全文获取类型
收费全文 | 545篇 |
免费 | 15篇 |
国内免费 | 2篇 |
专业分类
化学 | 373篇 |
晶体学 | 10篇 |
力学 | 6篇 |
数学 | 15篇 |
物理学 | 158篇 |
出版年
2023年 | 4篇 |
2021年 | 8篇 |
2020年 | 5篇 |
2019年 | 10篇 |
2018年 | 6篇 |
2017年 | 5篇 |
2016年 | 10篇 |
2015年 | 13篇 |
2014年 | 10篇 |
2013年 | 20篇 |
2012年 | 21篇 |
2011年 | 36篇 |
2010年 | 12篇 |
2009年 | 9篇 |
2008年 | 33篇 |
2007年 | 29篇 |
2006年 | 44篇 |
2005年 | 40篇 |
2004年 | 21篇 |
2003年 | 24篇 |
2002年 | 17篇 |
2001年 | 16篇 |
2000年 | 11篇 |
1999年 | 13篇 |
1998年 | 14篇 |
1997年 | 6篇 |
1996年 | 7篇 |
1995年 | 10篇 |
1994年 | 5篇 |
1992年 | 10篇 |
1991年 | 4篇 |
1990年 | 7篇 |
1989年 | 4篇 |
1988年 | 2篇 |
1987年 | 7篇 |
1986年 | 2篇 |
1985年 | 7篇 |
1984年 | 5篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1981年 | 6篇 |
1980年 | 7篇 |
1979年 | 7篇 |
1978年 | 4篇 |
1977年 | 4篇 |
1976年 | 3篇 |
1975年 | 6篇 |
1974年 | 3篇 |
1971年 | 2篇 |
1968年 | 2篇 |
排序方式: 共有562条查询结果,搜索用时 15 毫秒
1.
Masato Kawamoto Yasuyuki Mori Akihiko Tsuge Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》2022,60(8):1416-1421
Anionic ring-opening polymerization (ROP) behavior of trans-cyclohexene carbonate (CHC) using metal alkoxides as initiators was investigated. As a result, lithium tert-butoxide-initiated ROP of CHC with a high-monomer concentration (10 M) at low temperature (−15 to −10°C) proceeded to afford a poly(trans-cyclohexene carbonate) (PCHC) without undesired side reactions such as mainly backbiting. The suppression of side reactions enables the control of the molecular weight (Mn = 2400–6100) of PCHC with low molar-mass dispersity values (Mw/Mn = 1.16–1.22). Furthermore, by increasing the feed ratio of the monomer to the initiator, the molecular weight increases proportionally, indicating a controllable polymerization. The results of a matrix-assisted laser desorption/ionization time-of-flight mass spectrometry analysis, a kinetic study, and a chain extension experiment suggested a living nature of this ROP using lithium tert-butoxide. 相似文献
2.
Sol‐to‐Gel Transition in Fast Evaporating Systems Observed by in Situ Time‐Resolved Infrared Spectroscopy 下载免费PDF全文
Prof. Dr. Plinio Innocenzi Dr. Luca Malfatti Dr. Davide Carboni Prof. Dr. Masahide Takahashi 《Chemphyschem》2015,16(9):1933-1939
The in situ observation of a sol‐to‐gel transition in fast evaporating systems is a challenging task and the lack of a suitable experimental design, which includes the chemistry and the analytical method, has limited the observations. We synthesise an acidic sol, employing only tetraethylorthosilicate, SiCl4 as catalyst and deuterated water; the absence of water added to the sol allows us to follow the absorption from the external environment and the evaporation of deuterated water. The time‐resolved data, obtained by attenuated total reflection infrared spectroscopy on an evaporating droplet, enables us to identify four different stages during evaporation. They are linked to specific hydrolysis and condensation rates that affect the uptake of water from external environment. The second stage is characterized by a decrease in hydroxyl content, a fast rise of condensation rate and an almost stationary absorption of water. This stage has been associated with the sol‐to‐gel transition. 相似文献
3.
Conformational and Intermolecular Interaction Dynamics of Photolyase/Cryptochrome Proteins Monitored by the Time‐Resolved Diffusion Technique 下载免费PDF全文
Cryptochrome (CRY), a blue light sensor protein, possesses a similar domain structure to photolyase (PHR) that, upon absorption of light, repairs DNA damage. In this review, we compare the reaction dynamics of these systems by monitoring the reaction kinetics of conformational change and intermolecular interaction change based on time‐dependent diffusion coefficient measurements obtained by using the pulsed laser‐induced transient grating technique. Using this method, time‐dependent biomolecular interactions, such as transient dissociation reactions in solution, have been successfully detected in real time. Conformational change in (6‐4) PHR has not been detected after the photoexcitation by monitoring the diffusion coefficient. However, the repaired DNA dissociates from PHR with a time constant of 50 μs, which must relate to a minor conformational change. However, CRY exhibits a considerable diffusion change with a time constant of 400 ms, which indicates that the protein–solvent interaction is changed by the conformational change. The C‐terminal domain of CRY is shown to be responsible for this change. 相似文献
4.
Sorbitol was readily converted by heating in hydrophobic ionic liquids by the presence of ion exchange resins. Chemoseletivity of the dehydration depended on the choice of ion exchange resin; Nafion selectively produced isosorbide while Amberlite gave 1,5-anhydrosorbitol along with unreacted sorbitol. Ionic liquids used in the reaction were readily recovered by simple extraction procedure. With these procedures, we succeeded to prepare isosorbide in pure form, not contaminated with either ionic liquids or acid catalyst, by simple experimental procedure. 相似文献
5.
Effect of Acid Treatment of Montmorillonite on “Support‐Activator” Performance to Support Metallocene for Propylene Polymerization Catalyst 下载免费PDF全文
Takao Tayano Hideshi Uchino Takehiro Sagae Katsuyuki Yokomizo Koji Nakayama Shigeki Ohta Hiroshi Nakano Masahide Murata 《大分子反应工程》2017,11(2)
This work is focused on montmorillonite (MMT)‐based “support‐activators” (S‐As) for the metallocene‐catalyzed propylene polymerization. This catalyst was previously industrialized; however, for further technological advances, the activation mechanism is investigated. The chemical and morphological requirements of the S‐A are surveyed using both commercially available raw clay minerals (non‐acid‐treated) and acid‐treated clay minerals. The S‐A possessing strong‐acid sites (pK a < ?8.2) gives a highly active catalyst. Acid treatment of MMT induces morphological changes as well as the formation of strong acid sites. Based on pore size distribution analysis and atomic force microscopy observations, it is concluded that the strong acid sites are located in the small pores around the edge of the clay mineral (not in the interlayer), where the structure is disordered by the acid treatment.
6.
Paulo H. P. Macaúbas Hideo Kawamoto Masaoki Takahashi Kenzo Okamoto Toshikazu Takigawa 《Rheologica Acta》2007,46(7):921-932
Shape recovery of a droplet of liquid crystalline polymer (LCP) hydroxypropylcellulose in a matrix of poly(dimethyl siloxane) subjected to a step shear strain has been studied via optical microscopy. Just after application of a large strain, the LCP droplet shape is flat ellipsoid, and then the droplet takes cylindrical shape and band texture perpendicular to the flow direction appears. The band texture fades away before emergence of poly-domain structure. In the final process with the shape of spheroid, poly-domain structure recovers very slowly. Except for the final process, the shape change is identical with that of isotropic droplet at strains smaller than 3, when the LCP viscosity in Region II is taken as an equivalent viscosity for normalization. For a 20:80 blend, the excess relaxation modulus is calculated based on the Doi-Ohta theory, taking account of the distribution of droplet size and compared with experimental modulus data. 相似文献
7.
Nan Zhang Dr. Tohru Kawamoto Yong Jiang Dr. Akira Takahashi Dr. Manabu Ishizaki Miyuki Asai Prof. Masato Kurihara Prof. Zhenya Zhang Dr. Zhongfang Lei Dr. Durga Parajuli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(23):5950-5958
Cobalt hexacyanoferrate of various compositions was prepared in flow mode and the role of the vacancy on the structure, thermogravimetric (TG) properties, and the adsorption efficiency was studied. The material, NayCo[Fe(CN)6]1−x ⋅ z H2O, with a minimum vacancy of x=0.014 to the highest x=0.47, was obtained. The TG-differential scanning calorimetry (DSC) profile showed a distinct influence of the vacancy on the water release temperature. Materials with x>0.35 showed a smooth release of water at a relatively lower temperature. However, for the materials with x<0.35, water release took place in multiple steps, suggesting the existence of various forms of water. The FTIR profiles supported the existence of free and bonded water molecules. However, the materials with multiple water peaks in the FTIR spectra showed a shift of the major XRD peaks when heated at 285 °C in N2 atmosphere. Regarding the effect of the vacancy on the adsorption behavior, for NH4, the adsorption was found to be proportional to the number of Na atoms in the material, confirming the ion-exchange process. On the contrary, the materials with low vacancy and high Na content showed nominal Cs adsorption capacity. Interestingly, the K adsorption capacity was found to be in between that of the other two ions. This means the ionic size decides the rate of placement into the interstitial sites. For larger ions like Cs, the ease of percolation via the vacancy decides the overall adsorption efficiency. 相似文献
8.
Takumi Kobayashi Masahide Goto Masaki Minami Fumio Sanda 《Journal of polymer science. Part A, Polymer chemistry》2019,57(24):2581-2589
A novel polymer, poly( 1 ) containing benzoxazine and phenyleneethynylene moieties in the main chain with number‐average molecular weights ranging from 1400 to 9800 was obtained quantitatively by the Sonogashira–Hagihara coupling polymerization of the corresponding iodophenyl‐ and ethynylphenyl‐substituted monomer 1 . Poly( 1 ) was heated at 200 °C under N2 for 2 h to obtain the cured polymer, poly( 1 )′ via the ring‐opening polymerization of the benzoxazine moieties. The structures of the polymer before and after curing were confirmed by 1H‐NMR, IR, and UV–vis absorption and reflectance spectroscopies. Poly( 1 )′ was thermally more stable than monomer 1 and poly( 1 ). A specimen was prepared from a mixture of poly( 1 ) and phenol‐diaminodiphenylmethane type benzoxazine 2 by heating at 200 °C for 2 h under N2. The poly( 1 )/ 2 resin was thermally stable than bisphenol‐A type benzoxazine resin 3 . Poly( 1 ) exhibited XRD peaks corresponding to the d‐spacings of 1.26–0.98 and 0.40 nm, assignable to the repeating monomer unit and alignment of polymer molecules, respectively. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2581–2589 相似文献
9.
Abstract The activation field for the switching time (τ1/2) in the truly ferroelectric liquid crystal 8SI* (CE8; ΔS-(+)-4-(2′-methylbutyl) phenyl-4′-n-octylbiphenyl-4 carboxylate) has been studied for various surface conditions of the transparent electrode (SnO2), in order to understand the memory effect, the polarization reversal mechanism and its surface effect. We prepared five different surfaces, namely one coated with polyvinyl alcohol (PVA) and the other four by scratching N-times(N = 0, 10, 20 and 30) with a paste made of Cr2O3 powder (about 0·1 μm). The number and the area of scratches on the electrode surface obviously increase with N. The polarization reversal processes are influenced by this treatment. τ1/2 decreases with increasing N, but no change is observed in the contrast of the light transmittance. Two different activation fields, E a1, for the applied field E > E 0 and E a2 for E < E 0 are observed, where E 0 is a certain field depending on the sample. Here E a1 is much larger than E a2; typically E a1, = 260 kV cm?1 and E a2 = 144 kV cm?1 for N = 0. This means that nucleation for the higher field needs a large activation energy which therefore has strong barriers. In contrast with this, nucleation for the low field occurs easily. Changing a surface condition, E a2 clearly decreases with increasing N although E a1 is almost independent of the surface scratching. This may suggest that E a1 corresponds to the activation field for the bulk pinning and nucleation, and E a2 for the surface pinning. The PVA treatment gives an intermediate influence between N = 0 and 10. 相似文献
10.
Dr. Hajime Kameo Tatsuya Kawamoto Prof. Shigeyoshi Sakaki Prof. Didier Bourissou Prof. Hiroshi Nakazawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(7):2370-2375
Si?F bond cleavage of fluoro‐silanes was achieved by transition‐metal complexes under mild and neutral conditions. The Iridium‐hydride complex [Ir(H)(CO)(PPh3)3] was found to readily break the Si?F bond of the diphosphine‐ difluorosilane {(o‐Ph2P)C6H4}2Si(F)2 to afford a silyl complex [{[o‐(iPh2P)C6H4]2(F)Si}Ir(CO)(PPh3)] and HF. Density functional theory calculations disclose a reaction mechanism in which a hypervalent silicon species with a dative Ir→Si interaction plays a crucial role. The Ir→Si interaction changes the character of the H on the Ir from hydridic to protic, and makes the F on Si more anionic, leading to the formation of Hδ+???Fδ? interaction. Then the Si?F and Ir?H bonds are readily broken to afford the silyl complex and HF through σ‐bond metathesis. Furthermore, the analogous rhodium complex [Rh(H)(CO)(PPh3)3] was found to promote the cleavage of the Si?F bond of the triphosphine‐monofluorosilane {(o‐Ph2P)C6H4}3Si(F) even at ambient temperature. 相似文献