全文获取类型
收费全文 | 1684篇 |
免费 | 57篇 |
国内免费 | 12篇 |
专业分类
化学 | 1377篇 |
晶体学 | 23篇 |
力学 | 22篇 |
数学 | 121篇 |
物理学 | 210篇 |
出版年
2023年 | 10篇 |
2022年 | 16篇 |
2021年 | 20篇 |
2020年 | 23篇 |
2019年 | 34篇 |
2018年 | 24篇 |
2017年 | 16篇 |
2016年 | 48篇 |
2015年 | 30篇 |
2014年 | 44篇 |
2013年 | 117篇 |
2012年 | 97篇 |
2011年 | 112篇 |
2010年 | 77篇 |
2009年 | 59篇 |
2008年 | 109篇 |
2007年 | 89篇 |
2006年 | 89篇 |
2005年 | 88篇 |
2004年 | 80篇 |
2003年 | 77篇 |
2002年 | 57篇 |
2001年 | 19篇 |
2000年 | 17篇 |
1999年 | 22篇 |
1998年 | 16篇 |
1997年 | 25篇 |
1996年 | 13篇 |
1995年 | 13篇 |
1994年 | 20篇 |
1993年 | 20篇 |
1992年 | 18篇 |
1991年 | 20篇 |
1990年 | 9篇 |
1989年 | 9篇 |
1986年 | 10篇 |
1985年 | 14篇 |
1984年 | 21篇 |
1983年 | 10篇 |
1982年 | 18篇 |
1981年 | 12篇 |
1980年 | 11篇 |
1979年 | 8篇 |
1978年 | 8篇 |
1976年 | 13篇 |
1974年 | 13篇 |
1973年 | 8篇 |
1970年 | 9篇 |
1969年 | 11篇 |
1968年 | 7篇 |
排序方式: 共有1753条查询结果,搜索用时 15 毫秒
101.
Eiji Kobayashi Larisa S. Plashnitsa Takayuki Doi Shigeto Okada Jun-ichi Yamaki 《Electrochemistry communications》2010,12(7):894-896
All-solid-state phosphate symmetric cells using Li3V2(PO4)3 for both the positive and negative electrodes with the phosphate Li1.5Al0.5Ge1.5(PO4)3 as the solid electrolyte were proposed. Amorphous Li1.5Al0.5Ge1.5(PO4)3 was added into the electrode to increase the interface area between the active materials and the electrolyte. Any other phases were not formed at the electrode/electrolyte interface even after hot pressing at 600 °C. The discharge capacity was 92 mAh g? 1 at 22 µA cm? 2 at 80 °C, and 38 mAh g? 1 at 25 °C, respectively. Symmetric cell configuration leads to simplify the fabrication process for all-solid-state batteries and will reduce manufacturing costs. 相似文献
102.
SUPER TOUGH GELS WITH A DOUBLE NETWORK STRUCTURE 总被引:1,自引:0,他引:1
Tasuku Nakajima Takayuki Kurokawa Hidemitsu Furukawa Yoshimi Tanaka Yoshihito Osada 龚剑萍 《高分子科学》2009,27(1)
Living tissues work with fantastic functions in soft and wet gel-like state.Thus,hydrogels have attracted much attention as excellent soft and wet materials,suitable tot making artificial organs for medical treatments.However, conventional hydrogels are mechanically too weak for practical uses.We have created double network (DN) hydrogels with extremely high mechanical strength in order to overcome this problem.DN gels are interpenetrating network (IPN) hydrogels consisting of rigid polyelectrolyte and s... 相似文献
103.
Surface plasmon resonance sensor for lysozyme based on molecularly imprinted thin films 总被引:1,自引:0,他引:1
Molecularly imprinted polymers (MIPs) selective for lysozyme were prepared on SPR sensor chips by radical co-polymerization with acrylic acid and N,N′-methylenebisacrylamide. Gold-coated SPR sensor chips were modified with N,N′-bis(acryloyl)cystamine, on which MIP thin films were covalently conjugated. The presence of NaCl during the polymerization and the re-binding tests affected the selectivity and the optimization of NaCl concentration in the pre-polymerization mixture and the re-binding buffer could enhance the selectivity in the target protein sensing. When the lysozyme-imprinted polymer thin films were prepared in the presence of 40 mM NaCl, the selectivity factor (target protein bound/reference protein bound) of MIP in the re-binding buffer containing 20 mM NaCl was 9.8, meanwhile, that of MIP in the re-binding buffer without NaCl was 1.2. A combination of SPR sensing technology with protein-imprinted thin films is a promising tool for the construction of selective protein sensors. 相似文献
104.
Prof. Dr. Hiroyoshi Takamura Takayuki Fujiwara Yohei Kawakubo Prof. Dr. Isao Kadota Prof. Dr. Daisuke Uemura 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(6):1979-1983
Stereoselective and streamlined synthesis of the proposed C79–C104 fragment 2 of symbiodinolide ( 1 ), a polyol marine natural product with a molecular weight of 2860, was achieved. In the synthetic route, the proposed C79–C104 fragment 2 was synthesized by utilizing a Julia–Kocienski olefination and subsequent Sharpless asymmetric dihydroxylation as key transformations in a convergent manner. Detailed comparison of the 13C NMR chemical shifts between the natural product and the synthetic C79–C104 fragment 2 revealed that the stereostructure at the C91–C99 carbon chain moiety of symbiodinolide ( 1 ) should be reinvestigated. 相似文献
105.
Stereodivergent Synthesis and Stereochemical Reassignment of the C79–C104 Fragment of Symbiodinolide
Prof. Dr. Hiroyoshi Takamura Takayuki Fujiwara Yohei Kawakubo Prof. Dr. Isao Kadota Prof. Dr. Daisuke Uemura 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(6):1984-1996
We have synthesized eight possible diastereoisomers 3 a – h of the C79–C97 fragment of symbiodinolide ( 1 ) in a stereodivergent manner by utilizing a dithiane addition to the aldehyde as a key step. Comparison of the 13C NMR chemical shifts of the natural product 1 and the synthetic products 3 a – h indicated that the relative stereostructure of this fragment in symbiodinolide ( 1 ) is that represented in 3 a or f . We have stereodivergently synthesized eight possible diastereoisomers of the C94–C104 fragment 4 a – h , and we have compared their 13C NMR chemical shifts with those of the natural product, which established the relative stereochemistry of this fragment to be that described in diastereoisomers 4 a or e . By combining the stereostructural outcomes of the C79–C97 and C94–C104 fragments, we have proposed four candidate compounds of the C79–C104 fragment 2 a – d . We also synthesized diastereoisomers 2 a and b ( 2 a in the preceding article; Chem. Eur. J. 2015 , DOI: 10.1002/chem.201503880) by a Julia–Kocienski olefination and diastereoisomers 2 c and d by a Wittig reaction. By comparing the 13C NMR chemical shifts of natural symbiodinolide ( 1 ) with those of the synthetic products 2 a – d , we have reassigned the stereostructure of the C79–C104 fragment of natural product 1 to be that depicted in diastereoisomer 2 b . 相似文献
106.
Liquid crystalline (LC) polymer brushes containing a mesogenic azobenzene (Az) moiety are synthesized on a quartz or silicon substrate by surface-initiated atom transfer radical polymerization. The molecular orientation of the Az units and the LC properties in the grafted chains are evaluated by UV-vis spectroscopy, polarized optical microscopy, and grazing incidence X-ray diffraction measurements. The Az side chains of the grafted chains exhibited a smectic LC phase in which the smectic layers are oriented perpendicular to the substrate with a parallel orientation of the mesogens. In contrast, a spincast film of the identical LC polymer without grafting to the surface shows layer structures parallel to the substrate. A drastic effect of tethering one end to the substrate on the LC orientation is demonstrated. 相似文献
107.
Schröder G Okinaka T Mimura Y Watanabe M Matsuzaki T Hasuoka A Yamamoto Y Matsukawa S Akiba KY 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(9):2517-2529
All possible combinations of mixed pentaarylantimony compounds bearing p-methylphenyl and p-trifluoromethylphenyl groups were synthesized; ArnTol5-nSb (n=0-5: Ar=p-CF3C6H4, Tol=p-CH3C6H4): Tol5Sb (1), ArTol4Sb (2), Ar2Tol3Sb (3), Ar3Tol2Sb (4), Ar4TolSb (5), and Ar5Sb (6). Compounds 2-5 are the first well-characterized examples of mixed acyclic pentaarylantimony species. The structures of 2-6 were determined by X-ray crystallography to feature trigonal-bipyramidal (TBP) geometry with the more electronegative p-trifluoromethylphenyl substituents selectively occupying the apical positions. Consideration of the chemical shifts of the ipso carbons of the aryl and tolyl groups suggested that the solution structures of 1-6 were also TBP, although their pseudorotation could not be frozen even at -80 degrees C. Ligand-exchange reactions (LERs) took place between 1 and 6 at approximately 60 degrees C in [D6]benzene and all six species 1-6 were found in the equilibrium mixture. The relative stabilities of 1-6 were determined quantitatively by comparison of the observed molar ratios of 1-6 in equilibrium with calculated statistical molar ratios, and Ar2Tol3Sb (3) was found to be the most stable. The ligand-coupling reactions (LCRs) of 2-5 in solution were greatly accelerated by adding Cu(acac)2 or Li+TFPB- (TFPB: [3,5-(CF3)2 C6H3]4 B), whereby the rate becomes comparable to the LER. The use of flash vacuum thermolysis (FVT) allowed the LCR to occur with very little ligand-exchange; the exception ArTol4Sb had very fast ligand-exchange. The selectivities of the LCRs were calculated from the yield of the biaryls synthesized by using FVT. These results were highly consistent with reactions catalyzed in solution, in which bitolyl was not obtained at all. The experimental results suggested that the LCR of pentaarylantimony compounds proceeds in the manner of apical-apical coupling. 相似文献
108.
Takayuki Abe Shingo Higashide Mitsuhiro Inoue Satoshi Akamaru 《Plasma Chemistry and Plasma Processing》2007,27(6):799-811
Fine particles were modified with a thin film of SnO2 by using a barrel sputtering system that is a dry process. The conditions for the preparation of SnO2 were studied by reactive sputtering onto a glass plate substrate. The optimal conditions for the preparation of tetragonal
SnO2 were identified as 60% partial oxygen pressure and 1.0 Pa total gas pressure with the substrate at room temperature. Under
the optimized conditions, the surfaces of Al flake particles were modified with a thin film of SnO2. XRD and SEM/EDS analysis of the prepared samples showed that the Al particle surfaces were uniformly modified by a thin
film of SnO2 in all cases. The film thicknesses were 80, 130, and 180 nm at RF outputs of 195, 350, and 490 W. These measured thicknesses
coincided with the values estimated from the interference colors of the samples. 相似文献
109.
110.
Abou El-Nasr EA Fujii A Yahagi T Ebata T Mikami N 《The journal of physical chemistry. A》2005,109(11):2498-2504
Geometric structures and excited-state proton dislocation of size-selected salicylic acid clusters (salicylic acid and 5-methoxysalicylic acid) with water were studied by using laser spectroscopic techniques. Fluorescence excitation, dispersed fluorescence, and infrared (IR) spectra of those clusters in supersonic jets were examined for both the electronic ground (S0) and first excited (S1) states. The geometric structures of the clusters were determined on the basis of the IR spectra of the OH stretch region with the help of quantum chemical calculations. The hydroxyl group of the water moiety in the clusters forms a ring involving the carboxylic group of the salicylic acid moiety. The IR spectra in S0 show that the intramolecular hydrogen bond in the salicylic acid moiety is still held upon cluster formation, but the phenolic OH stretch band intensity is remarkably weaken in the clusters. The IR spectra in the S1 state and dispersed fluorescence spectra indicated that the intramolecular excited state proton dislocation is hardly affected by the microsolvation with water, in contrast with the strong suppression of the dislocation in the self-solvation. 相似文献