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91.
Caruntu D Remond Y Chou NH Jun MJ Caruntu G He J Goloverda G O'Connor C Kolesnichenko V 《Inorganic chemistry》2002,41(23):6137-6146
Study of the reactivity of 3d transition metal cations in diethylene glycol solutions revealed several key features that made it possible to develop a new method for synthesis of the nanocrystalline transition metal ferrites. The 3-7 nm particles of [MFe2O4]n[O2CR]m, where M = Mn, Fe, Co, Ni, and Zn, ligated on their surface with long-chain carboxylate anions, have been obtained in an isolated yield of 75-90%. The key features are the following. Complexation of the first-row transition metal cations with diethylene glycol at a presence of alkaline hydroxide is sufficient to enable control over the rate of their hydrolysis. The reaction of hydrolysis leads to the formation of metal oxide nanocrystals in colloidal solution. The nanoparticles growth is terminated by an added long-chain carboxylic acid, which binds to their surface and acts as a capping ligand. The isolated nanocrystalline powders are stable against agglomeration and highly soluble in nonpolar organic solvents. 相似文献
92.
The solid-phase synthesis of the octapeptide 1 AcGly-Ala-Lys-Arg-His-Arg-Lys-ValOMe, which represents the fragment 14-21 of the amino acid sequence of the chromosomal histone H4, as well as of the structurally related nonapeptide 2 AcGly-Ala-Lys-Leu-Arg-His-Arg-Lys-ValOMe, is described using a new polyacrylic resin containing a glycolamide ester linkage(resin-NHCO-CH2-OCO-peptide) acting as a labile anchoring moiety between the resin and the peptide.After elongation of the polypeptide chain using classical protecting groups, i.e. t-butyloxycarbonyl for the α-NH2 function, benzyloxycarbonyl, nitro and 2,4-dinitrophenyl groups for the side-chains of Lys, Arg and His respectively, both peptides 1 and 2 were obtained in good yields and with a high purity as shown by high-pressure liquid chromatography, by amino-acid analysis and by high-field proton NMR spectroscopy.This work demonstrates the ability of the newly introduced polyacrylic resin to act as a convenient support for solid-phase peptide synthesis. 相似文献
93.
The voltammogram of aryldiazonium tetrafluoroborates in acetonitrile (ACN), at low concentration, shows a first one-electron wave followed at a more negative potential by a small second wave; this last one corresponds to the reduction of the radical formed at the level of the first wave. Simulation of the voltammogram permits one to determine the standard redox potential of the radical/anion couple Eo(Ph./Ph-) = 0.05 V/SCE and the reduction mechanism of the diazonium cation. An electron transfer concerted with the cleavage of the C-N bond furnishes the aryl radical; this radical undergoes two competitive reactions: reduction at the electrode and H-atom transfer. 相似文献
94.
A study of the preparations of the complex hydridic anions [MH(6)](4)(-) (M = Fe and Ru) reveals a number of distinctive features. Here a soluble homoleptic ruthenium hydride has been prepared for the first time. For example, both FeX(2) and [Ru(eta(4)-1,5-COD)X(2)], X = Cl and Br, react with PhMgBr solutions under hydrogen to produce the title compounds. The benzene liberated in these reactions is more readily hydrogenated in the case of a homogeneous room temperature ruthenium hydride preparation to both cyclohexane and cyclohexene. The (1)H NMR spectroscopic data show that the two complex anions have hydride absorptions in the low-frequency region, delta -20.3 and -14.7, respectively. Further, (1)H spin-lattice relaxation times (T(1)) for M-H are longer in the case of Ru vs Fe. 相似文献
95.
The molecular energy of the complex (η5-C5H5)2TiCl2 has been calculated for experimental geometry and for several hypothetical forms by a semi-empirical CNDO/2 approach. The energy difference between experimental (quasi-tetrahedral) geometry and a planar geometry is ca. 20 kcal mol?1. This difference is sufficiently high to explain the difficulty of the inversion process. 相似文献
96.
Urs P. Wild Hans J. Griesser Vo Dinh Tuan Jean F.M. Oth 《Chemical physics letters》1976,41(3):450-455
The emission spectra of the second excited singlet state of [18] annulene and of monofluoro [18] annulene (in a 3-methylpentane glass at 4 K) are reported. The large energy gap between the first and second excited singlet states inhibits fast internal conversion and favours the appearance of S2 → S0 emission. In addition, fluorescence from the S1 state can be observed in monofluoro [13] annulene by exciting into the S2 or directly into the S1 absorption. 相似文献
97.
We describe the synthesis of 3-(2-thienyl)pyridazine and of some of its derivatives substituted on the 6 position eg., ethoxy, hydrazino and azido. Some of these compounds have lead to condensed rings systems, namely, triazolo- and tetrazolopyridazines. 相似文献
98.
The optically active methylphenyl-α-naphthylsilane racemises quickly in tetrahydrofuran in the presence of LiAlH4.Kinetic results show a different behaviour of the hydride depending on its concentration. Activation parameters have been obtained and mechanisms proposed. 相似文献
99.
Gérald Perron François Quirion Daniel Lambert Jean Ledoux Lahouari Ghaicha R. Bennes Mireille Privat Jacques E. Desnoyers 《Journal of solution chemistry》1993,22(2):107-124
Phase diagrams, volumes and heat capacities of aqueous mixtures of 2,6-dimethylpyridine (2,6-L) and 2-isobutoxyethanol (iBE) and activities of 2,6-L in aqueous mixtures were measured in the monophasic region near the lower critical solution temperature (LCST). With 2,6-L some measurement were also made just above the LCST. From the temperature dependence of these data, partial molar relative enthalpies (2,6-L), expansibilities and the temperature derivative of heat capacities were calculated and show that iBE undergoes a microphase transition at low concentration which is not related to the phase separation. On the other hand, the properties of 2,6-L in the water-rich region at temperatures well below the LCST indicates that this solute has only a slight tendency to associate. The heat capacities of 2,6-L show an important increase near the LCST. Such changes are not observed for iBE and other alkoxyethanols and amines since these systems already exist in the form of microphases; the partial molar properties of iBE near the LCST are nearly equal to the molar values of the pure liquid, and the changes in thermodynamic properties corresponding to the macroscopic phase transition, are therefore too small to be measured by the present techniques. 相似文献
100.
Christophe Biot Jean Dessolin Isabelle Ricard 《Journal of organometallic chemistry》2004,689(25):4678-4682
Starting from triazacyclononane, easily accessible ferrocenic quinoline derivatives were synthesized. Their antiplasmodial properties were investigated against chloroquine sensitive (HB3) and chloroquine-resistant (Dd2) Plasmodium falciparum. One of them, 7-chloro-4-[4-(7-chloro-4-quinolyl)-7-ferrocenylmethyl-1,4,7- triazacyclononan-1-yl]quinoline (4) showed potent antimalarial activity in vitro against the chloroquine-resistant strain Dd2 and therefore revealed to be the most promising lead from the present work for new organometallic antimalarial agents. 相似文献