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291.
Volodymyr Buturlim Michał Falkowski Mykhaylo Paukov Oleksandra Koloskova Daria Drozdenko Milan Dopita 《哲学杂志》2019,99(15):1881-1898
Uranium Laves phase UTi2 does not exist in a pure form, but can be stabilised by the presence of hydrogen, which can be absorbed in concentration exceeding 5?H atoms/f.u. Low temperature specific heat, magnetic susceptibility, and resistivity indicate that UTi2H5 is a spin fluctuator close to the verge of magnetic ordering. Its susceptibility follows at high temperatures the Curie–Weiss law with U effective moment µeff[ ?= 3.1?µB/U and paramagnetic Curie temperature Θp = ?200 K. The temperature dependence of specific heat exhibits a pronounced and weakly field dependent upturn in Cp/T versus T below 10 K reflecting the effect of spin fluctuations. It can be described by an additional T½ term. The Sommerfeld coefficient γ = 256?mJ/mol K2 classifies the compound as a mid-weight heavy fermion. Spin fluctuations are affecting also electrical and thermal transport and thermoelectric power, which all resemble UAl2. A lattice anomaly at ≈ 240?K, attributed to the melting of hydrogen sublattice, reflects in most of bulk properties. 相似文献
292.
Kamila Pruszkowska Olga A. Stasyuk Anna Zep Adam Krówczyński Rafal R. Sicinski Miquel Solà Michał K. Cyrański 《Chemphyschem》2022,23(2):e202100741
Two new square planar ONNO nickel(II) complexes C2_core and C3_core have been synthesized and characterized by single crystal X-ray diffraction, NMR spectroscopy, thermogravimetry, and DFT calculations. The experimental results revealed the effect of the length of diamine bridge in the ligand on the behavior of the studied complexes in the reaction with N-heterocyclic aromatic amines, while DFT calculations provided a basis for the rationalization of this observation. The complex with propylenediamine bridge ( C3_core ) readily reacts with pyridine and its derivatives to form high-spin (paramagnetic) complexes with octahedral geometry as characterized by X-ray diffraction; electron-donating substituents on the pyridine ring facilitate the coordination of axial ligands. In contrast, the complex with ethylenediamine bridge ( C2_core) does not undergo such a reaction because of the high deformation energy of the core required for the formation of C2_Py complex. 相似文献
293.
294.
We introduce a monoid corresponding to knotted surfaces in four space, from its hyperbolic splitting represented by marked diagram in braid like form. It has four types of generators: two standard braid generators and two of singular type. Then we state relations on words that follow from topological Yoshikawa moves. As a direct application we will reprove some known theorem about twist-spun knots. We wish then to investigate an index associated to the closure of surface singular braid. Using our relations we will prove that there are exactly six types of knotted surfaces with the index less or equal to two, and there are infinitely many types of surface-knots with index equal to three. Towards the end we will construct a family of classical diagrams such that to unlink them requires at least four Reidemeister III moves. 相似文献
295.
Weronika Buczyńska Jarosław Buczyński Kaie Kubjas Mateusz Michałek 《Central European Journal of Mathematics》2013,11(9):1577-1592
We study semigroups of labellings associated to a graph. These generalise the Jukes-Cantor model and phylogenetic toric varieties defined in [Buczynska W., Phylogenetic toric varieties on graphs, J. Algebraic Combin., 2012, 35(3), 421–460]. Our main theorem bounds the degree of the generators of the semigroup by g + 1 when the graph has first Betti number g. Also, we provide a series of examples where the bound is sharp. 相似文献
296.
We address the question of thermodynamical evolution of regular spherically symmetric cosmological black holes with de Sitter center. Space–time is asymptotically de Sitter as r→0 and as r→∞. A source term in the Einstein equations connects smoothly two de Sitter vacua with different values of cosmological constant and corresponds to anisotropic vacuum dark fluid defined by symmetry of its stress–energy tensor. In the range of masses Mcr1?M?Mcr2 it describes a regular cosmological black hole with three horizons, an internal horizon ra, a black hole horizon rb>ra, and a cosmological horizon rc>rb. Thermodynamical preference for a final product of evaporation is a double-horizon (ra=rb) black hole remnant with the positive specific heat. 相似文献
297.
Valsesia A Colpo P Meziani T Lisboa P Lejeune M Rossi F 《Langmuir : the ACS journal of surfaces and colloids》2006,22(4):1763-1767
This work presents an original and straightforward technique for antibody immobilization onto a surface, keeping the antibody in a biologically reactive configuration. Self-assembly of molecular monolayers and plasma-based colloidal lithography were combined to create chemical nanopatterns on the surface of a biosensing device. This technique was employed to create an array of 100 nm wide motifs having a hexagonal 2-D crystalline structure, characterized by COOH-terminated nanospots in a CH3-terminated matrix. The quality control of the chemical nanopattern was carried out by combining atomic force microscopy, ellipsometry, and contact angle measurements. Enzyme-linked immunosorbent assay experiments were set up showing that the COOH/CH3 nanopatterned surface constrains the immobilization of the antibodies in a biologically reactive configuration, thus significantly improving the device performances as compared to those of more conventional nonpatterned COOH-terminated or CH3-terminated surfaces. 相似文献
298.
Chrétien JM Zammattio F Gauthier D Le Grognec E Paris M Quintard JP 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(26):6816-6828
The preparation of polymer-supported allyltin reagents was shown to be possible for both unfunctionalized and functionalized allyl units. These reagents were treated with aldehydes in the presence of cerium(III) or indium(III) salts to afford high yields of homoallylic alcohols, practically uncontaminated with organotin residues (less than 5 ppm). Some mechanism aspects are briefly discussed and the potential for regeneration and reuse of these supported reagents is pointed out. 相似文献
299.
Although amide groups are important hydrogen-bond donors in natural and synthetic anion receptors, studies on structure-affinity relationships of amide-based macrocyclic receptors are still very limited. Therefore, we synthesized a series of macrocyclic tetraamides 5-8 derived from 1,3-benzenedicarboxylic (isophthalic) acid and aliphatic alpha,omega-diamines of different lengths. (1)H NMR titrations in DMSO solution show that the anion affinity of these receptors decreases with increasing size of the macrocycle irrespective of the anion, and this suggests a minor role of geometric complementarity. Comparison with their previously studied pyridine congeners reveals that the isophthalic acid based macrocycles are less potent, in contrast to what was found for simple model diamides. Combined theoretical and experimental structural studies were carried out to determine the reasons behind this behaviour. The results show that the unexpectedly low anion binding ability of the isophthalic acid-based receptors is due to the self-complementary nature of the isophthalic bis-amide fragments: when two such moieties are present within a sufficiently flexible macrocycle, they adopt syn-anti conformations and bind each other by two strong intramolecular hydrogen bonds that close the macrocyclic cavity. Nevertheless, anion binding is able to break these hydrogen bonds and switch a macrocycle into a convergent all-syn conformation. Despite the ill-preorganized conformation, 20-membered receptor 6 is better than either its open-chain analogue (macrocyclic effect) and/or its isomer having differently placed carbonyl groups. The crystal structures of four anion complexes of the macrocyclic receptors are reported. X-ray studies and solution NMR data confirmed the inclusive nature of the complexes and pointed to strong involvement of aromatic CH hydrogen atoms in anion binding. 相似文献
300.
A novel approach toward "locked" chlorins with increased stability has been studied in detail. The chlorin skeleton is assembled in a convergent fashion from two fragments via a porphyrin forming reaction, followed by 1,3-dipolar cycloaddition of azomethine ylides, which are formed in situ. Central to the success of the process is the presence of two electron-withdrawing groups in vicinal positions at the perimeter of the porphyrin. As a result, the 1,3-dipolar cycloaddition took place regioselectively, on the bond activated by two electron-withdrawing groups. Moreover, the chlorins formed are locked and hence more stable because of the presence of two quaternary carbon atoms. Overall, in just six steps locked chlorins were constructed from easily available materials. The large array of functionalities tolerated in this approach validates it for a broad use in more advanced studies. The correlation between the results of the 1,3-dipolar cycloaddition and dipolarophile (porphyrin) LUMO energy was extensively studied. There was a definite correlation between the reaction time and the LUMO energy level, and a partial correlation between the reaction yield and the distribution of the LUMO. Additionally, various approaches toward crucial building blocks, namely 3,4-disubstituted-2,5-diformylpyrroles, were investigated. 相似文献