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11.
T. M. Gorrie S. Kalyana Raman H. K. Rouette Heinrich Zollinger 《Helvetica chimica acta》1973,56(1):175-195
An NMR. investigation of the state of formaldehyde in acidic solutions has been carried out. Solutions of DCl/D2O/CD3COOD containing two sources of formaldehyde, i.e. paraformaldehyde (I) and trioxane (II), were used for this purpose. In systems I and II the effect of various D2O/CD3COOD ratios, at a constant DCl concentration, was studied, while for II the effect of changing DCl concentration was also investigated. The results show that in aqueous solution, formaldehyde exists primarily as the monomeric and linear oligomeric forms of methylene glycol. Reducing the amount of D2O (at constant DCl concentration), while increasing the CD3COOD content, results in an increase in the polymeric species and in trioxane. In addition, substitution of water by acetic acid results in systems that are catalytically more active than aqueous solutions of the same hydrochloric acid concentration. Along with the usual polymer-monomer equilibria which exist in such solutions, side reactions of methylene glycol with the hydrochloric acid present also occur to a small extent, e.g. acetylation, substitution of OH by Cl and the Cannizzaro reaction. It is suggested that these findings will result in a better understanding of the formaldehyde crosslinking reactions in cotton cellulose. 相似文献
12.
Krishna Raman Surendra S. Parmar Shiva P. Singh 《Journal of heterocyclic chemistry》1980,17(5):1137-1139
A series of 1-(5-phenyl-2H-tetrazol-2-ylacetyl)-4-substituted thiosemicarbazids were prepared as possible antiinflammatory agents. Their antiproteolytic activity was reported. 相似文献
13.
Samath S. Abdul Raman Mani Raman Natarajan Jeyasubramanian Kadarkarai Thangam Ramalingam Suthamalli K. 《Transition Metal Chemistry》1992,17(1):13-15
Transition Metal Chemistry - The synthesis and structural characterization of new metal(II) chelates (M = CoII, NiII, CuII and ZnII) of neutral conjugated bidentate β-diketone ligands, having... 相似文献
14.
A self-consistent estimation method for the thermochemical properties of polycyclic aromatic hydrocarbons (PAH) is presented. This method is based on enthalpies of formation (DeltaHf(degrees), entropies (S(degrees)298, and heat capacities (C(degrees)p obtained from B3LYP/6-31G(d) calculations of the total energies and frequencies for 139 PAHs, including C(60) and C(70) fullerenes. The enthalpies of formation were calculated using an optimized set of homodesmic reactions given the available experimental DeltaHf(degrees) of PAHs. The theoretical entropies were compared with the existing experimental entropies, and some inconsistencies in the experimental data were identified. The estimation method presented here is a systematic extension of the widely employed atom-centered group additivity method originally proposed by Benson. This new method is based on bond-centered groups that define bonds linking two atom-centered groups and specify the size of the rings to which they belong. In addition, a term to describe the resonance energy is included. The thermochemical properties of PAHs up to C(70) fullerene are estimated with a mean average deviation of 2.8 kcal mol(-1) in DeltaHf(degrees), 0.7 cal K(-1) mol(-1) in S(degrees)298, and about 0.5 cal K(-1) mol(-1) in the C(degrees)p. This bond-centered group additivity method for the thermochemical properties of PAHs significantly expands both the range of systems that can be estimated and the accuracy of the estimations. The results of this work also allow us to assess the quality of available experimental data. For example, there are strong indications that the literature DeltaHf(degrees)of benzo[k]fluoranthene is about 10 kcal mol(-1) too low. 相似文献
15.
Potential applications of nanoporous thermosetting polymers include polyelectrolytes in fuel cells, separation membranes, adsorption media, and sensors. Design of nanoporous polymers for such applications entails controlling permeability by tailoring pore size, structure, and interface chemistry. Nanoporous thermosetting polymers are often synthesized via free radical mechanisms using solvents that phase separate during polymerization. In this work, a novel technique for the synthesis of nanoporous thermosets is presented that is based on the reactive encapsulation of an inert solvent using step-growth cross-linking polymerization without micro/macroscopic phase separation. The criteria for selecting such a monomer-polymer-solvent system are discussed based on FTIR analysis, observed micro/macroscopic phase separation, and thermodynamics of swelling. Investigation of resulting network pore structures by scanning electron microscopy (SEM) and small-angle X-ray scattering following extraction and supercritical drying using carbon dioxide showed that nanoporous polymeric materials with pore sizes ranging from 1 to 50 nm can be synthesized by varying the solvent content. The differences in the porous morphology of these materials compared to more common free radically polymerized analogues that exhibit phase separation were evident from SEM imaging. Furthermore, it was demonstrated that the chemical activity of the nanoporous materials obtained by our method could be tailored by grafting appropriate functional groups at the pore interface. 相似文献
16.
A novel 14-membered macrocyclic Schiff base derived from 3-cinnamalideneacetoacetanilide and o-phenylenediamine acts as a tetradentate and strongly conjugated ligand to form a cationic solid complex with CuCl2/NiCl2/CoCl2/ZnCl2. The ligand and the complexes were characterized by the usual spectral and analytical techniques. The main i.r. band of the macrocyclic Schiff base was compared to that of its metal complexes. The C=N bands are shifted to the lower wave number. The cyclic voltammogram of the copper complex shows that the macrocyclic ligand is able to stabilize the copper(III) oxidation state. The e.s.r. spectra of the copper complex in DMSO solution at room temperature and liquid N2 temperature were recorded and their salient features thoroughly discussed. The antimicrobial screening tests were also recorded and gave good results in the presence of metal ions in the ligand system. 相似文献
17.
Darr JA Guo ZX Raman V Bououdina M Rehman IU 《Chemical communications (Cambridge, England)》2004,(6):696-697
For the first time, the MOCVD technique has been used to deposit carbonated hydroxyapatite onto Ti6AL4V substrates using volatile monomeric (liquid) complexes [Ca(beta-diketonate)(2)(L)] and P(OEt)(3). 相似文献
18.
The nucleophile [ArTe−] generated in situ borohydride solution of Ar2Te2, reacts with 2-(chloromethyl) tetrahydrofuran and 2-(2-bromoethyl)-1,3-dioxolane resulting in L1 and L2, respectively. The complexes of palladium(II) and platinum(II) with L1/L2 having stoichiometries [MCl2·L2], [ML2](ClO4)2, [(DPPE)ML2](ClO)4)2, [(PPh3)2ML2](ClO4)2 and [(phen)ML2](ClO4)2 (where L = L1/L2 DPPE = Ph2PC H2CH2PPh2, PHEN = 1,10-phenanthroline and M = Pd/Pt) have been synthesized. IR, 1H, 125Te{1H} and 31P{1H} NMR and UV-vis spectral data of these species in conjunction with their molar conductance and molecular weight data have been used to authenticate the new species. In all complexes (1–20) the ligands L1 and L2 are coordinated through tellurium and in the complexes of formula [ML2](ClO4)2 (M = Pd, Pt) the ligand is bidentate with the oxygen atom used in complexation. In solution, complexes PtCl2L2 exist as a mixture of cis and trans isomers whereas only the trans isomer was observed for the palladium analogues. The [(phen)PdL2](ClO4)2(Q) quenches 1O2 readily. The plot of log [Q] vs time is linear. Mechanism compatible with the experimental observations is proposed. 相似文献
19.
Two new iron nitrosyls derived from two designed pentadentate ligands N,N-bis(2-pyridylmethyl)-amine-N'-(2-pyridylmethyl)acetamide and N,N-bis(2-pyridylmethyl)-amine-N'-[1-(2-pyridinyl)ethyl]acetamide (PcPy(3)H and MePcPy(3)H, respectively, where H is the dissociable amide proton) have been structurally characterized. These complexes are similar to a previously reported (Fe-NO)6 complex, [(PaPy(3))Fe(NO)](ClO(4))(2) (1) that releases NO under mild conditions. The present nitrosyls, namely [(PcPy(3))Fe(NO)](ClO(4))(2) (2) and [(MePcPy(3))Fe(NO)](ClO(4))(2) (3), belong to the same (Fe-NO)6 family and exhibit (a) clean (1)H NMR spectra in CD(3)CN indicating S = 0 ground state, (b) almost linear Fe-N-O angles (177.3(5) degrees and 177.6(4) degrees for 2 and 3, respectively), and (c) N-O stretching frequencies (nu(NO)) in the range 1900-1925 cm(-)(1). The binding of NO at the non-heme iron centers of 1-3 is completely reversible and all three nitrosyls rapidly release NO when exposed to light (50 W tungsten bulb). In addition to acting as photoactive NO-donors, these complexes also nitrosylate thiols such as N-acetylpenicillamine, 3-mercaptopropionic acid, and N-acetyl-cysteine-methyl-ester in yields that range from 30 to 90% in the absence of light. The addition of alkyl or aryl thiolate (RS(-)) to the (Fe-NO)6 complexes in the absence of dioxygen results in the reduction of the iron metal center to afford the corresponding (Fe-NO)7 species. 相似文献
20.
Kotha A Raman RC Ponrathnam S Kumar KK Shewale JG 《Applied biochemistry and biotechnology》1998,74(3):191-203
Various glycidyl methacrylate (GMA) copolymers were synthesized by suspension polymerization, using pentaerythritol triacrylate (PETA), trimethylolpropane triacrylate (TMPTA), and trimethylolpropane trimethacrylate (TRIM) as crosslinking comonomers. These copolymers were evaluated for the immobilization of penicillin G acylase. Broad pore-size distribution that was observed was in the range 5-300 nm. Both surface area and pore volume increased with increase in the mole fraction of crosslinking comonomer (increasing crosslink density). The pore volume of the copolymers was more than doubled by including lauryl alcohol as porogen. Binding of penicillin G acylase (PGA) was quantitative on highly crosslinked copolymers. The expression of bound PGA was better on the relatively more hydrophilic GMA-TMPTA and GMA-PETA copolymer supports compared to the GMA-TRIM copolymers. Among the different copolymers studied, GMA-TMPTA copolymer 7411 exhibited highest activity of immobilized penicillin G acylase (167.4 IU/g) with 35.1% expression. 相似文献