Ni-Ce-B样品的稳定性有显著作用.本文首次报道了Ni-B和Ni-Ce-B超细非晶态合金中苯加氢催化活性中心为纳米晶Ni和类似于金属Ni的Ni-B非晶态合金. 相似文献
273.
A series of mononuclear [M(EAr)2(dppe)] [M = Pd, Pt; E = Se, Te; Ar = phenyl, 2-thienyl; dppe = 1,2-bis(diphenylphosphino)ethane] complexes has been prepared in good yields by the reactions of [MCl2(dppe)] and corresponding ArE− with a special emphasis on the aryltellurolato palladium and -platinum complexes for which the existing structural information is virtually non-existent. The complexes have crystallized in five isomorphic groups: (1) [Pd(SePh)2(dppe)] and [Pt(SePh)2(dppe)], (2) [Pd(TePh)2(dppe)] and [Pt(TePh)2(dppe)], (3) [Pd(SeTh)2(dppe)], (4) [Pt(SeTh)2(dppe)] and [Pd(TeTh)2(dppe)], and (5) [Pt(TePh)2(dppe)]. In addition, solvated [Pd(TePh)2(dppe)] · CH3OH and [Pd(TeTh)2(dppe)] · 1/2CH2Cl2 could be isolated and structurally characterized. The metal atom in each complex exhibits an approximate square-planar coordination. The Pd-Se, Pt-Se, Pd-Te, and Pt-Te bonds span a range of 2.4350(7)-2.4828(7) Å, 2.442(1)-2.511(1) Å, 2.5871(7)-2.6704(8) Å, and 2.6053(6)-2.6594(9) Å, respectively, and the respective Pd-P and Pt-P bond distances are 2.265(2)-2.295(2) Å and 2.247(2)-2.270(2) Å. The orientation of the arylchalcogenolato ligands with respect to the M(E2)(P2) plane has been found to depend on the E-M-E bond angle. The NMR spectroscopic information indicates the formation of only cis-[M(EAr)2(dppe)] complexes in solution. The trends in the 31P, 77Se, 125Te, and 195Pt chemical shifts expectedly depend on the nature of metal, chalcogen, and aryl group. Each trend can be considered independently of other factors. The 77Se or 125Te resonances appear as second-order multiplets in case of palladium and platinum complexes, respectively. Spectral simulation has yielded all relevant coupling constants. 相似文献
274.
Antonino Mazzaglia Domenico Garozzo Raffaello Romeo 《Journal of organometallic chemistry》2005,690(8):1978-1985
MALDI and ESI-MS have been applied to the characterization of the reaction products between the labile cis-[Pt(DMSO)2Cl2] (1) and trans-[Pt(DMSO)2Cl(CH3)] (2) complexes with the simplest poly(amidoamine) ligand (PAMAM, G = 0, 1,2-diaminoethane as core). The comparison of the mass spectra of the starting G0 and those of the metallo-dendrimers formed upon mixing of the reagents in an equimolecular ratio, and the analysis of the isotopic distribution in the ESI spectra, have revealed the formation of cationic and neutral mononuclear complexes with PAMAM as ligand, e.g., cis-[Pt(DMSO)(PAMAM)Cl]Cl or trans-(C,N)[Pt(DMSO)(PAMAM)Cl(CH3)], together with various minor components, which have been identified as derivatives from defective structures of PAMAM. The geometry of the main products has been deduced from the values of the protons coupling constants with the isotopically abundant 195Pt. The metal-to-ligand bond is restricted to the peripheral amino groups of PAMAM which shows sufficient flexibility to involve either one or two branches in the coordination bonding. 相似文献
275.
Darko P. Aanin Sneana Rajkovi Dora Molnar-Gabor Milos I. Djuran 《Monatshefte für Chemie / Chemical Monthly》2004,135(12):1445-1453
Summary. Hydrolytic reactions between various palladium(II) complexes of the type cis-[Pd(L)(H2O)2]2+ in which L is ethylenediamine (en), 1,2-propylenediamine (1,2-pn), isobutylenediamine (ibn), 1,2-diaminocyclohexane (1,2-dach), N-methylethylenediamine (Meen), N,N,N,N-tetramethylethylenediamine (Me4en), S-methyl L-cysteine (MeS-L-HCys), L-methionine (L-HMet), and 2,5-dithiahexane (dth) and dipeptide N-acetylated L-methionylglycine (MeCOMet-Gly) were studied by 1H NMR spectroscopy. The reactions were carried out in the pH range 2.0–2.5 and at 50°C. In all these reactions, palladium(II) complex bound to a methionine residue effects the regioselective cleavage of the amide bond involving the carboxylic group of methionine. We found that the rate of hydrolysis and mechanism of this reaction are strongly dependent from the nature of the chelate ligand L in palladium(II) complexes of the type cis-[Pd(L)(H2O)2]2+. 相似文献
276.
[RhH(CO)(PPh3)2] (1) reacts with Et3N·3HF to give the fluoro compound [RhF(CO)(PPh3)2] (2). In a comparable reaction [RhF(PEt3)3] (5) has been obtained from [RhH(PEt3)3] (3) or [RhH(PEt3)4] (4) with substoichiometric amounts of Et3N·3HF in THF. If the latter reaction is carried out in benzene, the complexes 5, cis-mer-[Rh(H)2F(PEt3)3] (6) and cis-fac-[Rh(H)2F(PEt3)3] (7) are obtained. Treatment of 5 with HCl in ether effects the generation of [RhCl(PEt3)3] (8) and the bifluoride compound [Rh(FHF)(PEt3)3] (9), which can be converted into 5 in the presence of Et3N and Cs2CO3. Treatment of 5 with HSiR2Ph (R=Ph, Me) leads to the formation of 3 and the rhodium(III) silyl complexes fac-[Rh(H)2(SiR2Ph)(PEt3)3] (10: R=Ph, 11: R=Me). 相似文献
277.
ágnes Zsigmond Ramóna Madácsi Ferenc Notheisz Erzsébet Mernyák and Ferenc Joó 《Reaction Kinetics and Catalysis Letters》2006,87(2):297-304
Summary [RuCl2(PPh3)3], [{RuCl2(TPPMS)2}2] and their heterogenized analogs were applied in the selective hydrogenation of 17-keto- and α,β-unsaturated ketosteroids.
In basic conditions these complexes selectively hydrogenated the C=O bonds, similarly to the results obtained in the case
of α,β-unsaturated aldehydes. A new method was developed for the synthesis of an expensive steroid alcohol, which can be prepared
traditionally in a more complicated way. 相似文献
278.
P. Fini L. Catucci M. Castagnolo P. Cosma V. Pluchinotta A. Agostiano 《Journal of inclusion phenomena and macrocyclic chemistry》2007,57(1-4):663-668
The interaction of Rose Bengal (RB) with hydroxypropyl-α-cyclodextrin (HP-α-CD), hydroxypropyl-β-cyclodextrin (HP-β-CD) and
hydroxypropyl-γ-cyclodextrin (HP-γ-CD) has been studied in water and in acetate buffer at pH 4.5 by UV–Vis absorption, fluorescence
spectroscopy and Induced Circular Dichroism at 298 K. Evidence of the complex formation between the RB and all HP-CDs have
been obtained both in water and in buffer. Binding constants and stoichiometry of RB/HP-CD complexes in water have been determined
by applying the modified Benesi-Hildebrand equation to the fluorescence measurements. 相似文献
279.
The key factors influencing the Diels—Alder reaction rate at ambient and elevated pressures were elucidated using data on the reactivity of various diene—dienophile systems in usual and Lewis acid-catalyzed Diels—Alder reactions, the reaction enthalpy, complex formation, dissolution, and solvation, and the donor-acceptor properties of the reactants. It was found that taking account of both the orbital interaction energy and the balance of bond rupture and formation energies allows correct prediction of the reaction rate in the absence or in the presence of Lewis acids. 相似文献
280.
Three new rigid bridging ligands for metal complexation (7=bmb, 8=bqb and 11=btb) were prepared from a rigid triptycene spacer connected to two bipyridine ligands using a Horner–Emmons type reaction. The triptycene spacer is substituted by methoxy groups in the case of bmb and in the case of bqb by a benzoquinone substituent. The corresponding metal complexes (ruthenium and/or osmium) were synthesised and the different luminescence behaviour was tested. They show great potential for the investigation of intramolecular electron and energy transfer reactions. The dinuclear metal complex Ru---bqb---Os is an interesting system in which the bridging ligand bqb acts as a redox switch, able to tune the conductivity for energy or electrons across the bridge. 相似文献