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21.
Changes in electronic structure upon lithium insertion into the A-site deficient perovskite type oxides (Li,La)TiO3 总被引:1,自引:0,他引:1
Nakayama M Usui T Uchimoto Y Wakihara M Yamamoto M 《The journal of physical chemistry. B》2005,109(9):4135-4143
Investigation on variation of the electronic structure accompanying the electrochemical lithium insertion into the perovskite type oxide, (Li,La)TiO3, has been carried out by X-ray absorption spectroscopy (XAS). During the electrochemical lithium insertion, titanium ion reduced its oxidation state from Ti4+ to Ti3+, while La3+ does not contribute to the reduction reaction resulting from Ti K-edge and La L3-edge XAS, respectively. Furthermore, O K-edge XAS showed marked spectral changes with electrochemical lithium insertion, indicating the electronic structure around oxide ion affected by lithium insertion reaction. From the XAS measurement, we have concluded the variation observed in O K-edge XAS was related to the strong interaction with inserted Li ion. To confirm this, first-principles band calculations were performed for the perovskite structure before and after electrochemical lithium insertion. The calculated results showed that the electron originated from inserted Li transferred to neighboring oxide ion locally as well as to Ti ion. This may be due to local neutralization effect of Li to reduce the electrostatic interaction in the crystal. 相似文献
22.
Yuichiro Haramoto Yoshiharu Kusakabe Masato Nanasawa Seiji Ujiie Stephan Mang Cladius Schwarzwalder 《Liquid crystals》2013,40(10):1393-1397
Side chain type ionic liquid crystalline polymers having a 4-(1,3-dioxan-2-yl)pyridinium structure in their mesogenic side chain were synthesized. These polymers exhibited the smectic A phase. The molecular weights of these ionic liquid crystalline polymers are very high, e.g. for compound 7 - 2 M w = 486 000. 相似文献
23.
Yasumasa Nishiwaki Kazunari Masutani Yoshiharu Kimura Chan-Woo Lee 《Journal of polymer science. Part A, Polymer chemistry》2022,60(14):2043-2054
The ABCBA pentablock copolymers (p-d -l -PPS) comprising poly(d -lactide) (PDLA: A), poly(l -lactide) (PLLA: B) and poly(propylene succinate) (PPS: C) were successfully synthesized by two-step ring-opening polymerization (ROP) of d - and l -lactide using a dihydroxy-terminated PPS as a macro-initiator. The pentablock copolymers revealed the high stereocomplex (sc) crystallinity, thermal stability and elastomeric property in their solution-cast films. It was found that the Tg was found to be proportional to the PPS content, whereas the Tm was proportional to their average block length. The thermal resistivity of the copolymer films was found to be as high as 202°C owing to their sc formation. The copolymers also showed improved stereocomplexibility compared to the enantiomeric mixtures of triblock copolymers (PLLA-PPS-PLLA and PDLA-PPS-PDLA) having similar PLLA and PDLA chain lengths. These pentablock copolymers can afford thermoplastic elastomers or flexible plastic materials having a 100% bio-based content, showing high heat-resistive property. 相似文献
24.
Pinacol-type coupling reaction products presenting a high meso-diastereoselectivity (the ratio dl/meso was 4/96 up to 1/99) were obtained in fair to good yields (24–69%) using several aromatic aldehydes as starting materials and aluminium powder/copper sulfate as catalysts, in water, under reflux conditions. 相似文献
25.
Sai Venkatesh Pingali Hugh M. O’Neill Yoshiharu Nishiyama Lilin He Yuri B. Melnichenko Volker Urban Loukas Petridis Brian Davison Paul Langan 《Cellulose (London, England)》2014,21(2):873-878
Morphological changes to the different components of lignocellulosic biomass were observed as they occurred during steam pretreatment by placing a pressure reaction cell in a neutron beam and collecting time-resolved neutron scattering data. Changes to cellulose morphology occurred mainly in the heating phase, whereas changes in lignin morphology occurred mainly in the holding and cooling phases. During the heating stage, water is irreversibly expelled from cellulose microfibrils as the elementary fibrils coalesce. During the holding phase lignin aggregates begin to appear and they increase in size most noticeably during the cooling phase. This experiment demonstrates the unique information that in situ small angle neutron scattering studies of pretreatment can provide. This approach could be useful in optimizing the heating, holding and cooling stages of pretreatments to allow the exact size and nature of lignin aggregates to be controlled in order to enhance enzyme accessibility to cellulose and therefore the efficiency of biomass conversion. 相似文献
26.
Pan Chen Yoshiharu Nishiyama Jean-Luc Putaux Karim Mazeau 《Cellulose (London, England)》2014,21(2):897-908
We have performed molecular dynamics calculations using a revised version of the Gromos56Acarbo force field to understand the consequences of the different potential hydrogen bonding patterns on the structural stability and thermal behavior of the Iα and Iβ forms of native cellulose. For each allomorph, we considered three patterns of hydrogen bonds: two patterns obtained from neutron diffraction data refinement and a regular mixture of the two. Upon annealing, the hydrogen bonding schemes of cellulose Iβ, irrespective of the starting structure, re-arranged into the main hydrogen bond pattern experimentally observed (pattern A). On the other hand, the Iα structures, irrespective of the starting hydrogen bonding pattern, converged to a non-experimental structure where the adjacent chains are shifted along the chain direction by 0.12 nm in the hydrogen-bonded plane, and the hydroxymethyl group conformation alternates between gt and tg along the chain. The exotic structure in Iα might be a consequence of a deficiency in force field parameters and/or potential molecular arrangement in less crystalline cellulose. 相似文献
27.
Shigeyoshí Nishino Yasuhiro Nagato Yoshihiro Hasegawa Hisanao Yamamoto Kazuo Kamaike Yoshiharu Ishido 《Heteroatom Chemistry》1991,2(1):187-196
Reagent systems of sodium– and tetrabutylammonium nitrite–acetic anhydride were proved to be extremely efficient for the deanilidation of nucleoside 3′-phosphoranilidates, whose reactions were rapid with the former and instant with the latter. It was further found that the reagent system is applicable to oligonucleotide synthesis provided that the exocyclic amino groups of 2′-deoxyadenosine, 2′-deoxyguanosine, and 2′-deoxycytidine were protected by succinylation. 相似文献
28.
Yoshiharu Kagami Jian Ping Gong Yoshihito Osada 《Macromolecular rapid communications》1996,17(8):539-543
Shape memory polymers were prepared by copolymerizing stearyl acrylate and methyl acrylate. The principle of this shape memory effect is based on reversible order-disorder transition of crystalline aggregates of stearyl moieties. A specific feature of this type of shape memory copolymer is that the transition temperature at which the polymer abruptly becomes soft and deforms can be controlled by changing the monomer composition, which enables one to adjust the shape memory effect at a desired temperature. Mechanism and process of the shape memory behaviors were discussed. 相似文献
29.
Toshihiro Okajima Hiroyuki Setoyama Marek Brancewicz Masahide Kawamoto Yoshiharu Sakurai 《X射线光谱测定》2020,49(3):390-397
X-ray fluorescence spectra of copper (Cu) metal, copper monoxide (CuO), and potassium chromate (K2CrO4) were recorded as a function of incident X-ray energy near the Cu K-edge and chromium (Cr) K-edge, respectively, using a conventional silicon drift detector. The spectra contained components due to elastic, inelastic, and multiple scattering, in addition to the Kα and Kβ lines. Cu and Cr K-edge X-ray absorption fine structure (XAFS) spectra of Cu, CuO, and K2CrO4 were obtained by an intensity analysis of the Kα and Kβ lines. The intensity of the Kβ line for the different incident photon energies was obtained by numerically removing the additional scattering components using the MUSCAT program. These spectra exhibited a jump near the K absorption edges, which reproduced the spectral features obtained in transmission mode for both Cu, CuO, and K2CrO4. A chemical shift was also clearly identified in the X-ray absorption near edges structure using the X-ray fluorescence Kβ line. In addition, the Cr K-edge extended XAFS spectrum of K2CrO4 was clearly observed using the Cr Kβ fluorescent line. The XAFS measurements on the Kα and Kβ lines are possible, and they carry equally valuable information. 相似文献
30.
Yusuke Sasano Shota Nagasawa Mai Yamazaki Dr. Masatoshi Shibuya Prof. Dr. Jaiwook Park Prof. Dr. Yoshiharu Iwabuchi 《Angewandte Chemie (International ed. in English)》2014,53(12):3236-3240
The direct oxidation of unprotected amino alcohols to their corresponding amino carbonyl compounds has often posed serious challenges in organic synthesis and has constrained chemists to adopting an indirect route, such as a protection/deprotection strategy, to attain their goal. Described herein is a highly chemoselective aerobic oxidation of unprotected amino alcohols to their amino carbonyl compounds in which 2‐azaadamantane N‐oxyl (AZADO)/copper catalysis is used. The catalytic system developed leads to the alcohol‐selective oxidation of various unprotected amino alcohols, carrying a primary, secondary, or tertiary amino group, in good to high yield at ambient temperature with exposure to air, thus offering flexibility in the synthesis of nitrogen‐containing compounds. 相似文献