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51.
The nanometer scale is a special place where all sciences meet and develop a particularly strong interdisciplinarity. While biology is a source of inspiration for nanoscientists, chemistry has a central role in turning inspirations and methods from biological systems to nanotechnological use. DNA is the biological molecule by which nanoscience and nanotechnology is mostly fascinated. Nature uses DNA not only as a repository of the genetic information, but also as a controller of the expression of the genes it contains. Thus, there are codes embedded in the DNA sequence that serve to control recognition processes on the atomic scale, such as the base pairing, and others that control processes taking place on the nanoscale. From the chemical point of view, DNA is the supramolecular building block with the highest informational content. Nanoscience has therefore the opportunity of using DNA molecules to increase the level of complexity and efficiency in self-assembling and self-directing processes. 相似文献
52.
Bruno Crociani Umberto Belluco Pierluigi Sandrini 《Journal of organometallic chemistry》1979,177(2):385-401
The reactions of the organometallic 1,4-diazabutadienes, RN=C(R′)C(Me)=NR″ [R = R″ = p-C6H4OMe, R′ = trans-PdCl(PPh3)2 (DAB); R = p-C6H4OMe, R″ = Me, R′ = trans-PdCl(PPh3)2 (DABI; R = R″ = p-C6H4OMe, R′ = Pd(dmtc)-(PPh3), dmtc = dimethyldithiocarbamate (DABII); R = R″ = p-C6H4OMe, R′ = PdCl(diphos), diphos = 1,2-bis(diphenylphosphino)ethane (DABIII)] with [RhCl(COD)]2 (COD = 1,5-cyclooctadiene, Pd/Rh ratio = ) depend on the nature of the ancillary ligands at the Pd atom in group R′. In the reactions with DAB and DABI transfer of one PPh3 ligand from Pd to Rh occurs yielding [RhCl(COD)(PPh3)] and the new binuclear complexes [Rh(COD) {RN=C(R?)-C(Me)=NR″}], in which the diazabutadiene moiety acts as a chelating bidentate ligand. Exchange of ligands between the two different metallic centers also occurs in the reaction with DABII. In this case, the migration of the bidentate dmtc anion yields [Rh(COD)Pdmtc] and [Rh(COD) {RN=C(R?)C(Me)=NR″}]. In contrast, the reaction with DABIII leads to the ionic product [Rh(COD)- (DABIII)][RhCl2(COD)], with no transfer of ligands. The cationic complex [Rh(COD)(DABIII)]+ can be isolated as the perchlorate salt from the same reaction (Pd/Rh ratio = 1/1) in the presence of an excess of NaClO4. In all the binuclear complexes the coordinated 1,5-cyclooctadiene can be readily displaced by carbon monoxide to give the corresponding dicarbonyl derivatives. The reaction of [RhCl(CO)2]2 with DAB and/or DABI yields trinuclear complexes of the type [RhCl(CO)2]2(DAB), in which the diazabutadiene group acts as a bridging bidentate ligand. Some reactions of the organic diazabutadiene RN=C(Me)C(Me)=NR (R = p-C6H4OMe) are also reported for comparison. 相似文献
53.
Bruno Gabutti 《Numerische Mathematik》1984,43(3):439-461
Summary The Euler-Knopp transformation and a recently considered transformation, effective for entire function of order 1, are applied to series involving completely monotonic coefficients. Some properties of the resulting series are analyzed; these include uniform convergence with respect to the index, a priori and a posteriori estimates of the remainder. For the latter transformation a compact recursive algorithm is established which enables one to make effective use of the transformation. To illustrate the effectiveness of the transformations three applications, with examples, are included. 相似文献
54.
Bruno Gabutti 《Zeitschrift für Angewandte Mathematik und Physik (ZAMP)》1984,35(3):265-281
Summary Considerf+
ff+ (1–f2)+
f=0 together with the boundary conditionsf(0)=f(0)=0,f ()=1. If=–1,>0, arbitrary there is at least one solution which satisfies 0<f<1 on (0, ). By the additional conditionf>0 on (0, ) or, alternately 0<1, the uniqueness of the solution is demonstrated.If=1,<0, arbitrary the existence of solutions for which –1<f<0 in some initial interval (0,t) and satisfying generallyf>1 is established. In both problems, bounds forf (0) and qualitative behavior of the solutions are shown.
Sommario Si consideri il problema definito dall'equazionef+ f f+ (1–f2)+ f=0 e dalle condizioni al contornof(0)=f (0)=0,f()=1. Assumendo=–1,>0, arbitrario si dimostra che esiste almeno una soluzione che soddisfa 0<f<1 nell'intervallo (0, ). Se in aggiunta si ipotizzaf>0 in (0, ), oppure 0<=1, l'unicità délia soluzione è assicurata.Successivamente si considéra il problema di valori al contorno con=1,<0, arbitrario. In questo caso esiste un'intera classe di soluzioni che soddisfano –1<f<0 in un intorno dell'origine e tali chef>1, in generale.Di detti problemi viene studiato il comportamento délle soluzioni e vengono determinate dalle maggiorazioni e minorazioni del valoref(0).相似文献
55.
Bellomio A Oliveira RG Maggio B Morero RD 《Journal of colloid and interface science》2005,285(1):118-124
Microcin J25 forms stable monolayers at the air-water interface showing a collapse at a surface pressure of 5 mN/m, 220 mV of surface potential, and 6 fV per squared centimeter of surface potential per unit of molecular surface density. The adsorption of microcin J25 from the subphase at clean interfaces leads to a rise of 10 mN/m in surface pressure and a surface potential of 220 mV. From these data microcin appears to be a poor surfactant per se. Nevertheless, the interaction with the lipid monolayer further increase the stability of the peptide at the interface depending on the mode in which the monolayer is formed. Spreading with egg PC leads to nonideal mixing up to 7 mN/m, with hyperpolarization and expansion of components at the interface, with a small excess free energy of mixing caused by favorable contributions to entropy due to molecular area expansion compensating for the unfavorable enthalpy changes arising from repulsive dipolar interactions. Above 7 mN/m microcin is squeezed out, leaving a film of pure phospholipid. Nevertheless, the presence of lipid at 10 and 20 mN/m stabilize further microcin at the interface and adsorption from the subphase proceeds up to 30 mN/m, equivalent to surface pressure in bilayers. 相似文献
56.
G. Bruno P. Capezzuto G. Cicala F. Cramarossa 《Plasma Chemistry and Plasma Processing》1986,6(2):109-125
Plasma-chemical reduction of SiCl4 in mixtures with H2 and Ar has been studied by optical emission spectroscopy (OES) and laser interferometry techniques. It has been found that the Ar:H2 ratio strongly affects the plasma composition as well as the deposition (r
D) and etch (r
E) rates of Si: H, Cl films and that the electron impact dissociation is the most important channel for the production of SiClx species, which are the precursors of the film growth. Chemisorption of SiClx and the reactive surface reaction SiClx+H–SiCl(x–1)0+HCl are important steps in the deposition process. The suggested deposition model givesr
D [SiClx][H], in agreement with the experimental data. Etching of Si: H, Cl films occurs at high Ar: H2 ratio when Cl atoms in the gas phase become appreciable and increases with increasing Cl concentration. The etch rate is controlled by the Cl atom chemisorption step. 相似文献
57.
Bruno Ameduri Bernard Boutevin Fouad Malek 《Journal of polymer science. Part A, Polymer chemistry》1994,32(16):3161-3169
The synthesis of maleimides that have pyrazolic or bipyrazolic pendant groups is described. Their homopolymerization and their copolymerization with 2-chloroethyl vinyl ether (CEVE) is reported. The homopolymerizations of such maleimides were performed under various conditions and led to low molecular-weight polymers. However, alternating copolymers were obtained from CEVE as comonomers whatever the monomers feed compositions. A similar behavior was also observed for maleimides that do not exhibit any spacer, whereas for bulky vinyl ethers, random copolymers were produced. A comparison of the thermal behavior between these copolymers (glass transition temperatures, Tg, and decomposition temperatures) and other copolymers having different spacers between the nitrogenated cycles and the chain are related. Thus, an important decrease of Tg, was observed when C3H6CO2CH2 groups were used as the spacer instead of methylene groups. Moreover, the thermal weakness of these copolymers may come from the substituents of the vinyl ether and is discussed. © 1994 John Wiley & Sons, Inc. 相似文献
58.
Bruno Jean Georges Bokias Lay-Theng Lee Ilias Iliopoulos Bernard Cabane 《Colloid and polymer science》2002,280(10):908-914
The structures of aqueous copolymer solutions have been examined through small angle neutron scattering. The copolymers contained mostly N-isopropylacrylamide (NIPAM) monomers. Poly (NIPAM) solutions have a lower critical solution temperature (LCST), above which the macromolecules separate from water. A small fraction of ionizable N,N-[(dimethylamino) propyl] methacrylamide (MADAP) monomers was introduced into the macromolecules. This had dramatic consequences on the solution behavior at temperatures above the LCST of PNIPAM, where phase separation would have been expected for the homopolymer. When all MADAP monomers were ionized, it was found that the solutions resisted the phase separation. At short spatial scales, the chains were collapsed but at large scales they formed branched aggregates that did not separate out of water. When only half of the MADAP monomers are ionized, the electrical charges were able to redistribute themselves along the chains. In this case, the rise in temperature caused a microphase separation where the electrical charges were relocated on a fraction of the chains that remained in solution.The other chains (or section of chains) formed large nodules of a polymer rich phase. 相似文献
59.
Zhdankin VV Maydanovych O Herschbach J Bruno J Matveeva ED Zefirov NS 《The Journal of organic chemistry》2003,68(3):1018-1023
The preparation and chemistry of novel phosphoranyl-derived lambda(3)-iodanes is reported. The phosphoranyl-derived phenyliodonium sulfonates were prepared in good yields by the reaction of stabilized phosphonium ylides [1-triphenylphosphoranylidene-2-propanone, methyl(triphenylphosphoranylidene)acetate, (triphenylphosphoranylidene)acetaldehyde, and (triphenylphosphoranylidene)acetonitrile] with the pyridinium complex of iodobenzene ditriflate or with [hydroxy(tosyloxy)iodo]benzene under mild conditions. These compounds represent a potentially useful class of reagents that combine in one molecule synthetic advantages of a phosphonium ylide and an iodonium salt. Specifically, phosphorane-derived phenyliodonium tosylates can react with soft nucleophiles, such as iodide, bromide, benzenesulfinate, and thiophenolate anions, with a selective formation of the respective alpha-functionalized phosphonium ylides, which can be further converted to alkenes by the Wittig reaction with benzaldehyde. The phosphoranyl-derived benziodoxoles can be prepared by the reaction of 1-acetoxybenziodoxole with stabilized phosphonium ylides. An unusual ligand exchange on the iodine(III) center resulting in the substitution of a carbon ligand with an oxygen ligand was observed in the reaction of these compounds with strong acids. 相似文献
60.
Calorimetric measurements of molar excess enthalpies, HE, at 298.15 K, of mixtures containing aromatic aldehydes of general formula C6H5(CH2)mCHO (with m = 0, 1 and 2) + n-hexane, n-heptane or benzene are reported, together with the values of HE at equimolar composition compared with the corresponding values of HE for the aromatic ketones in the same solvents. The experimental results clearly indicate that the intermolecular interactions between the carbonyl groups (CHO) are influenced by the intramolecular interactions between the carbonyl and phenyl groups, particularly for the mixtures containing benzaldehyde. 相似文献