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101.
The radical cation of an NADH analogue (BNAH: 1-benzyl-1,4-dihydronicotinamide) has been successfully detected as the transient absorption and ESR spectra in the thermal electron transfer from BNAH to Fe(bpy)33+ (bpy = 2,2'-bipyridine). The ESR spectra of the radical cations of BNAH and the dideuterated compound (BNAH-4,4'-d2) indicate that the observed radical cation is the keto form rather than the enol form in the tautomerization. The deprotonation rate and the kinetic isotope effects of the keto form of BNAH*+ were determined from the kinetic analysis of the electron-transfer reactions. 相似文献
102.
Yuasa J Suenobu T Ohkubo K Fukuzumi S 《Chemical communications (Cambridge, England)》2003,(9):1070-1071
Scandium ion-promoted electron transfer reactions of p-benzoquinone are remarkably accelerated when tetrakis(pentafluorophenyl)borate anion is used instead of trifluoromethanesulfonate anion as the counter anion of scandium ion. Only a catalytic amount of scandium borate salt (Sc[B(C6F5)4]3) accelerates significantly the Diels-Alder reaction of 9,10-dimethylanthracene with p-benzoquinone, which proceeds via Sc(3+)-promoted electron transfer from the anthracene to p-benzoquinone. 相似文献
103.
Yoshihisa Kurasawa Tomoyoshi Hosaka Atsushi Takada Ho Sik Kim Yoshihisa Okamoto 《Journal of heterocyclic chemistry》1995,32(2):531-535
The 3-(arylhydrazono)methyl-2-oxo-1,2-dihydroquinoxalines 1a-h and 2a-e showed tautomeric equilibria between the hydrazone imine A and diazenyl enamine B forms in a series of mixed trifluoroacetic acid/dimethyl sulfoxide media. The substituent and solvent effects on the tautomer ratios of A to B in a series of mixed media were studied for compounds 1a-h and 2a-e by the nmr spectroscopy. In compounds 1a-h and 2a-e , the ratios of the tautomer B gradually increased with elevation of acid concentration, and the tautomer B exclusively existed in trifluoroacetic acid media. The various acid concentrations (C v/v%, C' mol/1) giving the 1:1 tautomer ratios [C(A:B = 1:1), C'(A:B = 1:1)] were obtained from all compounds (Figures 1–13), and the linear correlation of the Hammett σp values with the log C'(A:B = 1:1) values were observed for compounds 1a-h. The larger Hammett σp values brought about the larger acid concentrations C(A:B = 1:1) in compounds 1a-h and 2a-e , indicating that the higher acid concentration was required for the stabilization of tautomer B possessing the electron-withdrawing p-substituents R1, which weakened the basicity of the azo nitrogen atom. Moreover, the ester group R2 of compounds 2a-e was found to decrease the electron density of the azo nitrogen atom, since the acid concentration C(A:B = 1:1) of compound 2c (R1 = H, R2 = COOMe, σp = O) was 52%, whose value was larger than that of compound 1b (R1 = CN, R2 = H, σp = 0.66) [C(A:B = 1:1) = 42%]. 相似文献
104.
Takashi MURAYAMA Kousuke TAKAHAMA Kazumasa JINBO Tomoyoshi KOBARI 《Physical Therapy Research》2021,24(2):163
Objectives: This study aimed to investigate anatomical changes in the brain following chronic complete traumatic thoracic spinal cord injury (ThSCI) using voxel-based morphometry (VBM). That is, it attempted to examine dynamic physical change following thoracic injury and the presence or absence of regions with decreased and increased changes in whole brain volume associated with change in the manner of how activities of daily living are performed. Methods: Twelve individuals with chronic traumatic complete ThSCI (age; 21-63 years, American Spinal Injury Association Impairment Scale; grade C-D) participated in this study. VBM was used to investigate the regions with increased volume and decreased volume in the brain in comparison with healthy control individuals. Results: Decreases in volume were noted in areas associated with motor and somatosensory functions, including the right paracentral lobule (PCL)―the primary motor sensory area for lower limbs, left dorsal premotor cortex, and left superior parietal lobule (SPL). Furthermore, increased gray matter volume was noted in the primary sensorimotor area for fingers and arms, as well as in higher sensory areas. Conclusions: Following SCI both regions with increased volume and regions with decreased volume were present in the brain in accordance with changes in physical function. Using longitudinal observation, anatomical changes in the brain may be used to determine the rehabilitation effect by comparing present cases with cases with cervical SCI or cases with incomplete palsy. 相似文献
105.
Hara H Uchimura T Akashi N Naganuma T Aizawa T Nagae Y Masuda N 《Rapid communications in mass spectrometry : RCM》2004,18(4):377-384
TCH346 (dibenzo[b,f]oxepin-10-ylmethyl-prop-2-ynylamine) is a novel propargylamine compound under investigation as a putative agent in the treatment of chronic neurodegenerative illnesses. To support clinical studies an analytical method was developed for TCH346 plus its three amine metabolites and a carboxylic acid metabolite in human plasma. Using a two-step liquid-liquid extraction, one under acidic and one under basic conditions, by pH-switching both the basic and acidic analytes were extracted from 0.5 mL of plasma. All these basic and acidic compounds could be analyzed simultaneously using gradient high-performance liquid chromatographic (HPLC) separation with positive/negative selected reaction monitoring mass spectrometry. As a result of the validation study, the analytical method was shown to be appropriate for the determination of TCH346 and its metabolites CGP70861, GP42120, CGP71090, and GP54840 in plasma for forthcoming clinical studies. The LLOQs were set to 2, 200, 20, 20, and 200 pg/mL for TCH346, CGP70861, GP42120, CGP71090, and GP54840, respectively, and the ULOQ for all analytes was 20 000 pg/mL. All analytes were stable in 50% MeOH at 4 degrees C for at least one year, in human plasma stored below -70 degrees C for at least 7 months, in human plasma below -18 degrees C for at least 6 months, in human plasma at room temperature for at least 1 day, and in the final extract solution at 4 degrees C for at least 3 days. 相似文献
106.
The radical cation of an NADH analogue (BNAH: 1-benzyl-1,4-dihydronicotinamide) has been successfully detected as the transient absorption and ESR spectra in the thermal electron transfer from BNAH to Fe(bpy)(3)(3+) (bpy = 2,2'-bipyridine) and Ru(bpy)(3)(3+). The ESR spectra of the radical cations of BNAH and the dideuterated compound (BNAH-4,4'-d(2)) indicate that the observed radical cation is the keto form rather than the enol form in the tautomerization. The deprotonation rate and the kinetic isotope effects of the keto form of BNAH(*)(+) were determined from the kinetic analysis of the electron-transfer reactions. In the case of electron transfer from BNAH to Ru(bpy)(3)(3+), the chemiluminescence due to Ru(bpy)(3)(2+) was observed in the second electron-transfer step from BNA(*), produced by the deprotonation of the keto form of BNAH(*)(+), to Ru(bpy)(3)(3+). The observation of chemiluminescence due to Ru(bpy)(3)(2+) provides compelling evidence that the Marcus inverted region is observed even for such an intermolecular electron-transfer reaction. When BNAH is replaced by 4-tert-butylated BNAH (4-t-BuBNAH), no chemiluminescence due to Ru(bpy)(3)(2+) has been observed in the electron transfer from 4-t-BuBNAH to Ru(bpy)(3)(3+). This is ascribed to the facile C-C bond cleavage in 4-t-BuBNAH(*)(+). In the laser flash photolysis of a deaerated MeCN solution of BNAH and CHBr(3), the transient absorption spectrum of the enol form of BNAH(*)(+) was detected instead of the keto form of BNAH(*)(+), and the enol form was tautomerized to the keto form. The rate of intramolecular proton transfer in the enol form to produce the keto form of BNAH(*)(+) was determined from the decay of the absorption band due to the enol form and the rise in the absorption band due to the keto form. The kinetic isotope effects were observed for the intramolecular proton-transfer process in the keto form to produce the enol form. 相似文献
107.
Tomoyoshi Ohwada Guoxing Ji Kichi-Suke Saito 《Proceedings of the American Mathematical Society》2001,129(12):3501-3510
Let be a covariant system and let be a covariant representation of on a Hilbert space . In this note, we investigate the representation of the covariance algebra and the -weakly closed subalgebra generated by and in the case of or when there exists a pure, full, -invariant subspace of .
108.
109.
110.
Hong Hai Tomoo Miura Tomoyoshi Kobayashi Yuichiro Maéda Masao Miki 《Journal of fluorescence》2000,10(2):193
Contraction of vertebrate striated muscle is regulated by the strong Ca2+-dependent interaction among troponin (Tn), tropomyosin (Tm), and actin on the thin filament. Using fluorescence resonance energy transfer (FRET), the interactions between Tm and the Tn complex or between Tm and the Tn subunit, TnI or TnC, with or without other troponin subunits, were characterized in the presence or absence of F-actin and Ca2+ ions. Cys-190 of Tm was selectively labeled with the acceptor probe, 4-dimethylaminophenylazophenyl 4-maleimide. Troponin was selectively labeled at position 9 or 133 of TnI and position 98 of TnC with a donor probe, 5-(2-iodoacetylaminoethyl)aminonaphtha lene 1-sulfonic acid. FRET measurements indicate that the interaction between TnI and Tm alone is very weak, but that in the presence of F-actin, TnI binds to the proper binding site on Tm even in the absence of TnT. The distances between Cys-190 of Tm on F-actin and Cys-9 or Cys-133 of Tnl or Cys-98 of TnC in the reconstituted Tn were determined to be 52.8, 53.7, Å and 56.5 Å, respectively, in the absence of Ca2+, indicating that the Tnl—TnC complex, the globular portion of Tn, is located near Cys-190 of Tm on the reconstituted thin filaments. Upon binding of Ca2+ to TnC, these distances increased by 5.6 and 1.4 Å or decreased by 5.4 Å, respectively. These Ca2+-induced changes in Tn—Tm seem to occur only when F-actin is present, suggesting that the stable complex formation of TnI with the outer domain of F-actin upon removal of Ca2+ is a very important event during inhibition. 相似文献