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排序方式: 共有842条查询结果,搜索用时 281 毫秒
91.
Lucimara Mendonça CostaEmerson Schwingel Ribeiro Mariana Gava SegatelliDanielle Raphael do Nascimento Fernanda Midori de OliveiraCésar Ricardo Teixeira Tarley 《Spectrochimica Acta Part B: Atomic Spectroscopy》2011,66(5):329-337
The present study describes the adsorption characteristic of Cd(II) onto Nb2O5/Al2O3 mixed oxide dispersed on silica matrix. The characterization of the adsorbent has been carried out by infrared spectroscopy (IR), scanning electronic microscopy (SEM), energy dispersive spectroscopy (EDS), energy dispersive X-ray fluorescence analysis (EDXRF) and specific surface area (SBET). From batch experiments, adsorption kinetic of Cd(II) was described by a pseudo-second-order kinetic model. The Langmuir linear isotherm fitted to the experimental adsorption isotherm very well, and the maximum adsorption capacity was found to be 17.88 mg g−1. Using the effective material, a method for Cd(II) preconcentration at trace level was developed. The method was based on on-line adsorption of Cd(II) onto SiO2/Al2O3/Nb2O5 at pH 8.64, in which the quantitative desorption occurs with 1.0 mol L−1 hydrochloric acid towards FAAS detector. The experimental parameters related to the system were studied by means of multivariate analysis, using 24 full factorial design and Doehlert matrix. The effect of SO42−, Cu2+, Zn2+ and Ni2+ foreign ions showed no interference at 1:100 analyte:interferent proportion. Under the most favorable experimental conditions, the preconcentration system provided a preconcentration factor of 18.4 times, consumption index of 1.08 mL, sample throughput of 14 h−1, concentration efficiency of 4.35 min−1, linear range from 5.0 up to 35.0 μg L−1 and limits of detection and quantification of 0.19 and 0.65 μg L−1 respectively. The feasibility of the proposed method for Cd(II) determination was assessed by analysis of water samples, cigarette sample and certified reference materials TORT-2 (Lobster hepatopancreas) and DOLT-4 (Dogfish liver). 相似文献
92.
Rivas MV De Leo LP Hamer M Carballo R Williams FJ 《Langmuir : the ACS journal of surfaces and colloids》2011,27(17):10714-10721
Metalloporphyrin molecules have a wide range of potential applications in diverse technological areas ranging from electronics to optoelectronics, electrochemistry, photophysics, chemical sensors, and catalysis. In particular, self-assembled monolayers of porphyrin molecules have recently attracted considerable interest. In this work we have studied for the first time the self-assembly of a novel Cu deutero porphyrin functionalized with disulfide moieties using electrochemical techniques, UV-vis absorption spectroscopy, polarization modulation infrared reflection absorption spectroscopy, and photoelectron spectroscopies (XPS and UPS). Experimental results indicate that the molecule adsorbs retaining its molecular integrity without forming molecular aggregates via the formation of Au-S covalent bonds. Furthermore, the monolayer consists of a packed array of molecules adsorbed with the plane of the porphyrin molecule at an angle of around 30° with respect to the surface normal. Interestingly, adsorption induces reduction of the Cu center and its consequent removal from the center of the porphyrin ring resulting in porphyrin demetalation. Our results are important in the design of self-assembled monolayers of metallo porphyrins where not only blocking of the metal center by the functional groups that drive the self-assembly should be considered but also possible adsorption induced demetalation with the consequent loss in the properties imparted by the metal center. 相似文献
93.
Chirea M Freitas A Vasile BS Ghitulica C Pereira CM Silva F 《Langmuir : the ACS journal of surfaces and colloids》2011,27(7):3906-3913
Gold nanowire networks (AuNWNs) with average widths of 17.74 nm (AuNWN(1)) or 23.54 nm (AuNWN(2)) were synthesized by direct reduction of HAuCl(4) with sodium borohydride powder in deep eutectic solvents, such as ethaline or reline, at 40 °C. Their width and length were dependent on the type of solvent and the NaBH(4)/HAuCl(4) molar ratio (32 in ethaline and 5.2 in reline). High resolution transmission electron microscopy (HR-TEM) analysis of the gold nanowire networks showed clear lattice fringes of polycrystalline nanopowder of d = 2.36, 2.04, 1.44, and 1.23 ? corresponding to the (111), (200), (220), or (311) crystallographic planes of face centered cubic gold. The purified AuNWNs were used as catalysts for the chemical reduction of p-nitroaniline to diaminophenylene with sodium borohydride in aqueous solution. The reaction was monitored in real time by UV-vis spectroscopy. The results show that the reduction process is six times faster in the presence of gold nanowire networks stabilized by urea from the reline (AuNWN(2)) than in the presence of gold nanowire networks stabilized by ethylene glycol from ethaline (AuNWN(1)). This is due to a higher number of corners and edges on the gold nanowires synthesized in reline than on those synthesized in ethaline as proven by X-ray diffraction (XRD) patterns recorded for both types of gold nanowire networks. Nevertheless, both types of nanomaterials determined short times of reaction and high conversion of p-nitroaniline to diaminophenylene. These gold nanomaterials represent a new addition to a new generation of catalysts: gold based catalysts. 相似文献
94.
Youssef El KhouryRuth Hielscher Mariana VoicescuJulien Gross Petra Hellwig 《Vibrational Spectroscopy》2011,55(2):258-266
In this work we analyzed the specificity of the amide VI band for different types of secondary structure elements in protein structures. This band involves the bending motion of the CO group of the peptide chain that is typically observed in the spectral region from 590 to 490 cm−1. The infrared absorbance spectra of a set of polypeptide model compounds of well known secondary structure was obtained at defined pH, including poly (l-lysine), poly (l-tyrosine), poly (l-alanine) and poly (l-histidine). In addition spectra of membrane proteins from the respiratory chain, namely the NADH:ubiquinone oxidoreductase, the cytochrome c oxidase and its CuA fragment, the cytochrome bc1 complex, a Rieske-type protein and in addition myoglobin, have been comparatively investigated. The systematic analysis of the amide VI band of the polypeptides and the proteins allowed correlating the signal appearing at ∼525 cm−1 to α-helical structures and signals at ∼545 cm−1 to β-sheet contributions. Random coils have been found to contribute at ∼535 cm−1 while the β-turns were observed at ∼560 cm−1. 相似文献
95.
Silva NL Betancur GJ Vasquez MP Gomes Ede B Pereira N 《Applied biochemistry and biotechnology》2011,163(7):928-936
Current research indicates the ethanol fuel production from lignocellulosic materials, such as residual wood chips from the
cellulose industry, as new emerging technology. This work aimed at evaluating the ethanol production from hemicellulose of
eucalyptus chips by diluted acid pretreatment and the subsequent fermentation of the generated hydrolysate by a flocculating
strain of Pichia stipitis. The remaining solid fraction generated after pretreatment was subjected to enzymatic hydrolysis, which was carried out simultaneously
with glucose fermentation [saccharification and fermentation (SSF) process] using a strain of Saccharomyces cerevisiae. The acid pretreatment was evaluated using a central composite design for sulfuric acid concentration (1.0–4.0 v/v) and solid to liquid ratio (1:2–1:4, grams to milliliter) as independent variables. A maximum xylose concentration of 50 g/L
was obtained in the hemicellulosic hydrolysate. The fermentation of hemicellulosic hydrolysate and the SSF process were performed
in bioreactors and the final ethanol concentrations of 15.3 g/L and 28.7 g/L were obtained, respectively. 相似文献
96.
Dinorah Gambino Mariana FernándezDiego Santos Gustavo A. EtcheverríaOscar E. Piro Fernando R. PavanClarice Q.F. Leite Isabel TomazFernanda Marques 《Polyhedron》2011,30(7):1360-1366
In the search for gallium bioactive compounds five Ga(III) complexes, [GaIII(L-H)2](NO3), with tridentate salicylaldehyde semicarbazone derivatives as ligands (L) have been synthesized and characterized in the solid state and in solution by different techniques. The crystal structure of [GaIII(L4-H)2](NO3)·2H2O, where L4 is 3-ethoxysalicylaldehyde semicarbazone, was solved by X-ray diffraction methods. The gallium(III) ion is in a distorted octahedral environment, coordinated to two nearly planar and mutually perpendicular 3-ethoxysalicylaldehyde semicarbazonato anions acting as tridentate ligands through their phenol and carbonyl oxygen atoms and their azomethine nitrogen atom. Their biological potential has been explored by evaluating their activity on Mycobacterium tuberculosis, causative agent of tuberculosis, and their cytotoxicity on tumor cell lines. Three different human tumor cell lines were selected that show different degrees of resistance to metallodrugs: ovarian A2780 (low resistance), breast MCF7 (medium resistance) and prostate PC3 (high resistance) cells. Although the complexes have not shown activity on M. tuberculosis, complexation with gallium has led to the enhancement of the cytotoxic potencies of the organic compounds. Those complexes that contain a bromide substituent at the phenolate ring have shown the highest cytotoxicities. In particular, [GaIII(L2-H)2](NO3), where L2 is 5-bromosalicylaldehyde semicarbazone,·has shown a remarkable cytotoxicity on A2780 tumor cell line with an IC50 value of the same order than cisplatin (IC50 Ga-L2 = 2.4 ± 0.3 μM; IC50 cisplatin = 2.0 ± 0.1 μM, 72 h incubation at 37 °C). Interestingly, this complex has also shown moderate cytotoxicity against MCF7 and PC3 cells (IC50 MCF7 = 30 ± 6; IC50 PC3 = 18 ± 3 μM). Therefore, this gallium compound could be considered a promising wide spectrum potential anti-tumor agent. 相似文献
97.
98.
Heparin Binding by Murine Recombinant Prion Protein Leads to Transient Aggregation and Formation of RNA-Resistant Species 总被引:1,自引:0,他引:1
Vieira TC Reynaldo DP Gomes MP Almeida MS Cordeiro Y Silva JL 《Journal of the American Chemical Society》2011,133(2):334-344
The conversion of cellular prion protein (PrP(C)) into the pathological conformer PrP(Sc) requires contact between both isoforms and probably also requires a cellular factor, such as a nucleic acid or a glycosaminoglycan (GAG). Little is known about the structural features implicit in the GAG-PrP interaction. In the present work, light scattering, fluorescence, circular dichroism, and nuclear magnetic resonance (NMR) spectroscopy were used to describe the chemical and physical properties of the murine recombinant PrP 23-231 interaction with low molecular weight heparin (LMWHep) at pH 7.4 and 5.5. LMWHep interacts with rPrP 23-231, thereby inducing transient aggregation. The interaction between murine rPrP and heparin at pH 5.5 had a stoichiometry of 2:1 (LMWHep:rPrP 23-231), in contrast to a 1:1 binding ratio at pH 7.4. At binding equilibrium, NMR spectra showed that rPrP complexed with LMWHep had the same general fold as that of the free protein, even though the binding can be indicated by significant changes in few residues of the C-terminal domain, especially at pH 5.5. Notably, the soluble LMWHep:rPrP complex prevented RNA-induced aggregation. We also investigated the interaction between LMWHep and the deletion mutants rPrP Δ51-90 and Δ32-121. Heparin did not bind these constructs at pH 7.4 but was able to interact at pH 5.5, indicating that this glycosaminoglycan binds the octapeptide repeat region at pH 7.4 but can also bind other regions of the protein at pH 5.5. The interaction at pH 5.5 was dependent on histidine residues of the murine rPrP 23-231. Depending on the cellular milieu, the PrP may expose different regions that can bind GAG. These results shed light on the role of GAGs in PrP conversion. The transient aggregation of PrP may explain why some GAGs have been reported to induce the conversion into the misfolded, scrapie conformation, whereas others are thought to protect against conversion. The acquired resistance of the complex against RNA-induced aggregation explains some of the unique properties of the PrP interaction with GAGs. 相似文献
99.
Fijalkowski KJ Genova RV Filinchuk Y Budzianowski A Derzsi M Jaroń T Leszczyński PJ Grochala W 《Dalton transactions (Cambridge, England : 2003)》2011,40(17):4407-4413
We describe the successful synthesis of the first mixed-cation (pseudoternary) amidoborane, Na[Li(NH(2)BH(3))(2)], with theoretical hydrogen capacity of 11.1 wt%. Na[Li(NH(2)BH(3))(2)] crystallizes triclinic (P1) with a = 5.0197(4) ?, b = 7.1203(7) ?, c = 8.9198(9) ?, α = 103.003(6)°, β = 102.200(5)°, γ = 103.575(5)°, and V = 289.98(5) ?(3) (Z = 2), as additionally confirmed by Density Functional Theory calculations. Its crystal structure is topologically different from those of its orthorhombic LiNH(2)BH(3) and NaNH(2)BH(3) constituents, with distinctly different coordination spheres of Li (3 N atoms and 1 hydride anion) and Na (6 hydride anions). Na[Li(NH(2)BH(3))(2)], which may be viewed as a product of a Lewis acid (LiNH(2)BH(3))/Lewis base (NaNH(2)BH(3)) reaction, is an important candidate for a novel lightweight hydrogen storage material. The title material decomposes at low temperature (with onset at 75 °C, 6.0% mass loss up to 110 °C, and an additional 3.0% up to 200 °C) while evolving hydrogen contaminated with ammonia. 相似文献
100.
This paper studies the asymptotic behavior of the steady-state waiting time, W ∞, of the M/G/1 queue with Subexponential processing times for different combinations of traffic intensities and overflow levels. In particular, we provide insights into the regions of large deviations where the so-called heavy-traffic approximation and heavy-tail asymptotic hold. For queues whose service time distribution decays slower than \(e^{-\sqrt{t}}\) we identify a third region of asymptotics where neither the heavy-traffic nor the heavy-tail approximations are valid. These results are obtained by deriving approximations for P(W ∞>x) that are either uniform in the traffic intensity as the tail value goes to infinity or uniform on the positive axis as the traffic intensity converges to one. Our approach makes clear the connection between the asymptotic behavior of the steady-state waiting time distribution and that of an associated random walk. 相似文献