全文获取类型
收费全文 | 336篇 |
免费 | 16篇 |
专业分类
化学 | 259篇 |
晶体学 | 6篇 |
力学 | 10篇 |
数学 | 12篇 |
物理学 | 65篇 |
出版年
2023年 | 2篇 |
2022年 | 4篇 |
2021年 | 6篇 |
2020年 | 6篇 |
2019年 | 8篇 |
2017年 | 1篇 |
2016年 | 9篇 |
2015年 | 14篇 |
2014年 | 10篇 |
2013年 | 17篇 |
2012年 | 21篇 |
2011年 | 15篇 |
2010年 | 14篇 |
2009年 | 14篇 |
2008年 | 20篇 |
2007年 | 20篇 |
2006年 | 20篇 |
2005年 | 25篇 |
2004年 | 16篇 |
2003年 | 17篇 |
2002年 | 9篇 |
2001年 | 10篇 |
2000年 | 3篇 |
1999年 | 6篇 |
1998年 | 3篇 |
1997年 | 5篇 |
1996年 | 4篇 |
1995年 | 2篇 |
1994年 | 4篇 |
1993年 | 2篇 |
1992年 | 1篇 |
1991年 | 3篇 |
1990年 | 3篇 |
1989年 | 5篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1983年 | 5篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1975年 | 3篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1885年 | 1篇 |
1866年 | 2篇 |
排序方式: 共有352条查询结果,搜索用时 203 毫秒
51.
Amandine Pons Jean Michalland Wojciech Zawodny Yong Chen Veronica Tona Nuno Maulide 《Angewandte Chemie (International ed. in English)》2019,58(48):17303-17306
The ability of silicon to stabilize vinyl cationic species leads to a redox arylation of alkynes whereby the stringent limitations of reactivity and regioselectivity of alkyl‐substituted alkynes are lifted. This allows the synthesis of a range of α‐silyl‐α′‐arylketones under mild conditions in good to excellent yields and with high functional group tolerance, whereby the silicon moiety in the final products can either be removed for a formal acetone monoarylation transform, or capitalized upon for subsequent electrophilic substitutions at either side of the carbonyl group. 相似文献
52.
Characterization of a Novel Intrinsic Luminescent Room‐Temperature Ionic Liquid Based on [P6,6,6,14][ANS]
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Joana M. Delgado Dr. Anabela Raymundo Dr. Márcia Vilarigues Dr. Luís C. Branco Dr. César A. T. Laia 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(2):726-732
Intrinsically luminescent room‐temperature ionic liquids (RTILs) can be prepared by combining a luminescent anion (more common) or cation with appropriate counter ions, rendering new luminescent soft materials. These RTILs are still new, and many of their photochemical properties are not well known. A novel intrinsic luminescent RTIL based on the 8‐anilinonaphthalene‐1‐sulfonate ([ANS]) anion combined with the trihexyltetradecylphosphonium ([P6,6,6,14]) cation was prepared and characterized by spectroscopic techniques. Detailed photophysical studies highlight the influence of the ionic liquid environment on the ANS fluorescence, which together with rheological and 1H NMR experiments illustrate the effects of both the viscosity and electrostatic interactions between the ions. This material is liquid at room temperature and possesses a glass transition temperature (Tg) of 230.4 K. The fluorescence is not highly sensitive to factors such as temperature, but owing to its high viscosity, dynamic Stokes shift measurements reveal very slow components for the IL relaxation. 相似文献
53.
Morla A Poirier F Pons S Beaulieu C Charrier JP Ataman-Onal Y Gléhen O Jolivet M Choquet-Kastylevsky G 《Electrophoresis》2008,29(20):4158-4168
Proteomic approaches including high-resolution 2-DE are providing the tools needed to discover disease-associated biomarkers in complex biological samples. Although 2-DE is an extremely powerful approach to analyze the proteome, the separation of proteins with extreme molecular masses still remains an issue requiring improvement. Because high molecular mass (HMM) proteins larger than 150 kDa have already been observed to be differentially expressed in several pathologies such as cancer, we developed an original strategy to analyze this part of the proteome that is not easily separated by 2-DE in polyacrylamide gels. This strategy is based on the 2-DE separation of cyanogen bromide (CNBr) fragments of purified HMM protein fractions, and combines techniques including SEC fractionation, TCA precipitation, CNBr cleavage, 2-DE and MS analysis. The method was first tested on a model protein, the BSA. Preliminary results obtained using colonic tissues led to the identification of six HMM proteins with M(r) comprised between 163 and 533 kDa in their reduced state. These results demonstrated that our CNBr/2-DE approach should provide a powerful tool for identification of new biomarkers larger than 150 kDa. 相似文献
54.
Fibrobacter succinogenes S85, a strictly anaerobic Gram-negative bacterium, was grown in continuous culture in a bioreactor at different dilution rates (0.02 to 0.092 h(-1)) on a fully synthetic culture medium with glucose as carbon source. Glucose and ammonium sulfate consumption, as well as biomass, succinate, acetate, formate, and carbohydrate production were regularly measured. The relevant biomass elemental compositions were established for each dilution rate. Robustness of the experimental information was checked by C and N mass balances estimation, which were satisfactory. A detailed overall stoichiometry analysis of the process, including all substrates and products of the culture, was proposed. Online and off-line parameters measured during the culture brought a large number of data which were weighted by their respective variance associated to the measured value. The material balance resulted in an overdetermined linear system of equations made of weighted relationships including experimental data, elemental balances (C, H, O, N, S, Na), and an additional constraint. The mass balances involved in stoichiometric equations were solved using data reconciliation and linear algebra methods to take into account error measurements. This methodology allowed to establish the overall stoichiometric equation for each dilution rate studied. 相似文献
55.
Noir R Kotera M Pons B Remy JS Behr JP 《Journal of the American Chemical Society》2008,130(40):13500-13505
Synthesis of oligonucleotide probes and control of their hybridization temperature are key aspects of polymerase chain reaction (PCR)-based detection of genetic sequences. A straightforward means to approach the last goal is to decrease the repulsion between the polyanionic probe and target strands. To this end, we have developed a versatile automated synthesis of oligonucleotide-oligospermine derivatives that gave fast access to a large variety of compounds. Plots of their hybridization temperatures T(m) vs overall charge provided a measure of the impact of interstrand phosphate repulsion (and of spermine-mediated attraction) on the main driving force of duplex formation, i.e., base pairing. It showed that stabilization brought about by excess cationic charges can be of larger absolute magnitude than interstrand repulsion, even in high salt media. Base sequence and conjugation site (3' or 5') hardly influenced the effect of spermine on T(m). In typical PCR probe conditions, the T(m) increased linearly with the number of grafted spermines (e.g., 6.2 degrees C per spermine for a decanucleotide probe). The large data set of T(m) vs number of spermines and oligonucleotide length allowed us to empirically derive a simple mathematical relation that is accurately predicting the T(m) of any oligonucleotide-oligospermine derivative. Zip nucleic acids (ZNA) are thus providing an interesting alternative to locked nucleic acids (LNA) or minor groove binders (MGB) for raising the stability of 8-12-mer oligonucleotides up to ca. 70 degrees C, the level required for quantitative PCR experiments. 相似文献
56.
Hebden TJ Denney MC Pons V Piccoli PM Koetzle TF Schultz AJ Kaminsky W Goldberg KI Heinekey DM 《Journal of the American Chemical Society》2008,130(32):10812-10820
Reaction of NaBH4 with (tBuPOCOP)IrHCl affords the previously reported complex (tBuPOCOP)IrH2(BH3) (1) (tBuPOCOP = kappa(3)-C6H3-1,3-[OP(tBu)2]2). The structure of 1 determined from neutron diffraction data contains a B-H sigma-bond to iridium with an elongated B-H bond distance of 1.45(5) A. Compound 1 crystallizes in the space group P1 (Z = 2) with a = 8.262 (5) A, b = 12.264 (5) A, c = 13.394 (4) A, and V = 1256.2 (1) A(3) (30 K). Complex 1 can also be prepared by reaction of BH3 x THF with (tBuPOCOP)IrH2. Reaction of (tBuPOCOP)IrH2 with pinacol borane gave initially complex 2, which is assigned a structure analogous to that of 1 based on spectroscopic measurements. Complex 2 evolves H2 at room temperature leading to the borane complex 3, which is formed cleanly when 2 is subjected to dynamic vacuum. The structure of 3 has been determined by X-ray diffraction and consists of the (tBuPOCOP)Ir core with a sigma-bound pinacol borane ligand in an approximately square planar complex. Compound 3 crystallizes in the space group C2/c (Z = 4) with a = 41.2238 (2) A, b = 11.1233 (2) A, c = 14.6122 (3) A, and V = 6700.21 (19) A(3) (130 K). Reaction of (tBuPOCOP)IrH2 with 9-borobicyclononane (9-BBN) affords complex 4. Complex 4 displays (1)H NMR resonances analogous to 1 and exists in equilibrium with (tBuPOCOP)IrH2 in THF solutions. 相似文献
57.
58.
Antonio de León Josefina Pons Jordi García-Antón Xavier Solans Mercè Font-Bardia Josep Ros 《Polyhedron》2007
The reaction between 1,2-bis[3-(3,5-dimethyl-1-pyrazolyl)-2-thiapropyl]benzene (bddf) and [MCl2(CH3CN)2] (M = Pd(II), Pt(II)) in a 1:1 M/L ratio in CH2Cl2 or acetonitrile solution, respectively, gave the complexes trans-[MCl2(bddf)] (M = Pd(II) (1), Pt(II) (4)), and in a 2:1 M/L ratio led to [M2Cl4(bddf)] (M = Pd(II) (2), Pt(II) (5)). Treatment of 1 and 4 with AgBF4 and NaBPh4, respectively, gave the compounds [Pd(bddf)](BF4)2 (3) and [Pt(bddf)](BPh4)2 (6). When complexes 3 and 6 were heated under reflux in a solution of Et4NBr in CH2Cl2/CH3OH (1:1) for 24 h, analogous complexes to 1 and 4 with bromides instead of chlorides bonded to the metallic centre were obtained. These complexes were characterised by elemental analyses, conductivity measurements, infrared, 1H, 1H{195Pt}, 13C{1H}, 195Pt{1H} NMR, HSQC and NOESY spectroscopies. The X-ray crystal structure of the complex [Pd(bddf)](BF4)2 · H2O has been determined. The metal atom is tetracoordinated by the two azine nitrogen atoms of the pyrazole rings and two thioether groups. 相似文献
59.
Pina F Parola AJ Melo MJ Laia CA Afonso CA 《Chemical communications (Cambridge, England)》2007,(16):1608-1610
Photochromism of trans-4-(N,N-diethylamino)-2,4'-dihydroxychalcone, with formation of the photoproduct 7-(N,N-diethylamino)-4'-hydroxyflavylium, is promoted in the ionic liquid phase of a water/[bmim][PF6] biphasic system. 相似文献
60.
Glutathione (GSH) was assayed in must and wine using capillary electrophoresis coupled with laser-induced fluorescence (LIF) detection. Sample preparation involved conjugating thiols with monobromobimane (MBB) in a 2-(N-cyclohexylamino)ethanesulfonic acid [CHES] buffer (179mM). The electrophoretic conditions were 30kV with a capillary length of 105cm from the inlet to the detector (120cm total length) and a 50microm inner diameter. Under these conditions, the complete separation from the other main non-volatile thiols took less than 20min. We also described the optimum conditions for derivatizing wine samples with MBB to increase eletrophoretic sensitivity. The detection limit for glutathione assay is 65nmol/L. This simple, sensitive method provides a specific assay of glutathione in reduced form, as the sample preparation technique does not modify the balance of oxidized and reduced forms. We used this method to monitor changes in the reduced glutathione content of a white wine during alcoholic fermentation and barrel aging. 相似文献