全文获取类型
收费全文 | 3913篇 |
免费 | 116篇 |
国内免费 | 15篇 |
专业分类
化学 | 2532篇 |
晶体学 | 25篇 |
力学 | 143篇 |
数学 | 713篇 |
物理学 | 631篇 |
出版年
2023年 | 26篇 |
2022年 | 92篇 |
2021年 | 99篇 |
2020年 | 53篇 |
2019年 | 91篇 |
2018年 | 60篇 |
2017年 | 80篇 |
2016年 | 132篇 |
2015年 | 119篇 |
2014年 | 111篇 |
2013年 | 223篇 |
2012年 | 215篇 |
2011年 | 251篇 |
2010年 | 154篇 |
2009年 | 129篇 |
2008年 | 236篇 |
2007年 | 192篇 |
2006年 | 217篇 |
2005年 | 200篇 |
2004年 | 139篇 |
2003年 | 134篇 |
2002年 | 96篇 |
2001年 | 51篇 |
2000年 | 50篇 |
1999年 | 47篇 |
1998年 | 37篇 |
1997年 | 38篇 |
1996年 | 47篇 |
1995年 | 41篇 |
1994年 | 43篇 |
1993年 | 42篇 |
1992年 | 33篇 |
1991年 | 22篇 |
1990年 | 24篇 |
1989年 | 24篇 |
1988年 | 21篇 |
1987年 | 23篇 |
1986年 | 18篇 |
1985年 | 44篇 |
1984年 | 36篇 |
1983年 | 41篇 |
1982年 | 30篇 |
1981年 | 23篇 |
1980年 | 35篇 |
1979年 | 25篇 |
1977年 | 25篇 |
1976年 | 18篇 |
1975年 | 19篇 |
1974年 | 15篇 |
1973年 | 16篇 |
排序方式: 共有4044条查询结果,搜索用时 0 毫秒
111.
Martin Winter Wolfgang K. Appel Bernd Evers Tomásě Hodal Kai-Christian Möller Ingo Schneider Mario Wachtler Markus R. Wagner Gerhard H. Wrodnigg Jürgen O. Besenhard 《Monatshefte für Chemie / Chemical Monthly》2001,132(4):473-486
Summary. Rechargeable lithium ion cells operate at voltages of 3.5–4.5 V, which is far beyond the thermodynamic stability window of
the battery electrolyte. Strong electrolyte reduction and anode corrosion has to be anticipated, leading to irreversible loss
of electroactive material and electrolyte and thus strongly deteriorating cell performance. To minimize these reactions, anode
and electrolyte components have to be combined that induce the electrolyte reduction products to form an effectively protecting
film at the anode/electrolyte interface, which hinders further electrolyte decomposition reactions, but acts as membrane for
the lithium cations, i.e. behaving as a solid electrolyte interphase (SEI). This paper focuses on important aspects of the SEI. By using key examples,
the effects of film forming electrolyte additives and the change of the active anode material from carbons to lithium storage
alloys are highlighted.
Received May 30, 2000. Accepted June 14, 2000 相似文献
112.
The π*, α, and β Kamlet–Taft solvatochromic solvent parameters have been determined for nonaqueous binary mixtures commonly used in normal-phase liquid chromatography (NPLC), such as ethyl acetate n-hexane, tetrahydrofurane n-hexane, and 2-propanol n-hexane from spectroscopic data by using several UV-visible absorbing probes. Because preferential solvation is almost nonexistent for the π* probes in the different binary mixtures, we conclude that the measured values reflect quite well the dipolarity–polarizability of the bulk solution. However, strong preferential solvation for the different α and β probes in all mixtures studied here shows that the solvent parameters obtained reflect the properties of the solvation shell more than the bulk properties. This observation does not necessarily mean that the α and β values obtained will not be useful in multiple linear regressions (MLR), but results should be interpreted with care and will depend on the particular situation. Actually, results will make sense only if the particular solute under study preferentially solvates in a fashion similar to that of the α and β solvatochromic probes. 相似文献
113.
Barbara Fumić Marijana Zovko Končić Mario Jug 《Journal of inclusion phenomena and macrocyclic chemistry》2018,92(3-4):369-379
A novel sustainable and eco-friendly procedure simultaneously combining the use of ultrasound irradiation and hydroxypropyl-β-cyclodextrin (HPβCD) complexation was used to extract phytochemicals from Lotus corniculatus and to prepare flavonoid rich extract having potential as substrate reduction therapy of mucopolysaccharidosis type III (MPS III), a rare autosomal recessive lysosomal storage disorder. For that instance, Box-Behnken design and response surface methodology was employed to statistically assess the influence of HPβCD concentration, ultrasonic power, and extraction time on the total phenolic compounds, total flavonoids, total phenolic acids and radical scavenging activity (RSA) of the extracts prepared, chosen as the responses indicative of the product quality and performance. The potential of such optimised extract to modulate accumulation of gylcosoaminoglycans (GAGs) was evaluated on the fibroblast obtained from patients suffering from MPS type III. Optimized extract prepared by 45 min extraction using HPβCD at concentration of 20 mM and ultrasonic irradiation of 648 W was rich in flavonoids (1.36 mg/mL) and showed notable RSA of 1.04 mg/mL. Freeze-dried extract, at concentration of 3 and 6 µg/mL, reduced GAG levels in skin fibroblasts by 33.97 and 50.08%, respectively, without any toxic effects at given doses, showing a potential to be considered as a part of the substrate reduction therapy of MPS III. 相似文献
114.
Vanessa R. Machado Louis P. Sandjo Giovanni L. Pinheiro Milene H. Moraes Mario Steindel Moacir G. Pizzolatti 《Natural product research》2018,32(3):275-281
The natural product lupeol 1 was isolated from aerial parts of Vernonia scorpioides with satisfactory yield, which made it viable to be used as starting material in semisynthetic approach. Ten lupeol derivatives 2–11 were prepared by classical procedures. Including, five new esters derivatives 7–11, which were obtained by structural modifications in the isopropylidene fragment. All semisynthetic compounds and lupeol 1–11 were confirmed by 1H NMR, 13C NMR and HRMS. Their antiprotozoal activity was evaluated in vitro against L. amazonensis and T. cruzi. Derivative 6 showed the best antitrypanosomal activity (IC50 = 12.48 μg/mL) and the lowest cytotoxic derivative (CC50 = 161.50 μg/mL). The mechanism of action of the most active derivatives (4, 6 and 11) is not dependent from the enzyme trypanothione reductase. 相似文献
115.
Alejandro R. Engelmann Mario A. Natiello Mikael Hghede Erik Engdahl Erkki Brndas 《International journal of quantum chemistry》1987,31(5):841-845
In the present article we show how the bound states of the Coulomb potential may be associated with resonances that occur when this potential is perturbed by a barrier potential. The main idea is to trace the bound states on successive switching on of the barrier perturbation. It is found that those bound states that are localized inside the barrier are highly sensitive to variation with respect to the barrier height, whereas those that are localized outside are less sensitive. However, there are certain intervals for the barrier height when the role of being “a state localized inside the barrier” is shifted from one bound state to another. The result can be pictured as a “relay race,” where the “deliveries of the baton” are carried out over corresponding avoided crossings. The baton is ultimately handed over to a shape-type resonance state. 相似文献
116.
An experimental study of the dependence of the OH uptake coefficient gamma OH over a relative humidity of 0-48% was carried out at 100 Torr and room temperature, using a differential bead-filled flow tube coupled to a high-pressure chemical ionization mass spectrometer. Various organic (paraffin wax, pyrene, glutaric acid, and soot) and inorganic (NaCl, KCl, MgCl2, CaCl2, Na2SO4, and sea salt) surfaces served as proxies for tropospheric aerosols. A virtual cylindrical flow tube approximation and a surface coating dilution technique were successfully employed in the study, which included measurements of high radical uptake with an initial probability of near unity. For inorganic salts, the effect of water vapor, enhancement or inhibition of gamma OH, was found to be dependent on the blocking of anions and changes in surface pH. Although OH uptake by NaCl, the major component of sea-salt aerosols, is weakly dependent on water vapor, it is enhanced by a factor of approximately 2 for MgCl2 and determines the net relative humidity dependence of the radical uptake on sea salt, which is enhanced by a factor of approximately 4. For the organic surfaces studied, the enhancement effect of a factor 4 was also observed only for a hydrophilic organic surface, namely, glutaric acid. Results of the uptake studies suggest that the effect of relative humidity is important and should be accounted for in atmospheric modeling of tropospheric aerosol chemistry. 相似文献
117.
Kiani A Alpuche-Aviles MA Eggers PK Jones M Gooding JJ Paddon-Row MN Bard AJ 《Langmuir : the ACS journal of surfaces and colloids》2008,24(6):2841-2849
Electron transfer (ET) rate kinetics through n-alkanethiol self-assembled monolayers (SAMs) of alkanethiols of different chain lengths [Me(CH2)nSH; n=8, 10, 11, 15] on Au and Hg surfaces and ferrocene (Fc)-terminated SAMs (poly-norbornylogous and HS(CH2)12CONHCH2Fc) on Au were studied using cyclic voltammetry and scanning electrochemical microscopy (SECM). The SECM results allow determination of the ET kinetics of solution-phase Ru(NH3)63+/2+ through the alkanethiol SAMs on Au and Hg. A model using the potential dependence of the measured rate constants is proposed to compensate for the pinhole contribution. Extrapolated values of koML for Ru(NH3)63+/2+ using the model follow the expected exponential decay (beta is 0.9) for different chain lengths. For a Fc-terminated poly-norbornyl SAM, the standard rate constant of direct tunneling (ko is 189+/-31 s(-1)) is in the same order as the ko value of HS(CH2)12CONHCH2Fc. In blocking and Fc SAMs, the rates of ET are demonstrated to follow Butler-Volmer kinetics with transfer coefficients alpha of 0.5. Lower values of alpha are treated as a result of the pinhole contribution. The normalized rates of ET are 3 orders of magnitude higher for Fc-terminated than for blocking monolayers. Scanning electron microscopy imaging of Pd nanoparticles electrochemically deposited in pinholes of blocking SAMs was used to confirm the presence of pinholes. 相似文献
118.
Ligand-biased ensemble receptor docking (LigBEnD): a hybrid ligand/receptor structure-based approach
Polo C.-H. Lam Ruben Abagyan Maxim Totrov 《Journal of computer-aided molecular design》2018,32(1):187-198
Ligand docking to flexible protein molecules can be efficiently carried out through ensemble docking to multiple protein conformations, either from experimental X-ray structures or from in silico simulations. The success of ensemble docking often requires the careful selection of complementary protein conformations, through docking and scoring of known co-crystallized ligands. False positives, in which a ligand in a wrong pose achieves a better docking score than that of native pose, arise as additional protein conformations are added. In the current study, we developed a new ligand-biased ensemble receptor docking method and composite scoring function which combine the use of ligand-based atomic property field (APF) method with receptor structure-based docking. This method helps us to correctly dock 30 out of 36 ligands presented by the D3R docking challenge. For the six mis-docked ligands, the cognate receptor structures prove to be too different from the 40 available experimental Pocketome conformations used for docking and could be identified only by receptor sampling beyond experimentally explored conformational subspace. 相似文献
119.
James A. Cox Kamila M. Wiaderek B. Layla Mehdi Benjamin P. Gudorf David Ranganathan Silvia Zamponi Mario Berrettoni 《Journal of Solid State Electrochemistry》2011,15(11-12):2409-2417
Silica sol-gel (SG) films with templated pores were deposited on glassy carbon (GC) electrodes by an electrochemically initiated process. Generation-4 poly(amidoamine), PAMAM, dendrimer was included in the tetraethoxysilane precursor to facilitate pore formation. The PAMAM adsorbs to the GC, which blocks SG formation at those sites on the electrode. The pore size was 10?±?5?nm. After removal of the PAMAM, cyclic voltammetry of Fe(CN)6 3? and Ru(NH3)6 3+ at pH?6.2 showed that the residual negative charge on the silica attenuated the current for the former and increased the current for the latter, presumably by electrostatic repulsion and ion-exchange preconcentration, respectively. This premise was supported by repeating the measurements at the isoelectric point. Methylation of the silanol sites was used to eliminate the charge of the SG. At the end-capped SG, the voltammetry of Fe(CN)6 3? and Ru(NH3)6 3+ yielded currents that were independent of pH over the range 2.1 to 7.2. Circumventing the need for the silanization by using (3-glycidyloxypropyl)trimethoxysilane as the sol-gel precursor failed because the oxygen plasma treatment to remove the PAMAM attacked the organically modified sol-gel backbone. The resulting modified electrode mitigated the influence of proteins on the voltammetry of test species and stabilized functionalize nanoparticle catalysts under hydrodynamic conditions. 相似文献
120.
Serge Beaupr Michel Belletête Gilles Durocher Mario Leclerc 《Macromolecular theory and simulations》2011,20(1):13-18
A reliable model that can be used to estimate the electronic properties (i.e., the HOMO, LUMO, and band gap energies) of conjugated polymers would be a great tool for applications in organic electronics such as light‐emitting diodes, field‐effect transistors, and photovoltaic cells. Recently, poly(2,7‐carbazole) derivatives have shown promising results when used as an active donor layer in bulk heterojunction photovoltaic cells with power conversion efficiency exceeding 7%. By using a simple correlation between density functional theory (DFT) theoretical calculations performed on six model compounds (using the repeating unit) and experimental data from the six corresponding polymers, an accurate estimation of the HOMO energy level, the LUMO energy levels, and the band gap of several poly(2,7‐carbazole) derivatives was obtained. According to the theoretical data obtained for more than one hundred repeating units, fourteen new copolymers that can be used as p‐type materials in bulk heterojunction solar cells were selected and synthesized. Experimental data obtained from these materials were then used to refine the correlation between DFT and experimental data of poly(2,7‐carbazole) derivatives.