全文获取类型
收费全文 | 2520篇 |
免费 | 85篇 |
国内免费 | 11篇 |
专业分类
化学 | 1589篇 |
晶体学 | 1篇 |
力学 | 78篇 |
数学 | 505篇 |
物理学 | 443篇 |
出版年
2023年 | 17篇 |
2022年 | 20篇 |
2021年 | 38篇 |
2020年 | 49篇 |
2019年 | 46篇 |
2018年 | 33篇 |
2017年 | 39篇 |
2016年 | 71篇 |
2015年 | 51篇 |
2014年 | 82篇 |
2013年 | 120篇 |
2012年 | 154篇 |
2011年 | 207篇 |
2010年 | 130篇 |
2009年 | 104篇 |
2008年 | 157篇 |
2007年 | 182篇 |
2006年 | 144篇 |
2005年 | 112篇 |
2004年 | 105篇 |
2003年 | 92篇 |
2002年 | 79篇 |
2001年 | 31篇 |
2000年 | 33篇 |
1999年 | 30篇 |
1998年 | 31篇 |
1997年 | 33篇 |
1996年 | 28篇 |
1995年 | 23篇 |
1994年 | 16篇 |
1993年 | 21篇 |
1992年 | 26篇 |
1991年 | 10篇 |
1990年 | 11篇 |
1989年 | 14篇 |
1988年 | 8篇 |
1987年 | 8篇 |
1986年 | 13篇 |
1985年 | 12篇 |
1984年 | 12篇 |
1983年 | 9篇 |
1982年 | 12篇 |
1981年 | 17篇 |
1980年 | 16篇 |
1979年 | 8篇 |
1978年 | 18篇 |
1977年 | 13篇 |
1976年 | 13篇 |
1975年 | 9篇 |
1974年 | 10篇 |
排序方式: 共有2616条查询结果,搜索用时 15 毫秒
981.
Comfort M. Nkambule Nomfundo W. KweziHenok H. Kinfe Mbulelo G. NokwequDavid W. Gammon Stefan Oscarson Erik Karlsson 《Tetrahedron》2011,67(3):618-623
A cis-1,2-cyclohexanediol, 1,4,5,6-tetra-O-benzyl-myo-inositol, was selectively protected at the axial C2-hydroxyl via acid-mediated rearrangement of the corresponding 1,2-orthoacetate, or via the base-induced migration of a protecting group that had previously been easily installed with complete regioselectivity at the adjacent equatorial hydroxyl. Esters 4a-6a were synthesized in high yields (75-82%) while sulfonate 7a and silyl ether 8a were obtained in 85 and 31% yields, respectively. The migration of the esters induced by DBU results in equilibrium between regioisomers favouring the C2 protected isomer, but NaH induced migration of sulfonyl and silyl groups results in complete migration from equatorial to axial hydroxyl groups. 相似文献
982.
983.
Cappel UB Plogmaker S Johansson EM Hagfeldt A Boschloo G Rensmo H 《Physical chemistry chemical physics : PCCP》2011,13(32):14767-14774
The energy loss in dye-sensitized solar cells calculated from the energy difference between the lowest electronic transition of the dye and the obtained open-circuit voltage is often 1 eV or even more. To minimize this loss, it is important to accurately determine the energy alignment at the TiO(2)/dye/redox-mediator interface. In this study, we compared the results from electrochemistry and photoelectron spectroscopy for determining the energy alignment of three rylene dyes, two of which absorb relatively far in the red. The trends observed with the methods were different, as in the former, the energy alignment is measured relative to an external reference and includes contributions from solvent reorganization energies, while in the latter, it is measured relative to the energetics of the TiO(2) and is lacking such contributions. The influence of the dyes' dipole moments on the energetics of the TiO(2) was also measured and explained some of the differences in trends. Finally, we compared the injection efficiencies of the two red-absorbing dyes and found that the differences in injection efficiencies can be better explained using the energy alignment determined from photoelectron spectroscopy. This shows that the method for measuring the energetics of a DSC should be chosen according to what process one intends to study. 相似文献
984.
985.
Daly AM Mitchell EG Sanchez DA Block E Kukolich SG 《The journal of physical chemistry. A》2011,115(50):14526-14530
The microwave spectrum for N-hydroxypyridine-2(1H)-thione (pyrithione) was measured in the frequency range 6-18 GHz, providing accurate rotational constants and nitrogen quadrupole coupling strengths for three isotopologues, C(5)H(4)(32)S(14)NOH, C(5)H(4)(32)S(14)NOD, and C(5)H(4)(34)S(14)NOH. Pyrithione was found to be in a higher concentration in the gas phase than the other tautomer, 2-mercaptopyridine-N-oxide (MPO). Microwave spectroscopy is best suited to determine which structure predominates in the gas phase. The measured rotational constants were used to accurately determine the coordinates of the substituted atoms and provided sufficient data to determine some of the important structural parameters for pyrithione, the only tautomer observed in the present work. The spectra were obtained using a pulsed-beam Fourier transform microwave spectrometer, with sufficient resolution to allow accurate measurements of the (14)N nuclear quadrupole hyperfine interactions. Ab initio calculations provided structural parameters and quadrupole coupling strengths that are in very good agreement with measured values. The experimental rotational constants for the parent compound are A = 3212.10(1), B = 1609.328(7), and C = 1072.208(6) MHz, yielding the inertial defect Δ(0) = -0.023 amu·?(2) for the C(5)H(4)(32)S(14)NOH isotopologue. The observed near zero inertial defect clearly indicates a planar structure. The least-squares fit structural analysis yielded the experimental bond lengths R(O-H) = 0.93(2) ?, R(C-S) = 1.66(2) ?, and angle (N-O-H) = 105(4)° for the ground state structure. 相似文献
986.
Arrays of supported lipid bilayers (SLBs) provide great potential for future drug development and multiplexed biological research, but are difficult to prepare due to the sensitivity of both the lipid and protein structural arrangement to air exposure. A novel way to produce arrays of SLBs is presented based on non-contact dispensing of vesicles to a substrate through a thin surface confined water film. The approach presents many degrees of freedom since it is not limited to a specific substrate, lipid composition, linker or controlled environment. The method allows adjustment of spot size (180-360 μm) by repeated dispensing as well as control over the composition of the spots and subsequent analytes. SLB formation by vesicle adsorption and rupture allows for incorporation of membrane proteins through pre-formed proteoliposomes. Dispensing through a dip-and-rinse water film avoids contamination, disruptive drying and the need for complex buffer compositions. Furthermore, no humidity control is necessary which simplifies the production step and prolongs the life-time of the spotting system. We characterize the method with respect to control over spot size, bilayer mobility and the formation process as well as demonstrate the possibility to fuse bilayer spots with subsequently added vesicles. Since complex lipid compositions and multiple spotting nozzles can be used, this novel technique is expected to be a promising platform for future applications, e.g. patterning to monitor peptide/protein-lipid interactions, for glycomics using glycolipids or lipopolysaccharides, and to study mixing of spatially confined lipid membranes. 相似文献
987.
988.
989.
Kapinos LE Operschall BP Larsen E Sigel H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(29):8156-8164
Adenosine (Ado) can accept three protons, at N1, N3, and N7, to give H(3) (Ado)(3+) , and thus has three macro acidity constants. Unfortunately, these constants do not reflect the real basicity of the N sites due to internal repulsions, for example, between (N1)H(+) and (N7)H(+). However, these macroconstants are still needed for the evaluations and the first two are taken from our own earlier work, that is, pK(H)(H(3))((Ado)) = -4.02 and pK(H)(H(2))((Ado)) = -1.53; the third one was re-measured as pK(H)(H)((Ado)) = 3.64 ± 0.02 (25 °C; I=0.5 M, NaNO(3)), because it is the main basis for evaluating the intrinsic basicities of N7 and N3. Previously, contradicting results had been published for the micro acidity constant of the (N7)H(+) site; this constant has now been determined in an unequivocal manner, and that of the (N3)H(+) site was obtained for the first time. The micro acidity constants, which describe the release of a proton from an (N)H(+) site under conditions for which the other nitrogen atoms are free and do not carry a proton, decrease in the order pk(N7-N1)(N7(Ado)N1·H)) = 3.63 ± 0.02 > pk(N7-N1)(H·N7(Ado)N1) = 2.15 ± 0.15 > pk(N3-N1,N7)(H·N3(Ado)N1,N7) =1.5 ± 0.3, reflecting the decreasing basicity of the various nitrogen atoms, that is, N1>N7>N3. Application of the above-mentioned microconstants allows one to calculate the percentages (formation degrees) of the tautomers formed for monoprotonated adenosine, H(Ado)(+) , in aqueous solution; the results are 96.1, 3.2, and 0.7% for N7(Ado)N1·H(+), (+)H·N7(Ado)N1, and (+)H·N3(Ado)N1,N7, respectively. These results are in excellent agreement with theoretical DFT calculations. Evidently, H(Ado)(+) exists to the largest part as N7(Ado)N1·H(+) having the proton located at N1; the two other tautomers are minority species, but they still form. These results are not only meaningful for adenosine itself, but are also of relevance for nucleic acids and adenine nucleotides, as they help to understand their metal ion-binding properties; these aspects are briefly discussed. 相似文献
990.
Among the fundamental transformations in the field of synthetic organic chemistry, transition-metal-catalyzed reactions provide some of the most attractive methodologies for the formation of C-C and C-heteroatom bonds. As a result, the application of these reactions has increased tremendously during the past decades and cross-coupling reactions became a standard tool for synthetic organic chemists. Furthermore, a tremendous upsurge in the development of new catalysts and ligands, as well as an increased understanding of the mechanisms, has contributed substantially to recent advances in the field. Traditionally, organic reactions are carried out by conductive heating with an external heat source (for example, an oil bath). However, the application of microwave irradiation is a steadily gaining field as an alternative heating mode since its dawn at the end of the last century. This tutorial review focuses on some of the recent developments in the field of cross-coupling reactions assisted by microwave irradiation. 相似文献