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91.
Praseetha E. Kesavan Vijayalakshmi Pandey Masatoshi Ishida Hiroyuki Furuta Shigeki Mori Iti Gupta 《化学:亚洲杂志》2020,15(13):2015-2028
Beta‐pyrrole‐substituted porphyrin dyads connected by ethynyl linkage to N‐butylcarbazole or triphenylamine donors are reported. Donor‐π‐acceptor type beta‐substituted porphyrin dyads and their Zn(II) and Pd(II) complexes were characterized by MALDI‐MS, NMR, UV‐vis absorption, fluorescence and cyclic voltammetry techniques. The S1 emission dynamics were analyzed by time‐resolved spectroscopy (TCSPC); dyads exhibited efficient energy transfer up to 93% from beta‐donors (N‐butylcarbazole or triphenylamine group) to the porphyrin core. The efficiency of energy transfer for the beta‐substituted porphyrin dyads were much higher than those of the corresponding meso‐substituted porphyrin dyads, reflecting enhanced communications between the beta‐donors and the porphyrin core. The Pd(II) dyads, showed characteristic phosphorescence in the near IR region and very efficient singlet oxygen quantum yields (53–60%); these dyads are promising candidates for photocatalytic oxidations of organic compounds. The donor‐acceptor interaction between the porphyrin core and the beta‐donors was supported by the DFT studies in the porphyrin dyads. 相似文献
92.
Shota Ooi Takayuki Tanaka Takahisa Ikeue Kazuhisa Yamasumi Kento Ueta Daiki Shimizu Masatoshi Ishida Hiroyuki Furuta Atsuhiro Osuka 《化学:亚洲杂志》2019,14(10):1771-1776
Copper complexes of corroles have recently been a subject of keen interest due to their ligand non‐innocent character and unique redox properties. Here we investigated bis‐copper complex of a triply‐linked corrole dimer that serves as a pair of divalent metal ligands but can be reduced to a pair of trivalent metal ligands. Reaction of triply‐linked corrole dimer 2 with Cu(acac)2 (acac=acetylacetonate) gave bis‐copper(II) complex 2Cu as a highly planar molecule with a mean‐plane deviation value of 0.020 Å, where the two copper ions were revealed to be divalent by ESR, SQUID, and XPS methods. Oxidation of 2Cu with two equivalents of AgBF4 gave complex 3Cu , which was characterized as a bis‐copper(II) complex of a dicationic triply‐linked corrole dimer not as the corresponding bis‐copper(III) complex. In accord with this assignment, the structural parameters around the copper ions were revealed to be quite similar for 2Cu and 3Cu . Importantly, the magnetic spin–spin interaction differs depending on the redox‐state of the ligand, being weak ferromagnetic in 2Cu and antiferromagnetic in 3Cu . 相似文献
93.
Yohsuke Yamamoto Shiro Matsukawa Shin-ya Furuta Kin-ya Akiba 《Phosphorus, sulfur, and silicon and the related elements》2013,188(6-7):1375-1379
Solution and crystal structures of monocyclic pentacoordinate phosphoranes bearing two Martin ligands and two carbon substituents are described. When the two carbon substituents are different, relative apicophilicity of the two monodentate carbon substituents could be determined based on the equilibrium ratio of the pseudorotamers. In some cases, x-ray structural analysis could be carried out and the crystallized structure from CH 3 CN is consistent with the major pseudorotamer in solution (CD 3 CN). Furthermore, when the equilibrium ratio of pseudorotamers is almost unity, novel cocrystallization of two pseudorotamers in a single crystal was observed. 相似文献
94.
E. Furuta H. Nakahara Y. Hatsukawa H. Matsue H. Sakane 《Journal of Radioanalytical and Nuclear Chemistry》2008,278(3):553-557
In Japan, cosmetics claiming hormesis effect are available through Internet. Although these cosmetics show the contents, they
never mention the minor elements and radioactive sources. The existence of radioisotopes, however, was observed by measurements
of the gamma-rays with a HPGe detector. In this study, in order to clarify the contents of trace elements, the hormesis cosmetics
including radioactive sources were analyzed using INAA, PGAA and NAA with multiple gamma-ray detection (NAAMG). Nineteen elements
were analyzed quantitatively in hormesis cosmetics by INAA, PGAA and NAAMG and 16 elements were detected qualitatively by
SEM-EPMA. 相似文献
95.
Yue Wang Koki Ogasahara Daisuke Tomihama Radomir Mysliborski Masatoshi Ishida Yongseok Hong Yusuke Notsuka Yoshihisa Yamaoka Tomotaka Murayama Atsuya Muranaka Masanobu Uchiyama Shigeki Mori Yuhsuke Yasutake Susumu Fukatsu Dongho Kim Hiroyuki Furuta 《Angewandte Chemie (International ed. in English)》2020,59(37):16161-16166
The synthesis of organometallic complexes of modified 26π‐conjugated hexaphyrins with absorption and emission capabilities in the third near‐infrared region (NIR‐III) is described. Symmetry alteration of the frontier molecular orbitals (MOs) of bis‐PdII and bis‐PtII complexes of hexaphyrin via N‐confusion modification led to substantial metal dπ–pπ interactions. This MO mixing, in turn, resulted in a significantly narrower HOMO–LUMO energy gap. A remarkable long‐wavelength shift of the lowest S0→S1 absorption beyond 1700 nm was achieved with the bis‐PtII complex, t ‐Pt2‐3 . The emergence of photoacoustic (PA) signals maximized at 1700 nm makes t ‐Pt2‐3 potentially useful as a NIR‐III PA contrast agent. The rigid bis‐PdII complexes, t ‐Pd2‐3 and c ‐Pd2‐3 , are rare examples of NIR emitters beyond 1500 nm. The current study provides new insight into the design of stable, expanded porphyrinic dyes possessing NIR‐III‐emissive and photoacoustic‐response capabilities. 相似文献
96.
T Furuta P C Canfell K P Castagnoli M L Sharma R D Miller 《Journal of chromatography. A》1988,427(1):41-53
A sensitive and specific capillary gas chromatographic (GC) assay was developed for the quantitation of the quaternary ammonium steroidal neuromuscular blocking drugs pancuronium (PANC), vecuronium (VEC) and pipecuronium (PIP), as well as the metabolites 3-desacetylpancuronium (3-desPANC) and 3-desacetylvecuronium (3-des VEC) in plasma, bile and urine; the putative metabolite 3-desacetylpipecuronium (3-des PIP) was extracted and quantitated only in urine. The procedure employed a single dichloromethane extraction of the iodide ion-pairs of the monoquaternary or bisquaternary ammonium compounds (including internal and external standards) from acidified, ether-washed biological fluid followed by the formation of stable O-tert.-butyldimethylsilyl derivatives at the 3-hydroxy steroidal position of the metabolites. An automated capillary GC system fitted with a nitrogen-sensitive detector and an integrator was then used to analyze and quantitate both parent compounds and their derivatized metabolites. Optimal extraction, derivatization and GC conditions, as well as short-term stability and recoveries of these drugs and metabolites in plasma, are reported. Electron ionization mass spectrometry combined with GC was used to confirm the identities of compounds eluted from the column. The assay demonstrated a 10(3)-fold linear range up to 5000 ng/ml for PANC, VEC, 3-des VEC and PIP, and lower limits of detection with adequate precision of 2 ng/ml for PANC, VEC and PIP, and 4 ng/ml for 3-des VEC; 3-des PANC was linear from 8 to 500 ng/ml while 3-des PIP was linear from 25 to 1000 ng/ml. The precision (coefficient of variation) of the calibration curves for underivatized drugs and their derivatized metabolites over the linear ranges was 2-20% and the reproducibility of the assay over a range of clinical concentrations of these drugs found in human plasma was 5-16% for PANC, 2-4% for VEC and 6-11% for PIP. No interferences were detected in the assay of plasma samples from 106 surgical patients. 相似文献
97.
Dr. Toshiharu Ishizaki Hideaki Karasaki Dr. Yuto Kage Misaki Kamioka Yitong Wang Dr. Shigeki Mori Prof. Dr. Naoto Ishikawa Prof. Dr. Takamitsu Fukuda Prof. Dr. Hiroyuki Furuta Prof. Dr. Soji Shimizu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(49):12686-12692
A novel pyrrolopyrrole azadipyrrin ( Janus-PPAD ) with Janus duality was synthesized by a Schiff base–forming reaction of diketopyrrolopyrrole. The orthogonal interactions of the hydrogen-bonding ketopyrrole and metal-coordinating azadipyrrin moieties in Janus-PPAD enabled the metal ions to be arranged at regular intervals: zinc(II) and cobalt(II) coordination provided metal-coordinated Janus-PPAD dimers, which can subsequently form hydrogen-bonded one-dimensional arrays both in solution and in the solid state. The supramolecular assembly of the zinc(II) complex in solution was investigated by 1H NMR spectroscopy based on the isodesmic model, in which a binding constant for the elongation of assemblies is constant. Owing to the tetrahedral coordination, in the solid state, the cobalt(II) complex exhibited a slow magnetic relaxation due to the negative D value of −27.1 cm−1 with an effective relaxation energy barrier Ueff of 38.0 cm−1. The effect of magnetic dilution on the relaxation behavior is discussed. The relaxation mechanism at low temperature was analyzed by considering spin lattice interactions and quantum tunneling effects. The easy-axis magnetic anisotropy was confirmed, and the relevant wave functions were obtained by ab initio CASSCF calculations. 相似文献
98.
Hidefumi Yoshii Aya Sakane Daisuke Kawamura Tze Loon Neoh Hayato Kajiwara Takeshi Furuta 《Journal of inclusion phenomena and macrocyclic chemistry》2007,57(1-4):591-596
The release kinetics of (−)-menthol from chewing gum was investigated using various encapsulated powder of (−)-menthol. The
apparatus of flavor release of chewing gum was made with a glass container of mashing homogenizer. Flavor release behavior
could be correlated with Avrami’s equation. Chewing gum containing (−)-menthol/γ-CD complex powder had longer retention of
(−)-menthol compared with the β-CD complex powder and the (−)-menthol encapsulated in modified starches. The activation energies
of (−)-menthol release from chewing gum were 106 kJ/mol for γ-CD complex and 74 kJ/mol for (−)-menthol/β-CD complex powder
and emulsified (−)-menthol encapsulated in HI-CAP, respectively. 相似文献
99.
Takayoshi Kasakado Yuki Hirobe Akihiro Furuta Mamoru Hyodo Takahide Fukuyama Ilhyong Ryu 《Molecules (Basel, Switzerland)》2021,26(19)
Our previous work established a continuous-flow synthesis of pristane, which is a saturated branched alkane obtained from a Basking Shark. The dehydration of an allylic alcohol that is the key to a tetraene was carried out using a packed-bed reactor charged by an acid–silica catalyst (HO-SAS) and flow hydrogenation using molecular hydrogen via a Pd/C catalyst followed. The present work relies on the additional propensity of Pd/C to serve as an acid catalyst, which allows us to perform a flow synthesis of pristane from the aforementioned key allylic alcohol in the presence of molecular hydrogen using Pd/C as a single catalyst, which is applied to both dehydration and hydrogenation. The present one-column-two-reaction-flow system could eliminate the use of an acid catalyst such as HO-SAS and lead to a significant simplification of the production process. 相似文献
100.
Osamu Iwanaga Mayuko Miyanishi Toshihiro Tachibana Takaaki Miyazaki Yoshihito Shiota Kazunari Yoshizawa Hiroyuki Furuta 《Molecules (Basel, Switzerland)》2022,27(21)
The factors that affect acceleration and high trans/cis selectivity in the catalytic cyclopropanation reaction of styrene with ethyl diazoacetate by cobalt N-confused porphyrin (NCP) complexes were investigated using density functional theory calculations. The reaction rate was primarily related to the energy gap between the cobalt–carbene adduct intermediates, A and B, which was affected by the NCP skeletons and axial pyridine ligands more than the corresponding porphyrin complex. In addition, high trans/cis stereoselectivity was determined at the TS1 and, in part, in the isomerization process at the carbon-centered radical intermediates, Ctrans and Ccis. 相似文献