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101.
Reactive oxygen species (ROS) forming enzymes are of significant interest as anticancer agents due to their potent cytotoxicity. A key challenge in their clinical translation is attaining site‐specific delivery and minimizing biodistribution to healthy tissues. Here, complexes composed of the ROS enzyme glucose oxidase (GOX), poly‐l ‐lysine‐grafted‐polyethylene glycol (PLL‐g‐PEG), and anti‐prostate specific membrane antigen (anti‐PSMA) monoclonal antibody are synthesized for localized delivery and uptake in prostate cancer cells. Formation of anti‐PSMA‐PLL‐g‐PEG/GOX results in nanoscale complexes ≈30 nm in diameter with a ζ‐potential of 6 mV. The anti‐PSMA‐PLL‐g‐PEG/GOX complexes show significant cytotoxicity (≈60% reduction in cell viability) against PSMA‐expressing LNCaP cells compared to unmodified GOX. Importantly, cytotoxicity in LNCaP cells occurrs concurrently with anti‐PSMA‐PLL‐g‐PEG/GOX uptake and increases in intracellular generation of ROS. These results demonstrate that cytotoxicity of ROS inducing enzymes can be enhanced by intracellular delivery compared to equivalent concentrations of free enzyme, providing a novel means for cancer therapy. 相似文献
102.
The reaction of free base or Ni(II) complex secochlorin bisaldehydes 4H2 and 4Ni regenerates the ultimate starting material of the bisaldehydes, meso-tetraphenylporphyrin 2H2 and 2Ni, respectively. Depending on the reaction conditions employed (hydrazine hydrate in pyridine at reflux or hydrazine hydrate activated with sulfur in the presence of aqueous NaOH at ambient temperature), either porphyrin 2H2 is formed together with known dihydroxymorpholinochlorin 9H2 or known 2-hydroxychlorin 8H2. Two different reaction pathways for the hydrazine reaction can be derived, either involving the formation of a meso-tetraphenyl-1,4,5-triazepinoporphyrin that loses spontaneously N2 or a Wolff-Kishner-type pathway that also involves an intramolecular aldol-type reaction. Neither reaction is synthetically useful but both highlight in an impressive fashion the high thermodynamic stability of porphyrins. They also bring the ‘breaking and mending of porphyrin’ strategy to its ultimate conclusion by regenerating the starting porphyrin. 相似文献
103.
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105.
The trans-palladium bis(σ-acetylide) complex (Et3P)2Pd(C30H12) (2) was synthesized from hexane 4 in 77% yield via a simple three-step process. The X-ray crystal structure of 2 shows a strained and warped annulenic core upon insertion of the organometallic fragment. UV-vis data of the molecule suggest limited electronic delocalization throughout the metallacycle. 相似文献
106.
The interfacial tension of hybrids composed of a tin-based phosphate glass (Pglass) and thermoplastic polymers, low-density polyethylene (LDPE), polystyrene (PS), and polypropylene (PP) was investigated using pendant drop and droplet deformation methods. High surface tension values were determined for the pure Pglass and subsequently used to obtain interfacial tension values that were found to be greater than that of most polymer blends reported in the literature. Small amplitude oscillatory shear data were fitted to the Choi-Schowalter and Palierne emulsion models in order to estimate the interfacial tension and to validate the accuracy (or lack thereof) of using a polymer emulsion model on the special Pglass-polymer systems. Although some of the hybrids showed satisfactory agreement with the emulsion models, wide ranges of interfacial tensions were obtained, suggesting that a more complicated theory that explicitly takes the Pglass-polymer interactions, shape factor, and size distributions of the dispersed Pglass phase into account may be necessary for more accurate modeling of these special hybrid systems with enhanced benefits. 相似文献
107.
Van Veldhuizen JJ Gillingham DG Garber SB Kataoka O Hoveyda AH 《Journal of the American Chemical Society》2003,125(41):12502-12508
Design, synthesis, characterization, and catalytic activity of six enantiomerically pure Ru-based metathesis catalysts are disclosed (3a-3f). The new chiral catalysts were prepared through steric and electronic alterations of the parent catalyst system (3). The present studies indicate that the effect of structural modifications of chiral complex 3 does not always correspond to those of the related achiral complexes. The present findings illustrate that modified Ru complexes (3e and 3f) deliver reactivity levels that are more than 2 orders of magnitude higher than 3. Reactivity and physical data are provided that shed light on the origin of activity differences. Some members of the new generation of chiral Ru catalysts promote asymmetric ring-opening (AROM) and ring-closing (ARCM) metatheses that cannot be effected by the first generation chiral catalyst (3). 相似文献
108.
Williams JR Smalley AL Sellinschegg H Daniels-Hafer C Harris J Johnson MB Johnson DC 《Journal of the American Chemical Society》2003,125(34):10335-10341
A series of samples ((AB)(x)(CD)(y))(z) were prepared containing both short repeat units (AB and CD) and long repeat units ((AB)(x)(CD)(y)), where the short repeat units were designed to have the composition appropriate to form square M(4)Sb(12) skutterudites (M = Fe, Co, or Ir; square = vacancy, La, or Y). X-ray diffraction and reflectivity were used to follow the evolution of the films from amorphous, layered materials to crystalline skutterudite superlattices as a function of annealing temperature and time. In all cases, the short repeat units interdiffused and crystallized the expected skutterudite, while the long repeat period persisted after annealing. The skutterudites crystallize with random crystallographic orientation with respect to the substrate. The observed splitting of the peaks in the high-angle diffraction data from the IrSb(3)/CoSb(3) sample indicates the formation of a novel superlattice structure with each grain having a random crystallographic orientation of the skutterudite lattice with respect to the superlattice direction. 相似文献
109.
Dixon FM Masar MS Doan PE Farrell JR Arnold FP Mirkin CA Incarvito CD Zakharov LN Rheingold AL 《Inorganic chemistry》2003,42(10):3245-3255
The ligand 1,4-bis[4-(diphenylphosphino)butyl]-2,3,5,6-tetramethylbenzene, 3, was used to synthesize a mononuclear Rh(II) complex [(eta(1):eta(6):eta(1)-1,4-bis[4-(diphenylphosphino)butyl]-2,3,5,6-tetramethylbenzene)Rh][PF(6)](2), 6+, in a two-legged piano-stool geometry. The structural and electronic properties of this novel complex including a single-crystal EPR analysis are reported. The complex can be cleanly interconverted with its Rh(I) form, allowing for a comparison of the structural properties and reactivity of both oxidation states. The Rh(I) form 6 reacts with CO, tert-butyl isocyanide, and acetonitrile to form a series of 15-membered mononuclear cyclophanes [(eta(1):eta(1)-1,4-bis[4-(diphenylphosphino)butyl]-2,3,5,6-tetramethylbenzene)Rh(CO)(3)][PF(6)] (8), [(eta(1):eta(1)-1,4-bis[4-(diphenylphosphino)butyl]-2,3,5,6-tetramethylbenzene)Rh(CNC(CH(3))(3))(2)][PF(6)] (10), and [(eta(1):eta(1)-1,4-bis[4-(diphenylphosphino)butyl]-2,3,5,6-tetramethylbenzene)Rh(CO)(CH(3)CN)][PF(6)] (11). The Rh(II) complex 6+ reacts with the same small molecules, but over shorter periods of time, to form the same Rh(I) products. In addition, a model two-legged piano-stool complex [(eta(1):eta(6):eta(1)-1,4-bis[3-(diphenylphosphino)propoxy]-2,3,5,6-tetramethylbenzene)Rh][B(C(6)F(5))(4)], 5, has been synthesized and characterized for comparison purposes. The solid-state structures of complexes 5, 6, 6+, and 11 are reported. Structure data for 5: triclinic; P(-)1; a = 10.1587(7) A; b = 11.5228(8) A; c = 17.2381(12) A; alpha = 96.4379(13) degrees; beta = 91.1870(12) degrees; gamma = 106.1470(13) degrees; Z = 2. 6: triclinic; P(-)1; a = 11.1934(5) A; b = 12.4807(6) A; c = 16.1771(7) A; alpha = 81.935(7) degrees; beta = 89.943(1) degrees; gamma = 78.292(1) degrees; Z = 2. 6+: monoclinic; P2(1)/n; a = 11.9371(18) A; b = 32.401(5) A; c = 12.782(2) A; beta = 102.890(3) degrees; Z = 4. 11: triclinic; P(-)1; a = 13.5476(7) A; b = 13.8306(7) A; c = 14.9948(8) A; alpha = 74.551(1) degrees; beta = 73.895(1) degrees; gamma = 66.046(1) degrees; Z = 2. 相似文献
110.
Joshua Qingsong Li Ronald Salovey 《Journal of polymer science. Part A, Polymer chemistry》2000,38(17):3181-3187
A “continuous” emulsifier‐free emulsion copolymerization (CEFEP) of styrene and divinylbenzene (DVB) or methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDMA) has been devised to produce uniform polymeric microspheres of narrow size distribution from 74 nm to 2 μm, depending on reaction time. Monomer and crosslinker vapors were fed continuously into a small reactor. We suggest that after initial nucleation, subsequent CEFEP proceeds near the surfaces of growing particles in a monomer‐swollen outer shell. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3181–3187, 2000 相似文献