全文获取类型
收费全文 | 420篇 |
免费 | 20篇 |
国内免费 | 3篇 |
专业分类
化学 | 331篇 |
晶体学 | 1篇 |
力学 | 7篇 |
数学 | 39篇 |
物理学 | 65篇 |
出版年
2024年 | 1篇 |
2023年 | 1篇 |
2022年 | 12篇 |
2021年 | 15篇 |
2020年 | 9篇 |
2019年 | 10篇 |
2018年 | 8篇 |
2017年 | 7篇 |
2016年 | 24篇 |
2015年 | 12篇 |
2014年 | 18篇 |
2013年 | 29篇 |
2012年 | 17篇 |
2011年 | 33篇 |
2010年 | 14篇 |
2009年 | 22篇 |
2008年 | 24篇 |
2007年 | 20篇 |
2006年 | 19篇 |
2005年 | 17篇 |
2004年 | 19篇 |
2003年 | 18篇 |
2002年 | 12篇 |
2001年 | 6篇 |
2000年 | 5篇 |
1999年 | 6篇 |
1998年 | 7篇 |
1997年 | 5篇 |
1996年 | 8篇 |
1995年 | 5篇 |
1994年 | 4篇 |
1993年 | 3篇 |
1992年 | 4篇 |
1990年 | 2篇 |
1989年 | 5篇 |
1986年 | 4篇 |
1985年 | 5篇 |
1984年 | 3篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1975年 | 3篇 |
1972年 | 1篇 |
排序方式: 共有443条查询结果,搜索用时 15 毫秒
1.
F. M. Bautista J. M. Campelo A. Garcia D. Luna J. M. Marinas A. A. Romero M. R. Urbano 《Reaction Kinetics and Catalysis Letters》1997,62(1):47-54
The vapor-phase catalytic alkylation of phenol with methanol and dimethyl carbonate on a series of differently prepared CrPO4 (Cr/P=1) and CrPO4-AlPO4 (CrAIP) catalysts, has been studied at different temperatures (473–673 K). The reaction is first order in phenol, giving
a mixture of O- and C-alkylated products (C-alkylation taking place preferentially at theortho-position). Moreover, dimethyl carbonate is a better methylating agent than methanol. 相似文献
2.
Carlos Cativiela Jos Ma Fraile Jos I. García Jos A. Mayoral Juan M. Campelo Diego Luna Jos M. Marinas 《Tetrahedron: Asymmetry》1993,4(12):2507-2512
Reactions of cyclopentadiene with several chiral acrylates are studied and compared with the same reactions catalysed by Zn(II)-exchanged K10 montmorillonite. In general, amorphous AlPO4 is a more efficient catalyst than the clay. In particular, the reaction of cyclopentadiene with (−)-8-phenylmenthyl acrylate leads to 74% diastereomeric excess (d.e.) in methylene chloride at low temperatures. This result constitutes the highest asymmetric induction described to date for a solid-catalysed asymmetric Diels-Alder reaction. When the reactions are carried out in the absence of a solvent a noticeable decrease in selectivity is observed, probably due to an extensive competition of the non-catalysed reaction. 相似文献
3.
Slaughter BD Unruh JR Price ES Huynh JL Bieber Urbauer RJ Johnson CK 《Journal of the American Chemical Society》2005,127(34):12107-12114
We used single-pair fluorescence resonance energy transfer (spFRET) measurements to characterize denatured and partially denatured states of the multidomain calcium signaling protein calmodulin (CaM) in both its apo and Ca(2+)-bound forms. The results demonstrate the existence of an unfolding intermediate. A CaM mutant (CaM-T34C-T110C) was doubly labeled with fluorescent probes AlexaFlour 488 and Texas Red at opposing globular domains. Single-molecule distributions of the distance between fluorophores were obtained by spFRET at varying levels of the denaturant urea. Multiple conformational states of CaM were observed, and the amplitude of each conformation was dependent on urea concentration, with the amplitude of an extended conformation increasing upon denaturation. The distributions at intermediate urea concentrations could not be adequately described as a combination of native and denatured conformations, showing that CaM does not denature via a two-state process and demonstrating that at least one intermediate is present. The intermediate conformations formed upon addition of urea were different for Ca(2+)-CaM and apoCaM. An increase in the amplitude of a compact conformation in CaM was observed for apoCaM but not for Ca(2+)-CAM upon the addition of urea. The changes in the single-molecule distributions of CaM upon denaturation can be described by either a range of intermediate structures or by the presence of a single unfolding intermediate that grows in amplitude upon denaturation. A model for stepwise unfolding of CaM is suggested in which the domains of CaM unfold sequentially. 相似文献
4.
A. Blanco J. M. Campelo A. Garcia D. Luna J. M. Marinas M. S. Moreno 《Reaction Kinetics and Catalysis Letters》1989,38(2):223-228
The effects of surface dehydration on textural properties, crystallinity and the structure of AlPO4–ZrO2 (weight ratio AlPO4/ZrO2=3) systems precipitated with ethylene oxide have been studied by N2 adsorption and XRD measurements. The increase in calcination temperature in the range 773–1273 K decreases the textural parameters as a consequence of AlPO4 crystallization to the tridymite form.
, AlPO4–ZrO2 ( AlPO4/ZrO2=3), , N2 - . 773 1273 , AlPO4 .相似文献
5.
In the present work, the nonisothermal imbibition process in a porous medium was numerically analyzed using a non-Darcian model for the momentum equation and energy equations for the wetting and dry zones. In order to show the thermal character of the problem, we assume initially that the porous medium is found at a uniform temperature T0 and suddenly begins the imbibition process into the porous medium with a penetrating fluid at temperature T1. The physical influence of nondimensional parameters such as Peclet number, Pe, effective heat capacity number, beta(w), porous Reynolds number, Re(p), and the inertial coefficient of the porous medium, F, serve us to evaluate the position and velocity of the imbibition front as well as temperature profiles in both zones. In particular, for values of Re(p)F/beta(w)>1, we recover a type of nonisothermal Washburn law. The numerical predictions show that the imbibition front and the temperature fields strongly depend on the above nondimensional parameters, revealing a clear deviation of the simple Washburn law. 相似文献
6.
Carmen Luna Concepción Lloreda Juan F. Almagro Bello Jaime Botella Maria J. Orts Ana Gozalbo 《Mikrochimica acta》2004,145(1-4):121-127
Non-metallic inclusions in steel are formed due to interactions between liquid steel and its environment in the melting shop (refractories and slags). Particles not trapped in the slag remain in the cast steel, impairing steel properties in service. Inclusion composition varies and certified standards covering the whole compositional range are unavailable.The present study describes the preparation of a set of homogeneous, glassy and crystalline standards with a wide compositional range for use in analysing non-metallic steel inclusions. For this, materials were designed based on knowledge of the compositional range of interest in the Al2O3–SiO2–CaO–MgO–CaF2 system, which is the matrix of the most frequent steel inclusions. The composition and microstructural homogeneity of the reference materials was verified. 相似文献
7.
Sander Bekeschus Lea Miebach Jonas Pommerening Ramona Clemen Katharina Witzke 《Molecules (Basel, Switzerland)》2022,27(14)
Gas plasma is an approved technology that generates a plethora of reactive oxygen species, which are actively applied for chronic wound healing. Its particular antimicrobial action has spurred interest in other medical fields, such as periodontitis in dentistry. Recent work has indicated the possibility of performing gas plasma-mediated biofilm removal on teeth. Teeth frequently contain restoration materials for filling cavities, e.g., resin-based composites. However, it is unknown if such materials are altered upon gas plasma exposure. To this end, we generated a new in-house workflow for three commonly used resin-based composites following gas plasma treatment and incubated the material with human HaCaT keratinocytes in vitro. Cytotoxicity was investigated by metabolic activity analysis, flow cytometry, and quantitative high-content fluorescence imaging. The inflammatory consequences were assessed using quantitative analysis of 13 different chemokines and cytokines in the culture supernatants. Hydrogen peroxide served as the control condition. A modest but significant cytotoxic effect was observed in the metabolic activity and viability after plasma treatment for all three composites. This was only partially treatment time-dependent and the composites alone affected the cells to some extent, as evident by differential secretion profiles of VEGF, for example. Gas plasma composite modification markedly elevated the secretion of IL6, IL8, IL18, and CCL2, with the latter showing the highest correlation with treatment time (Pearson’s r > 0.95). Cell culture media incubated with gas plasma-treated composite chips and added to cells thereafter could not replicate the effects, pointing to the potential that surface modifications elicited the findings. In conclusion, our data suggest that gas plasma treatment modifies composite material surfaces to a certain extent, leading to measurable but overall modest biological effects. 相似文献
8.
Bulk Free Radical Polymerization of Methyl Methacrylate and Vinyl Acetate: A Comparative Study 下载免费PDF全文
David Victoria‐Valenzuela Jorge Herrera‐Ordonez Gabriel Luna‐Barcenas George D. Verros Dimitris S. Achilias 《大分子反应工程》2016,10(6):577-587
The model and methodology for estimating diffusion‐controlled rate coefficients for the methyl methacrylate (MMA) polymerization system is extended to the vinyl acetate (VAc) case. Comparison of the kinetic behavior and termination rate coefficients (kt) of both monomers suggests that at low conversions the termination reaction is controlled by the chemical step, whereas at moderate and high conversions it is controlled by the diffusive step which in turn is determined by the segmental diffusion of the long radicals and not by the center of mass diffusion of short radicals. It is found that, for most of the conversion range, diffusion coefficient for VAc is lower than the one for MMA notwithstanding that ktVAc > ktMMA. An explanation of this apparent inconsistency on the base of the model results and in terms of segmental mobility is proposed.
9.
10.
Sebastian Weske Ramona Schoop Prof. Dr. Konrad Koszinowski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(32):11310-11316
Trifluoromethylation reactions have recently received increased attention because of the beneficial effect of the trifluoromethyl group on the pharmacological properties of numerous substances. A common method to introduce the trifluoromethyl group employs the Ruppert–Prakash reagent, that is, Si(CH3)3CF3, together with a copper(I) halide. We have applied this method to the trifluoromethylation of aromatic alkynes and used electrospray‐ionization mass spectrometry to investigate the mechanism of these reactions in tetrahydrofuran, dichloromethane, and acetonitrile as well as with and without added 1,10‐phenanthroline. In the absence of the alkyne component, the homoleptic ate complexes [Cu(CF3)2]? and [Cu(CF3)4]? were observed. In the presence of the alkynes RH, the heteroleptic complexes [Cu(CF3)3R]? were detected as well. Upon gas‐phase fragmentation, these key intermediates released the cross‐coupling products R?CF3 with perfect selectivity. Apparently, the [Cu(CF3)3R]? complexes did not originate from homoleptic cuprate anions, but from unobservable neutral precursors. The present results moreover point to the involvement of oxygen as the oxidizing agent. 相似文献