全文获取类型
收费全文 | 1535篇 |
免费 | 76篇 |
国内免费 | 7篇 |
专业分类
化学 | 1289篇 |
晶体学 | 12篇 |
力学 | 16篇 |
数学 | 83篇 |
物理学 | 218篇 |
出版年
2024年 | 3篇 |
2023年 | 21篇 |
2022年 | 18篇 |
2021年 | 20篇 |
2020年 | 34篇 |
2019年 | 49篇 |
2018年 | 38篇 |
2017年 | 18篇 |
2016年 | 38篇 |
2015年 | 59篇 |
2014年 | 55篇 |
2013年 | 94篇 |
2012年 | 105篇 |
2011年 | 101篇 |
2010年 | 71篇 |
2009年 | 63篇 |
2008年 | 111篇 |
2007年 | 86篇 |
2006年 | 116篇 |
2005年 | 109篇 |
2004年 | 89篇 |
2003年 | 67篇 |
2002年 | 54篇 |
2001年 | 12篇 |
2000年 | 13篇 |
1999年 | 10篇 |
1998年 | 8篇 |
1997年 | 8篇 |
1996年 | 10篇 |
1995年 | 8篇 |
1994年 | 8篇 |
1993年 | 10篇 |
1992年 | 6篇 |
1991年 | 5篇 |
1990年 | 5篇 |
1988年 | 6篇 |
1987年 | 3篇 |
1986年 | 3篇 |
1985年 | 8篇 |
1984年 | 3篇 |
1983年 | 8篇 |
1982年 | 9篇 |
1981年 | 11篇 |
1980年 | 8篇 |
1979年 | 4篇 |
1978年 | 10篇 |
1977年 | 4篇 |
1975年 | 5篇 |
1911年 | 2篇 |
1910年 | 2篇 |
排序方式: 共有1618条查询结果,搜索用时 15 毫秒
101.
The treatment of octafluorocyclopentene with organolithium reagents gave the corresponding symmetrical disubstituted perfluorocyclopentenes in good to high yields. The reaction with Grignard reagents led to the monosubstituted perfluorocyclopentenes, which were subjected to the further nucleophilic substitution reaction using another Grignard or aryllithium reagents, unsymmetrical disubstituted perfluorocyclopentenes being obtained in high yields. 相似文献
102.
Koyuki Sakai Hiroki Nishiyama Shinsuke Inagi Ikuyoshi Tomita Yusuke Hibi Motonori Komura Keiji Nose Tomokazu Iyoda 《Journal of polymer science. Part A, Polymer chemistry》2019,57(24):E1-E8
A block copolymer composed of a flexible polar poly(ethylene glycol) (PEG) and a less polar liquid crystalline poly(allene) segments is prepared by the living coordination polymerization of an allene derivative possessing trans‐azobenzene‐containing mesogenic substituent by the use of a π‐allylnickel macroinitiator bearing PEG segment. The thin film of the block copolymer is prepared by the spin coating of its solution onto mica or silicon wafer which proves to possess perpendicularly oriented nanocylindrical microphase separated structures as supported by the differential calorimetric, polarized optical microscopic, grazing‐incidence small‐angle X‐ray scattering, transmission electron microscope, and atomic force microscope measurements. 相似文献
103.
Dr. Yoshifumi Sasano Dr. Yohei Haketa Hiroki Tanaka Dr. Nobuhiro Yasuda Prof. Ichiro Hisaki Prof. Hiromitsu Maeda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(27):6712-6717
Phenyl groups were introduced at the β-positions proximal to the meso-hydroxy moiety in hydroxyporphyrin NiII complexes by oxidized BINAP PdII complexes. Ion-pairing assemblies of deprotonated π-electronic anions, anionic site of which was stabilized by the introduced phenyl moieties with a bulky cation, were formed. They showed charge-by-charge assemblies, assembly modes of which were modulated by the anionic building units. 相似文献
104.
Takiue T Hirose D Murakami D Sakamoto H Matsubara H Aratono M 《The journal of physical chemistry. B》2005,109(34):16429-16434
The interfacial tension gamma of the hexane solution of 1H,1H-perfluorononanol (FDFC(9)OH) and its omega-hydrogenated analogue, 1H,1H,9H-perfluorononanol (HDFC(9)OH), against water was measured as a function of pressure and concentration at 298.15 K in order to clarify the effect of omega-dipole on the orientation of fluorononanol molecules from the viewpoint of volume. The adsorbed films of both alcohols exhibit two kinds of phase transitions among three different states: the gaseous, expanded, and condensed states. The partial molar volume changes of adsorption - in the expanded and condensed states were evaluated and compared between the two systems. The - values of both alcohols are negative, and thus the alcohol molecules have smaller volume in the adsorbed film than in the bulk solution. Furthermore, the value was obtained through the evaluation of by the density measurement of the bulk hexane solution. It was found that the value of HDFC(9)OH is smaller than that of FDFC(9)OH in the condensed state. On the basis of three matters concerning the molecular structure of alcohols, the occupied area at the interface, and the orientation of FDFC(9)OH in the adsorbed film deduced from the earlier results of X-ray reflectivity measurement, the mean tilt angle of HDFC(9)OH from the interface normal in the condensed film was estimated to be 15 degrees . The thermodynamic estimation demonstrated here is highly valuable one to provide structure information on an adsorbed film. 相似文献
105.
Masayuki Nagai Koh Nakamura Hiroki Uehara Tetsuo Kanamoto Yoshiyuki Takahashi Takeo Furukawa 《Journal of Polymer Science.Polymer Physics》1999,37(18):2549-2556
Oriented poly(vinylidene fluoride) (PVDF) films with β‐form crystals have been commonly prepared by cold drawing of a melt‐quenched film consisting of α‐form crystals. In this study, we have successfully produced highly oriented PVDF thin films (20 µm thick) with β‐crystals and a high crystallinity (55–76%), by solid‐state coextrusion of a gel film to eight times the original length at an established optimum extrusion temperature of 160°C, some 10°C below the melting temperature. The resultant drawn films had a highly oriented (orientation function fc = 0.993) fibrous structure, showing high mechanical properties of an extensional elastic modulus of 8.3 GPa and tensile strength of 0.84 GPa, along the draw direction. Such highly oriented and crystalline films exhibited excellent ferroelectric and piezoelectric properties. The square hysteresis loop was significantly sharper than that of a conventional sample. The sharp switching transient yielded the remnant polarization Pr of 90 mC/m2, and the electromechanical coupling factor kt was 0.24 at room temperature. These values are about 1.5 times greater than those of a conventional β‐PVDF film. Thus, solid‐state coextrusion near the melting point was found to be a useful technique for the preparation of highly oriented and highly crystalline β‐PVDF films with superior mechanical and electrical properties. The morphology of the extrudate relevant to such properties is discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2549–2556, 1999 相似文献
106.
Ellipsometry, surface tensiometry, and contact-angle measurement have been used to study the transition between partial wetting and pseudo-partial wetting of surfactant solutions by alkanes. In the partial wetting regime, the air-water surface tension is the same with and without alkane. In the pseudo-partial wetting regime, the air-water surface tension is lowered by the presence of alkane, showing that oil is solubilised into the surfactant monolayer. A discontinuous change in the coefficient of ellipticity with increasing surfactant concentration provides unequivocal evidence for the first-order nature of the wetting transitions. Ellipsometry has been used to explore the generality of wetting transitions of alkanes (dodecane, hexadecane, and squalane) on surfactant solutions [dodecyltrimethylammonium bromide, tetredecyltrimethylammonium bromide, dibucaine hydrochloride, and Aerosol OT (AOT)]. Of the systems studied, only hexadecane on AOT solutions did not show a wetting transition. Excess alkane remains as a lens on the surface of the surfactant solutions at all concentrations, but the contact angle is a minimum at the wetting transition. A semiquantitative model for the variation of the contact angle with surfactant concentration is provided. 相似文献
107.
Kawasaki I Tsunoda K Tsuji T Yamaguchi T Shibuta H Uchida N Yamashita M Ohta S 《Chemical communications (Cambridge, England)》2005,(16):2134-2136
A novel task-specific ionic ligand with an imidazolium salt moiety was synthesized, and its catalytic ability and recyclability for asymmetric transfer hydrogenation of acetophenone derivatives with a formic acid-triethylamine azeotropic mixture in an ionic liquid [bmim][PF6] was examined. 相似文献
108.
Imabayashi S Mita T Kakiuchi T 《Langmuir : the ACS journal of surfaces and colloids》2005,21(6):2474-2479
The effect of charge-inverting modification of single surface lysine residue on the electron transfer (ET) reaction of horse heart cytochrome c (cyt c) is examined for 12 different types of mono-4-chloro-2,5-dinitrobenzoic acid substituted cyt c (mCDNPc) adsorbed on a Au(111) electrode modified with a self-assembled monolayer (SAM) of 7-mercapto-heptanoic acid (MHA). A negative shift in the redox potential by 10-35 mV as compared to that of native cyt c and a monolayer coverage in the range of 13-17 pmol cm(-2) are observed for electroactive mCDNPc's. The magnitude of the decrease in the ET rate constant (k(et)) of mCDNPc's compared with that of native cyt c depends on the position of the CDNP substitution. For mCDNPc's in which the modified lysine residue is outside of the interaction domain of cyt c with the SAM, the ratio of the k(et) of mCDNPc to that of native cyt c is correlated to the change in the dipole moment vector of cyt c due to the CDNP modification. This correlation suggests that the dipole moment of cyt c determines its orientation of adsorption on the SAM of MHA and significantly affects the rate of the ET. The CDNP modification of lysine residues at the interaction domain significantly decreases the rate, demonstrating the importance of the local charge environment in determining the rate of ET. 相似文献
109.
Itoh T Shichi T Yui T Takahashi H Inui Y Takagi K 《The journal of physical chemistry. B》2005,109(8):3199-3206
The present study is an investigation of a reversible thermal color change induced in lamella hybrids of poly(diacetylenecarboxylates) incorporated in layered double hydroxide (LDH) nanosheets. These poly-[m,n]/LDH hybrids prepared by the photo- or gamma-ray-induced polymerization of diacetylenecarboxylates, i.e., CH(3)(CH(2))(m)()(-)(1)CC-CC(CH(2))(n)()(-)(1)CO(2)(-) (mono-[m,n]), and intercalated in LDH lamella sheets, were observed to develop colors ranging from yellow to blue. The change in color was found to depend greatly on the alkyl carbon numbers of the mono-[m,n] (m,n = 10,11; 5,11; 10,5; 16,1) values. Moreover, the conformational alignment of the mono-[m,n] within the LDH was observed to be a crucial factor in color development, which was greatly affected by the intercalation degrees and extent of poly(ene-yne) linkage elongation of the polymers. For the poly-[m,n]/LDH hybrids investigated, a reversible color change was found to occur repeatedly and remarkably for the poly-[10,11]/LDH hybrid. This color change occurred at temperatures between ca. 20 and 80 degrees C back and forth from purple red to bright orange, in stark contrast to the irreversible color change for poly-[10,11] without LDH. Moreover, DSC and Raman spectroscopic studies of the LDH hybrids showed that the thermochromic temperature corresponded to the phase transition temperature of 80 degrees C. XRD analysis also indicated that the poly-[m,n]/LDH hybrid could retain its lamella structure during such thermochromic color changes, enabling conformational recovery in the polymer chains by a cooling down of the hybrids to temperatures lower than the transition temperature, while the nonhybrid poly-[10,11] powders exhibited an irreversible color change at 60 degrees C, above which the polymer powder turned amorphous. 相似文献
110.
Shigekazu Ito Hideaki Miyake Hiroki Sugiyama Masaaki Yoshifuji 《Heteroatom Chemistry》2005,16(5):357-360
Kinetically stabilized 2‐lithio‐1‐(2,4,6‐tri‐t‐butylphenyl)‐1‐phosphapropene was allowed to react with a bulky phosphaalkyne Mes*CP (Mes* = 2,4,6‐t‐Bu3C6H2) followed by quenching with iodomethane or benzyl bromide to give the corresponding 1,3‐diphosphabuta‐1,3‐dienes. The presence of the bulky Mes* group on the 1‐phosphorus atom prevents intramolecular [2+2] cyclization and gave the PC PC skeleton, whereas Mes*CP reacted with half an equivalent of nucleophile to afford the PCPC four‐membered ring compounds. X‐ray crystallography of 4‐benzyl‐1,3‐diphosphabuta‐1,3‐diene confirmed the molecular structure showing conjugation on the 1,3‐diphosphabuta‐1,3‐diene moiety. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:357–360, 2005; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20104 相似文献