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941.
Qing Guo He~ 《中国化学快报》2008,19(4):431-434
A binaphthyl derivative with pyrene on 3 and 3' positions was synthesized and characterized via Suzuki coupling reaction. Emission maximum in solution was located at 390 nm with a quantum efficiency of 68% by taking 9,10-diphenyl anthracene as reference,while it is shifted to 450 nm with FWHM of 104 nm resulting from aggregation state in solid film.Glass transition temperature(Tg)and decomposition temperature were measured to be 184 and 447℃,respectively,by DSC and TGA.Unlike its photoluminescence spectrum,electroluminescent spectrum peaked at about 460 nm and shows a FWHM of 69 nm corresponding to a pure blue emission.The turn-on voltage,luminance and efficiency maximum were 5 V,2953 cd/m^2 and 1.37cd/A with CIE color coordinate of(0.16,0.15),in the device structure of ITO/NPB(40nm)/PY-BN-PY(15nm)/BPhen(40nm)/Mg:Ag. 相似文献
942.
Based on atmospheric chemical kinetics, the rate constant of overall pseudo-first order oxidation re-moval of gaseous pollutants (Kpor,T) is proposed to characterize the atmospheric oxidation capacity in troposphere. Being a quantitative parameter, Kpor,T can be used to address the issues related to at-mospheric oxidation capacity. By applying this method, the regional oxidation capacity of the atmos-phere in Pearl River Delta (PRD) is numerically simulated based on CBM-IV chemical mechanism. Re-sults show the significant spatio-temporal variation of the atmospheric oxidation capacity in PRD. It is found that OH initiated oxidations, heterogeneous oxidation of SO2, and photolysis of aldehydes are the three most important oxidation processes influencing the atmospheric oxidation capacity in PRD. 相似文献
943.
Tao Liu Xin Zhou FuQuan Bai JianPo Zhang BaoHui Xia QingJiang Pan HongXing Zhang 《中国科学B辑(英文版)》2008,51(12):1211-1220
A series of ruthenium(II) complexes Ru(fppz)2(CO)L [fppz = 3-trifluoromethyl-5(2-pyridyl)pyrazole; L = pyridine (1), 4-dimethylaminopyridine (2), 4-cyanopyridine (3)]
were designed and investigated theoretically to explore their electronic structures, absorption, and emissions as well as
the solvatochromism. The singlet ground state and triplet excited state geometries were fully optimized at the B3LYP/LANL2DZ
and CIS/LANL2DZ level, respectively. The HOMO of 1–3 is composed of dyz(Ru) atom and π(fppz). The LUMO of 1 and 2 is dominantly contributed by π*(fppz) orbital, but that of 3 is contribute by π*(L).
Absorption and phosphorescence in vacuo, C6H12, and CH3CN media were calculated using the TD-DFT level of theory with the PCM model based on the optimized ground and excited state
geometries, respectively. The lowest-lying absorption of 1 and 2 at 387 and 391 nm is attributed to {[dyz(Ru) + π(fppz)] → [π*(fppz)]} transition, but that of 3 at 479 nm is assigned to {[dyz(Ru) + π(fppz)] → [π*(L)]} transition. The phosphorescence of 1 and 2 at 436 and 438 nm originates from 3{[dyz(Ru) + π(fppz)] [π*(fppz)]} excited state, while that of 3 at 606 nm is from 3{[dyz(Ru) + π(fppz)] [π*(L)]} excited state. The calculation results showed that the absorption and emission transition character
can be changed from MLCT/ILCT to MLCT/LLCT transition by altering the substituent on the L ligand. The phosphorescence of
1 and 2 does not have solvatochromism, but that of 3 at 606 nm (vacuo), 584 nm (C6H12), and 541 nm (CH3CN) is strongly dependent on the solvent polarity, so introducing electron-withdrawing group on ligand L will induce remarkable
solvatochromism.
Supported by the National Natural Science Foundation of China (Grant Nos. 20573042, 20703015, and 20333050) 相似文献
944.
This paper reports two important results with cross-linked precipitation polymerization. (1) Acetonitrile, a substance harmful to human health, is the most commonly used solvent for the synthesis of cross-linked polymeric microspheres by precipitation polymerization. Here, the much safer acetic acid replaced acetonitrile as a solvent in the precipitation polymerization of monodisperse cross-linked poly(divinylbenzene) (PDVB-55) microspheres. Pumpkin-like particles and microspheres were obtained. XPS results displayed a significant amount of double bonds on the surface of the particles. The effect of monomer content, temperature, and initiator amount on the formed particles were studied. For a DVB loading below 1 vol % at 70 degrees C, monodisperse microspheres with smooth surfaces and narrow diameters were successfully obtained. With a DVB loading of 2 vol % and by observing the shapes of particles obtained with three different temperature(60, 70, and 80 degrees C), we found that more spherical particles were obtained at higher temperatures and pumpkin-like particles were obtained at lower temperatures. No significant differences in morphology or the coefficient of variation (CV) of the particles were obtained for different initiator loadings, whereas the particle diameters could be increased with increased initiator concentrations. (2) In order to obtain a better understanding of the formation mechanism of these particles, time-dependent experiments, for the first time, were conducted in a hydrophobic monomer system. By tracing the whole polymerization process, some important results were found. First, with the polymerization time at 70 degrees C, the particle diameters were found to increase from 800 nm to 3.0 microm, the CV displayed a decrease, and the amount of spheres and the spherical evenness of the particle surfaces improved. Second, by quantitatively calculating the particle number from the yields and diameters data, it is found that starting from 3.1% yield or two hours reaction time the total amount of particles in the system is almost a constant (about 9.6 x 10 (8)/L), which means that no homocoagulation occurred and no new particles were generated after nucleation, and there is a linear relation between cubic diameters and yields. These two results give us a distinct impression that particle growth almost comes from capturing of newly formed oligomers. Based on the above results, a scheme for the particle formation is proposed, which shows that that pumpkin-like particles are caused by a prolonged nucleation including the homocoagulation of primary nuclei. The growth of the particles includes two modes, an in situ surface polymerization of monomer and the adsorption of PDVB-55 oligomers. The differences between results in acetonitrile and in acetic acid (higher yields, smaller size, not spherical but pumpkin-like particles in acetic acid) were due to the lower solubilizability of acetic acid which is the so-called proton-containing solvent with the hydrogen bonding structure. 相似文献
945.
Dr. Peng Luo Dr. Xue-Jing Zhai Dr. Sha Bai Dr. Yu-Bing Si Dr. Xi-Yan Dong Prof. Dr. Ying-Feng Han Prof. Dr. Shuang-Quan Zang 《Angewandte Chemie (International ed. in English)》2023,62(22):e202219017
Chiral Au nanoclusters have promising application prospects in chiral sensing, asymmetric catalysis, and chiroptics. However, enantiopure superatomic homogold clusters with crystallographic structures emitting bright circularly polarized luminescence (CPL) remain challenging. In this study, we designed chiral N-heterocyclic carbenes (NHCs), and for the first time enantioselectively synthesized a pair of monovalent cationic superatomic Au13 clusters. This new enantiomeric pair of clusters has a quasi-C2 symmetric core and exhibited CPL with an unprecedent solution-state quantum yield (QY) of 61 % among those of the atomically precise Au nanoclusters. DFT calculations provided insights into the circular dichroism behavior, and revealed the origin of CPL from superatomic Au clusters. This work opens a new avenue for developing novel homochiral nanoclusters using chiral NHC ligands and provides fundamental understanding of the origin of the chiroptics of metal clusters. 相似文献
946.
Yan Bai Gui-Ying Xu Xia Xin Hong-Yuan Sun Hong-Xing Zhang Ai-You Hao Xiao-Deng Yang Lin Yao 《Colloid and polymer science》2008,286(13):1475-1484
The interaction between cetyltrimethylammonium bromide (CTAB) and β-cyclodextrin (β-CD) was studied via surface tension and
dilational viscoelasticity methods. The effect of sodium bromide and sodium chloride on the interaction between CTAB and β-CD
were studied as well. The surface tension isotherms provided a series of parameters, including apparent critical micelle concentration
(cmc*), surface tension at the cmc* (γcmc), stoichiometry of the complex (R), and the efficiency of adsorption (pC
20
). The addition of NaBr and NaCl decreases the cmc* of CTAB/β-CD solution. CTAB molecules enter the cavities of β-CD molecules
thus formed both 1:1 and 1:2 inclusion complexes. From the change of γcmc, it can be seen that the CTAB/β-CD complexes (1:1) act as short-chain alcohol, which decrease γcmc, but the depression of cmc* is too small to be detected. R first decreases then increases as a function of NaBr and NaCl. Compared to NaCl, NaBr increases R more efficiently. The presence of NaBr and NaCl increases pC
20
of CTAB/β-CD solution. The results obtained from the dilational viscoelasticity measurements at low dilational frequencies
(0.005–0.1 Hz) reveal that the dilational modulus passes through a maxium value with increasing concentration of β-CD at a
given concentration of CTAB. The addition of both NaBr and NaCl decreases the dilational modulus of a given concentration
CTAB/β-CD solution.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
947.
948.
Fan LF He W Bai M Du Q Xiang B Chang YZ Cao DY 《Chemical & pharmaceutical bulletin》2008,56(8):1118-1125
The major objectives of this study were i) to evaluate the permeability and swelling characteristics of isolated films prepared by mixing of pectin with ethylcellulose; and ii) to assess the absorption and in vitro/in vivo correlation (IVIVC) of 5-FU film-coated colon-targeted pellets in dogs. Free films were prepared by casting and solvent evaporation method. These free films were evaluated by swelling experiment and permeability to 5-FU in different media. Pectin/ethylcellulose films had suitable characteristics for colonic delivery; and when the addition of pectin was up to the ratio of 30%, the swelling and permeability of the mixed films was significantly increased in the simulated colonic fluid (SCF). Pharmacokinetic study in dogs gave Tmax/Cmax of 14 h/1.6 microg/ml and 16 h/1.7 microg/ml for total weight gain (TWG)-22% and 18% coated pellets, respectively. The plasma 5-FU levels of the TWG-22% and 18% coated pellets were maintained at a much lower level with a mean residence time (MRT) of 18-20 h, longer than 2.1 h for 5-FU uncoated pellets, confirming delayed absorption. There was no statistically significant difference in the area under the plasma concentration vs. times curve (AUC) values between the uncoated pellets and the coated pellets. Moreover, a good linear regression relationship was observed between the percent in vitro dissolution in SCF and the percent absorption or percent AUC. It was concluded that i) pectin within the mixed films were susceptible to colonic enzymes, and the film-coated pellets are potentially useful for colonic drug delivery; and ii) in vitro dissolution testing in SCF could be used to establish certain IVIVC for the colon-specific drug delivery systems activated by microflora. 相似文献
949.
Willi R. Berg Dr. Jonathan F. Berengut Changzhuang Bai Dr. Laura Wimberger Prof. Lawrence K. Lee Dr. Felix J. Rizzuto 《Angewandte Chemie (International ed. in English)》2023,62(51):e202314458
Hierarchical DNA nanostructures offer programmable functions at scale, but making these structures dynamic, while keeping individual components intact, is challenging. Here we show that the DNA A-motif—protonated, self-complementary poly(adenine) sequences—can propagate DNA origami into one-dimensional, micron-length fibrils. When coupled to a small molecule pH regulator, visible light can activate the hierarchical assembly of our DNA origami into dissipative fibrils. This system is recyclable and does not require DNA modification. By employing a modular and waste-free strategy to assemble and disassemble hierarchical structures built from DNA origami, we offer a facile and accessible route to developing well-defined, dynamic, and large DNA assemblies with temporal control. As a general tool, we envision that coupling the A-motif to cycles of dissipative protonation will allow the transient construction of diverse DNA nanostructures, finding broad applications in dynamic and non-equilibrium nanotechnology. 相似文献
950.
Yinghao Liu Xingxing Wang Dr. Junyan Li Dr. Qiang Zhang Zijian Niu Dr. Sen Wang Yanjing Gao Mingkun Gao Dr. Risheng Bai Dr. Yida Zhou Dr. Weibin Fan Prof. Osamu Terasaki Prof. Jun Xu Prof. Jihong Yu 《Angewandte Chemie (International ed. in English)》2023,62(49):e202312131
Creation of intrapenetrated mesopores with open highway from external surface into the interior of zeolite crystals are highly desirable that can significantly improve the molecular transport and active sites accessibility of microporous zeolites to afford enhanced catalytic properties. Here, different from traditional zeolite-seeded methods that generally produced isolated mesopores in zeolites, nanosized amorphous protozeolites with embryo structure of zeolites were used as seeds for the construction of single-crystalline hierarchical ZSM-5 zeolites with intrapenetrated mesopores (mesopore volume of 0.51 cm3 g−1) and highly complete framework. In this strategy, in contrast to the conventional synthesis, only a small amount of organic structure directing agents and a low crystallization temperature were adopted to promise the protozeolites as the dominant growth directing sites to induce crystallization. The protozeolite nanoseeds provided abundant nucleation sites for surrounding precursors to be crystallized, followed by oriented coalescence of crystallites resulting in the formation of intrapenetrated mesopores. The as-prepared hierarchical ZSM-5 zeolites exhibited ultra-long lifetime of 443.9 hours and a high propylene selectivity of 47.92 % at a WHSV of 2 h−1 in the methanol-to-propylene reaction. This work provides a facile protozeolite-seeded strategy for the synthesis of intrapenetrated hierarchical zeolites that are highly effective for catalytic applications. 相似文献