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41.
Krzysztof Matyjaszewski Przemysaw Kubisa Stanisaw Penczek 《Journal of polymer science. Part A, Polymer chemistry》1975,13(4):763-784
Polymerization of THF in CCl4 solvent was initiated with 1,3-dioxolan-2-ylium eations with AsF6?, PF6?, and SbF6? anions as well as with esters of fluorosulfonic and trifluoromethanesulfonic acids. With these esters polymerization proceeds with a marked acceleration period, due to slow initiation. The corresponding rate constants of initiation and their dependence on the polarity of the THF/CCl4 mixture were determined. The rate constant of propagation on the macroion-pairs (kp±) of the polytetrahydrofurylium cation with AsF6?, PF6?, and SbF6? and CF3SO3?, anions was found to be independent in CCl4 solvent on the anion structure and given by the expression: kp± = 2.93 × 10?2 exp {?4.7 × 103/T} at [THF]0 = 8.0M. This constant depends on the polarity of the polymerization mixture, and at 25°C for the THF-CCl4 system, kp± = 1.78 × 10?2 exp {?4.9/D}; thus, in CCl4 at [THF]0 = 8.0M, and at 25° kp± = 4.0 × 10?21/mole-sec. In the polymerization with derivatives of CF3SO3H (able to form the corresponding macroester) the overall polymerization rate is much lower than that with complex anions because of the reversible conversion of the macroion-pairs into the macroester (internal return). The macroester is much less reactive than the macroionpair (102–103 times) in the monomer addition reaction. At [THF]0 = 8.0M and at 25°C, 96.5% of the growing species exists in the macroester form. Polymerization of THF initiated with derivatives of CF3SO3H is a subject of a strong special salt-effect. At a sufficiently high ratio of [AgSbF6] to [I]0, where the initiator I is C2H5OSO2CF3, the overall polymerization rate is equal to that observed for the polymerization of THF on the macroion-pairs, since the internal return within the triflate ion-pair (the macroester formation) is eliminated and polymerization proceeds on the macroion-pairs with SbF6- anions exclusively. 相似文献
42.
The role of different H-bonds in phases II, III, IV, and V of triammonium hydrogen disulfate, (NH(4)(+))(3)H(+)(SO(4)(2)(-))(2), has been studied by X-ray diffraction and (1)H solid-state MAS NMR. The proper space group for phase II is C2/c, for phases III and IV is P2/n, and for phase V is P onemacr;. The structures of phases III and IV seem to be the same. The hydrogen atom participating in the O(-)-H(+).O(-) H-bond in phase II of (NH(4)(+))(3)H(+)(SO(4)(2)(-))(2) at room temperature is split at two positions around the center of the crucial O(-)-H(+).O(-) H-bonding, joining two SO(4)(2)(-) tetrahedra. With decreasing temperature, it becomes localized at one of the oxygen atoms. Further cooling causes additional differentiation of possibly equivalent sulfate dimers. The NH(4)(+) ions participate mainly in bifurcated H-bonds with two oxygen atoms from sulfate anions. On cooling, the major contribution of the bifurcated H-bond becomes stronger, whereas the minor one becomes weaker. This is coupled with rotation of sulfate ions. In all the phases of (NH(4)(+))(3)H(+)(SO(4)(2)(-))(2), some additional, weak but significant, reflections are observed. They are located between the layers of the reciprocal lattice, suggesting possible modulation of the host (NH(4)(+))(3)H(+)(SO(4)(2)(-))(2) structure(s). According to (1)H MAS NMR obtained for phases II and III, the nature of the acidic proton disorder is dynamic, and localization of the proton takes place in a broader range of temperatures, as can be expected from the X-ray diffraction data. 相似文献
43.
Maksymilian Chruszcz Krzysztof Lewinski 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(3):m150-m151
The structural data for sodium 2‐hydroxy‐5‐nitrobenzylsulfonate monohydrate, Na+·C7H6NO6S?·H2O, which mimics an artificial substrate for human arylsulfatase A, viz. p‐nitrocatechol sulfate, reveal that the geometric parameters of the substrate and its analogue are very similar. Two water molecules, the phenolic O atom and three sulfonate O atoms form the coordination sphere of the Na+ ion, which is a distorted octahedron. The Na+ cations and the O atoms join to form a chain polymer. 相似文献
44.
Anna Rakowska Robert Filipek Krzysztof Sikorski Marek Danielewski Renata Bachorczyk 《Mikrochimica acta》2004,145(1-4):183-186
The interdiffusion process in thin and thick (500nm–60µm) Au–Ni layers deposited on different substrates is studied using the EDS technique. In-depth X-ray analysis based on the Pouchou and Pichoir method is applied for obtaining the concentration profiles in nanometre scale multi-layers. A theoretical analysis using the Darken method is employed for modelling interdiffusion in the Au–Ni system. Computer simulations, where intrinsic diffusivities of the Au and Ni are functions of composition, are presented and compared with experimental results. 相似文献
45.
Jacek Gruszczak Michael Heller Zdzisław Pogoda 《International Journal of Theoretical Physics》1991,30(4):555-565
It is shown that if a space-time (M, g) is time-orientable and its Levi-Civita connection [in the bundle of orthonormal frames over (M, g)] is reducible to anO(3) structure, one can naturally select a nonvanishing timelike vector field and a Riemann metricg
+ onM. The Cauchy boundary of the Riemann space (M, g
+) consists of endpoints ofb-incomplete curves in (M, g); we call it theCauchy singular boundary. We use the space-time of a cosmic string with a conic singularity to test our method. The Cauchy singular boundary of this space-time is explicitly constructed. It turns out to consist of what should be expected. 相似文献
46.
Adams methods for neutral functional differential equations 总被引:1,自引:0,他引:1
Zdzisław Jackiewicz 《Numerische Mathematik》1982,39(2):221-230
Summary In this paper Adams type methods for the special case of neutral functional differential equations are examined. It is shown thatk-step methods maintain orderk+1 for sufficiently small step size in a sufficiently smooth situation. However, when these methods are applied to an equation with a non-smooth solution the order of convergence is only one. Some computational considerations are given and numerical experiments are presented. 相似文献
47.
Krzysztof Ejsmont Magorzata Broda Andrzej Domaski Janusz B. Kyzio Jacek Zaleski 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(9):o545-o548
The two isomeric compounds 4‐amino‐ONN‐azoxybenzene [or 1‐(4‐aminophenyl)‐2‐phenyldiazene 2‐oxide], i.e. the α isomer, and 4‐amino‐NNO‐azoxybenzene [or 2‐(4‐aminophenyl)‐1‐phenyldiazene 2‐oxide], i.e. the β isomer, both C12H11N3O, crystallized from a polar solvent in orthorhombic space groups, and their crystal and molecular structures have been determined using X‐ray diffraction. There are no significant differences in the bond lengths and valence angles in the two isomers, in comparison with their monoclinic polymorphs. However, the conformations of the molecules are different due to rotation along the Ar—N bonds. In the α isomer, the benzene rings are twisted by 31.5 (2) and 14.4 (2)° towards the plane of the azoxy group; the torsion angles along the Ar—N bond in the β isomer are 24.3 (3) and 23.5 (3)°. Quantum‐mechanical calculations indicate that planar conformations are energetically favourable for both isomers. The N—H?O hydrogen bonds observed in both networks may be responsible for the deformation of these flexible molecules. 相似文献
48.
49.
Krzysztof Winkler Alan L. Balch Włodzimierz Kutner 《Journal of Solid State Electrochemistry》2006,10(10):761-784
The recent results of investigations involving the electrochemical formation of polymers containing fullerenes and studies of their properties and applications are critically reviewed. From a structural point of view, these polymers can be divided into four main categories including (1) polymers with fullerenes physically incorporated into the foreign polymeric network without forming covalent bonds, (2) fullerene homopolymers formed via [2+2] cycloaddition, (3) “pearl necklace” polymers with fullerenes mutually linked covalently to form polymer chains, and (4) “charm bracelet” polymers containing pendant fullerene substituents. The methods of electrochemical polymerization of these systems are described and assessed. The structural features and properties of the electrochemically prepared polymers and their chemically synthesized analogs are compared. Polymer films containing fullerenes are electroactive in the negative potential range due to electroreduction of the fullerene moieties. Related films made with fullerenes derivatized with electron-donating moieties as building blocks are electroactive in both the negative and positive potential range. These can be regarded as “double cables” as they exhibit both p- and n-doping properties. Fullerene-based polymers may find numerous applications. For instance, they can be used as charge-storage and energy-converting materials for batteries and photoactive units of photovoltaic cell devices, respectively. They can be also used as substrates for electrochemical sensors and biosensors. Films of the C60/Pt and C60/Pd polymers containing metallic nano-particles of platinum and palladium, respectively, effectively catalyze the hydrogenation of olefins and acetylenes. Laser ablation of electrochemically formed C60/M and C70/M polymer films (M=Pt or Ir) results in fragmentation of the fullerenes leading to the formation of hetero-fullerenes, such as [C59M]+ and [C69M]+.Dedicated to Professor Dr. Alan M. Bond on the occasion of his 60th birthday. 相似文献
50.
Karolina Kucharska Marta Pilz Krzysztof Bielec Tomasz Kalwarczyk Patrycja Ku
ma Robert Hoyst 《Molecules (Basel, Switzerland)》2021,26(12)
The oxazole yellow dye, YOYO-1 (a symmetric homodimer), is a commonly used molecule for staining DNA. We applied the brightness analysis to study the intercalation of YOYO-1 into the DNA. We distinguished two binding modes of the dye to dsDNA: mono-intercalation and bis-intercalation. Bis-intercalation consists of two consecutive mono-intercalation steps, characterised by two distinct equilibrium constants (with the average number of base pair per binding site equals 3.5): and , respectively. Mono-intercalation dominates at high concentrations of YOYO-1. Bis-intercalation occurs at low concentrations. 相似文献