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排序方式: 共有161条查询结果,搜索用时 304 毫秒
31.
Dr. Yuma Otake Yusuke Shibata Dr. Yoshihiro Hayashi Prof. Dr. Susumu Kawauchi Prof. Dr. Hiroyuki Nakamura Prof. Dr. Shinichiro Fuse 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(31):13025-13030
The development of a robust amide-bond formation remains a critical aspect of N-methylated peptide synthesis. In this study, we synthesized a variety of dipeptides in high yields, without severe racemization, from equivalent amounts of amino acids. Highly reactive N-methylimidazolium cation species were generated in situ to accelerate the amidation. The key to success was the addition of a strong Brønsted acid. The developed amidation enabled the synthesis of a bulky peptide with a higher yield in a shorter amount of time compared with the results of conventional amidation. In addition, the amidation can be performed by using either a microflow reactor or a conventional flask. The first total synthesis of naturally occurring bulky N-methylated peptides, pterulamides I–IV, was achieved. Based on experimental results and theoretical calculations, we speculated that a Brønsted acid would accelerate the rate-limiting generation of acyl imidazolium cations from mixed carbonic anhydrides. 相似文献
32.
Komiyama M Kina S Matsumura K Sumaoka J Tobey S Lynch VM Anslyn E 《Journal of the American Chemical Society》2002,124(46):13731-13736
The cooperative action of multiple Cu(II) nuclear centers is shown to be effective and selective in the hydrolysis of 2'-5' and 3'-5' ribonucleotides. Reported herein is the specific catalysis by two trinuclear Cu(II) complexes of L3A and L3B. Pseudo first-order kinetic studies reveal that the L3A trinuclear Cu(II) complex effects hydrolysis of Up(2'-5')U with a rate constant of 28 x 10(-)(4) min(-)(1) and Up(3'-5')U with a rate constant of 0.5 x 10(-)(4) min(-)(1). The hydrolyses of Ap(3'-5')A and Ap(2'-5')A proceed with rate constants of 24 x 10(-)(4) min(-)(1) and 0.5 x 10(-)(4) min(-)(1) respectively. The L3A trinuclear Cu(II) complex demonstrates high specificity for Up(2'-5')U and Ap(3'-5')A. Similar studies with the more rigid L3B trinuclear Cu(II) complex shows no selectivity and yields lower rate constants for hydrolysis. The selectivity observed with the L3A ligand is attributed to the geometry of the ligand-bound diribonucleotide which ultimately dictates the proximity of the attacking hydroxyl and the phosphoester to a Cu(II) center for activation and subsequent hydrolysis. 相似文献
33.
Observation of cerium isotope fractionation in ion-exchange chromatography of Ce(III)-malate complex
The cerium isotope fractionation between Ce(III)-malate complex in aqueous solution and cerium ions in a cation-exchange resin was conducted by displacement chromatography. The pH and the chemical composition of the eluent were optimized for maintaining the self-sharpening band boundaries and the 21 m chromatographic migration of the Ce band underwent. Graphite slurry was coated on the tantalum filament prior to sample loading for reducing the isobaric interferences in cerium isotopic ratio determination by mass spectrometry. From the experimental results, it was found that the heavier isotope was enriched in the front boundary part of the cerium adsorption band, which meant that the heavier isotope was preferentially fractionated into the Ce3+ malate complex rather than simply hydrated Ce3+ ions. The isotope separation coefficient for the 136Ce/140Ce and 142Ce/140Ce was 5.2 x 10(-5) and -1.9 x 10(-5), respectively, at 298 K. 相似文献
34.
Inside Cover: Directing/Protecting‐Group‐Free Synthesis of Tetraaryl‐Substituted Pyrazoles through Four Direct Arylations on an Unsubstituted Pyrazole Scaffold (Chem. Eur. J. 41/2015)
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Sequential SNAr Reaction/Suzuki–Miyaura Coupling/C−H Direct Arylations Approach for the Rapid Synthesis of Tetraaryl‐Substituted Pyrazoles
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Taiki Morita Daisuke Kobayashi Keisuke Matsumura Dr. Kohei Johmoto Dr. Hidehiro Uekusa Dr. Shinichiro Fuse Prof. Dr. Takashi Takahashi 《化学:亚洲杂志》2015,10(8):1626-1630
A rapid synthesis of 1,3,4,5‐tetraaryl‐substituted pyrazoles has been achieved through a sequence of SNAr reaction/Suzuki–Miyaura coupling/Pd‐catalyzed direct arylations that used 3‐iodo‐1H‐pyrazole as a scaffold. Pyrazoles with four different aryl groups were synthesized in a straightforward manner with no extra synthetic steps, such as protection/deprotection or the introduction of activating/directing groups, using readily available substrates and reagents. The developed synthetic approach enabled the structurally diverse synthesis of multiaryl‐substituted pyrazoles without using a glovebox technique. 相似文献
38.
Tajiri S Kanamaru T Yoshida K Hosoi Y Konno T Yada S Nakagami H 《Chemical & pharmaceutical bulletin》2010,58(10):1295-1300
After the dosing of an extended-release (ER) formulation, compounds may exist in solutions at various concentrations in the colon because the drugs are released at various speeds from the ER dosage form. The aim of this study was to investigate the relationship between the drug concentration profiles in plasma and the drug doses in the colon. Several drug solutions of different concentrations were directly administered into the ascending colon of dogs using a lubricated endoscope, and the effects of the drug dose on colonic absorption were estimated. As a result, dose-dependency of colonic absorption varied from compound to compound. Although the relative bioavailability of colonic administration of diclofenac, metformin and cevimeline compared to oral administration was similar regardless of the drug doses in the colon, colonic absorption of diltiazem varied according to the doses. From the results of the co-administration of verapamil and fexofenadine, it was clear that diltiazem underwent extensive hepatic and gastrointestinal first-pass metabolism, resulting in a low area under the curves (AUC) at a low drug dose. During the design of oral ER delivery systems, a colonic absorption study of candidate compounds should be carried out at several solutions of different drug concentrations and assessed carefully. 相似文献
39.
Kamino S Horio Y Komeda S Minoura K Ichikawa H Horigome J Tatsumi A Kaji S Yamaguchi T Usami Y Hirota S Enomoto S Fujita Y 《Chemical communications (Cambridge, England)》2010,46(47):9013-9015
A new class of rhodamine luminophores, 3',3'-bis(oxospiroisobenzofuran)-3,7-bis(dialkylamino)benzopyrano-xanthene derivatives (ABPX), have been successfully developed. The emission behavior of ABPX series is directly opposite to the concentration quenching of conventional rhodamine dyes. ABPX series exhibit aggregation-induced emission enhancement (AIEE). 相似文献
40.
Harada T Hiraoka Y Kusukawa T Marutani Y Matsui S Nakatsugawa M Kanda K 《Organic letters》2003,5(26):5059-5062
Bis-BINOLs 7a-c in which two BINOL units are tethered by phenylenebis(ethynyl) groups react with titanium tetraisopropoxide (2 equiv) to form intramolecular dimeric titanium(IV) aggregates 2a-c. Of these, 2a,b with an o-phenylenebis(ethynyl) tether are stable in the presence of excess titanium tetraisopropoxide. Complex 2a exhibits a relatively high enantioselectivity in asymmetric addition of diethylzinc to an aldehyde. [structure: see text] 相似文献