全文获取类型
收费全文 | 1179篇 |
免费 | 29篇 |
国内免费 | 6篇 |
专业分类
化学 | 984篇 |
晶体学 | 12篇 |
力学 | 8篇 |
数学 | 48篇 |
物理学 | 162篇 |
出版年
2023年 | 5篇 |
2022年 | 3篇 |
2021年 | 7篇 |
2020年 | 13篇 |
2019年 | 15篇 |
2018年 | 7篇 |
2017年 | 9篇 |
2016年 | 23篇 |
2015年 | 22篇 |
2014年 | 39篇 |
2013年 | 35篇 |
2012年 | 64篇 |
2011年 | 89篇 |
2010年 | 43篇 |
2009年 | 44篇 |
2008年 | 82篇 |
2007年 | 88篇 |
2006年 | 89篇 |
2005年 | 76篇 |
2004年 | 83篇 |
2003年 | 59篇 |
2002年 | 50篇 |
2001年 | 17篇 |
2000年 | 12篇 |
1999年 | 8篇 |
1998年 | 3篇 |
1997年 | 10篇 |
1996年 | 11篇 |
1995年 | 10篇 |
1994年 | 13篇 |
1993年 | 8篇 |
1992年 | 12篇 |
1991年 | 9篇 |
1990年 | 12篇 |
1989年 | 5篇 |
1988年 | 9篇 |
1987年 | 7篇 |
1986年 | 7篇 |
1985年 | 13篇 |
1984年 | 15篇 |
1983年 | 13篇 |
1982年 | 15篇 |
1981年 | 15篇 |
1980年 | 9篇 |
1979年 | 3篇 |
1978年 | 6篇 |
1977年 | 5篇 |
1976年 | 6篇 |
1975年 | 5篇 |
1968年 | 3篇 |
排序方式: 共有1214条查询结果,搜索用时 156 毫秒
61.
Ryoichi Suzuki Yoshinori Kobayashi Tomohisa Mikado Hideaki Ohgaki Mitsukuni Chiwaki Tetsuo Yamazaki 《Hyperfine Interactions》1994,84(1):345-353
A positron pulsing system for an intense positron beam generated by an electron linac is reported. The pulsing system generates an intense pulsed positron beam of variable energy and variable pulse period. The pulsed positron beam is used as a non-destructive probe for various material research. In this paper, we also discuss applications of the pulsed positron beam: positron lifetime spectroscopy, age-momentum correlation spectroscopy, positronium time-of-flight measurement, and positron annihilation-induced Auger electron spectroscopy with a time-of-flight technique. 相似文献
62.
Akio Maeda Jun Sasaki Jean-Marc Pfefferl Yoshinori Shichida Tru Yoshizawa 《Photochemistry and photobiology》1991,54(6):911-921
Abstract– Difference Fourier transform infrared spectra were recorded for bacteriorhodopsin upon irradiation at 230, 170 or 77 K, which gave, respectively, the spectrum of the M, L or K intermediate minus unphotolyzed all-trans bacteriorhodopsin (denoted as BR). By replacement of the Schiff base nitrogen with 15N, or of either its hydrogen at N or C15 with deuterium, the vibrational bands related to the Schiff base were identified and the isotope-shifts evaluated for BR, K and L. The 1348 cm?l band of BR and K and the 1400 cm?1 band of L were sensitive to each of these isotope substitutions. The 1254 cm?1 band of BR, the 1245 cm?1 band of K and the 1301 cm?1 band of L were sensitive to either N- or C15-deuteration but not to 15N-substitution. The N—D in-plane bending vibration of K and L appeared at 969 and 997 cm?1, respectively, upon substitution with D2O. All the results show that L is larger in frequencies related to the N—H in-plane bending vibration than K or BR and suggest that L has the strongest interaction with the protein. Among the bands containing an N—H bending vibration, the 1348 cm?1 band of K was more intense than the corresponding band of L at 1400 cm?1. The C15-deuteration-induced upshift of the 1245 cm?1 band of K was unobservable for the 1301 cm?1 band of L. Such differences between L and K might be brought about by a distortion in the retinal moiety close to the protonated Schiff base of the 13-cis chromophore. 相似文献
63.
Hideaki Furukawa Tsuyoshi Konishi Yoshinori Oshita Wanji Yu Kazuyoshi Itoh Yoshiki Ichioka 《光学学报》2003,23(Z1)
We demonstrate a suppression effect of a crosstalk among a target and similar header signals using the header recognition filter designed by a design technique of the multiple-object discriminant filter. 相似文献
64.
Yoshinori Kamiya Keishin Mizoguchi Yasutoshi Naito Dominique Bourbon 《Journal of Polymer Science.Polymer Physics》1991,29(2):225-234
Sorption and dilation isotherms for argon in poly(ethyl methacrylate) (PEMA) are reported for pressures up to 50 atm over the temperature range 5–85°C. At temperatures below the glass transition (Tg=61°C), sorption isotherms are well described by the dual-mode sorption model; and isotherms above Tg follow Henry's law. However, isotherms for dilation due to sorption are linear in pressure at all temperatures over the range investigated. Partial molar volumes of Ar in PEMA are obtained from these isotherms. The volumes are approximately constant above Tg (about 40 cm3/mol), whereas the volumes below Tg are smaller and dependent on both temperature and concentration (19–26 cm3/mol). By analyzing the experimental data according to the dual-mode sorption and dilation model, the volume occupied by a dissolved Ar molecule and the mean size of microvoid in the glass are estimated to be 67 129 Å3, respectively. The cohesive energy density of the polymer is also estimated as 61 cal/cm3 from the temperature dependence of the dual-mode parameters. 相似文献
65.
Atsuko Kawata Tadashi Oishi Yoshitaka Fukada Yoshinori Shichida Tôru Yoshizawa 《Photochemistry and photobiology》1992,56(6):1157-1166
Types of photoreceptor cells in the retinas of 36 species of vertebrates (5 classes, 14 orders) were investigated immunocytochemically with monoclonal antibodies against chicken iodopsin (Io-mAb) and antiserum against bovine rhodopsin (Rh-As). In mammals, Rh-As labeled the outer segments of some photoreceptor cells in striped squirrels (a diurnal mammal) and those of most photoreceptor cells in mice (a nocturnal mammal), while Io-mAb labeled any photoreceptor cells in either of them. In all species of birds studied, Io-mAb labeled the principal and accessory members of double cones and single cones with a red oil droplet. Rh-As labeled single cones with a yellow or clear oil droplet in addition to rods. In turtles, both Rh-As and Io-mAb labeled single cones with a red or clear oil droplet and the principal (with a yellow oil droplet) and accessory members of double cones. This suggests that the visual pigments in these cones of turtles have common epitopes with bovine rhodopsin and chicken iodopsin. In Japanese grass lizards, single cones with a yellow oil droplet and double cones were immunoreactive to both Rh-As and Io-mAb. In snakes, rods and cones could not be distinguished but both positively and negatively stained cells were observed by the use of each antibody. In geckos, however, all photoreceptor cells were immunonegative to Io-mAb. In all species studied in amphibians, Rh-As labeled rods but not cones. Neither rods nor cones reacted with Io-mAb. In fishes, almost all species studied had well developed cones, and some of these cones were labeled by Rh-As. However, Io-mAb labeled the outer segments of some cones only in loaches. Rh-As labeled photoreceptor cells in all species of fishes studied. Thus, Rh-As recognized the outer segments of rods in all species studied from fishes to mammals, whereas the epitope recognized by Io-mAb is conserved in some species of fishes, most species of reptiles and all species of birds studied. 相似文献
66.
Three-dimensional porous coordination polymer functionalized with amide groups based on tridentate ligand: selective sorption and catalysis 总被引:1,自引:0,他引:1
Hasegawa S Horike S Matsuda R Furukawa S Mochizuki K Kinoshita Y Kitagawa S 《Journal of the American Chemical Society》2007,129(9):2607-2614
To create a functionalized porous compound, amide group is used in porous framework to produce attractive interactions with guest molecules. To avoid hydrogen-bond formation between these amide groups our strategy was to build a three-dimensional (3D) coordination network using a tridentate amide ligand as the three-connector part. From Cd(NO3)2.4H2O and a three-connector ligand with amide groups a 3D porous coordination polymer (PCP) based on octahedral Cd(II) centers, {[Cd(4-btapa)2(NO3)2].6H2O.2DMF}n (1a), was obtained (4-btapa = 1,3,5-benzene tricarboxylic acid tris[N-(4-pyridyl)amide]). The amide groups, which act as guest interaction sites, occur on the surfaces of channels with dimensions of 4.7 x 7.3 A2. X-ray powder diffraction measurements showed that the desolvated compound (1b) selectively includes guests with a concurrent flexible structural (amorphous-to-crystalline) transformation. The highly ordered amide groups in the channels play an important role in the interaction with the guest molecules, which was confirmed by thermogravimetric analysis, adsorption/desorption measurements, and X-ray crystallography. We also performed a Knoevenagel condensation reaction catalyzed by 1a to demonstrate its selective heterogeneous base catalytic properties, which depend on the sizes of the reactants. The solid catalyst 1a maintains its crystalline framework after the reaction and is easily recycled. 相似文献
67.
Kondo Y Morey JV Morgan JC Naka H Nobuto D Raithby PR Uchiyama M Wheatley AE 《Journal of the American Chemical Society》2007,129(42):12734-12738
Sequential reaction of HTMP (= 2,2,6,6-tetramethylpiperidine) with nBuLi and Et2Zn affords unsolvated polymer chains of EtZn(micro-Et)(micro-TMP)Li 6. The scope of this reagent in directed ortho metalation (DoM) chemistry has been tested by its reaction with N,N-diisopropylnaphthamide in THF to give EtZn(micro-C10H6C(O)NiPr2-2)2Li.2THF 7. Data reveal that 6 has undergone reaction with 2 equiv of aromatic tertiary amide and imply that it exhibits dual alkyl/amido basicity. DFT calculations reveal that direct alkyl basicity is kinetically disfavored and instead point to a stepwise mechanism whereby 6 acts as an amido base, liberating HTMP during the first DoM event. Re-coordination of the amine at lithium then incurs the elimination of EtH. Reaction of the resulting alkyl(amido)(arylamido)zincate with a second equivalent of N,N-diisopropylnaphthamide eliminates HTMP and affords 7. Both DoM steps involve the exhibition of amido basicity and each reveals a low kinetic barrier to reaction. Understanding of this reaction sequence is tested by treating 6 with N,N-diisopropylbenzamide in THF. On the basis of theory and experiment, the presence of THF solvent (in place of stronger Lewis bases) combined with the use of a sterically less congested aromatic amide is expected to encourage threefold, stepwise reaction. Isolation and characterization of the resulting tripodal zincate Zn(micro-C6H4C(O)NiPr2-2)3Li.THF 8 bears this out and suggests a significant new level of control in zincate-induced DoM chemistry through the combination of experiment and DFT studies. 相似文献
68.
Shimazaki Y Tashiro M Motoyama T Iwatsuki S Yajima T Nakabayashi Y Naruta Y Yamauchi O 《Inorganic chemistry》2005,44(17):6044-6051
Synthetic, structural, spectroscopic, and kinetic studies have been carried out on the Pd(II) complexes of new 2N1O-donor ligands containing a pendent indole, 3-(N-2-pyridylmethyl-N-2-hydroxy-5-methoxybenzylamino)ethylindole (HMeO-iepp), 3-(N-2-pyridylmethyl-N-2-hydroxy-5-nitrobenzylamino)ethylindole (HNO2-iepp), and (N-2-pyridylmethyl-3-indolylethylamino)acetic acid (Hiepc) (H denotes a dissociable proton). [Pd(MeO-iepp)Cl] (2), [Pd(NO2-iepp)Cl] (3), and [Pd(iepc)Cl] (4) were prepared and revealed by X-ray analysis to have a pyridine nitrogen, an amine nitrogen, a phenolate or carboxylate oxygen, and a chloride ion in the coordination plane. UV absorption and 1H NMR spectral changes indicated that all the complexes could be converted to the indole-binding complexes where the O donor was replaced by the indole C2 atom by cyclopalladation in DMSO or DMF in the temperature range of 40-60 degrees C. Formation of the indole-binding complex species obeyed the first-order kinetics, from which the activation parameters were estimated. The formation rate was dependent on the properties of the O-donor group, a lower pKa value of its conjugate acid causing faster conversion to the indole-binding species in the order 2 (methoxyphenolate) < 3 (nitrophenolate) < 4 (carboxylate). On the other hand, the ratio of the indole-binding complex to the O-donor complex as a result of the conversion was greater for the complexes with a higher pKa value of the ligand OH group, the order being 2 > 3 > 4. 相似文献
69.
Yoshinori Kadoma Takashi Toida Kenji Takeda Keikichi Uno Yoshio Iwakura 《Journal of polymer science. Part A, Polymer chemistry》1975,13(3):707-716
The polymerization of picryl (PMA), 2,4-dinitrophenyl (2,4-DNMA),2,6-dinitrophenyl (2,6-DNMA), 2-methyl-4,6-dinitrophenyl (MDNMA), and 2,6-dimethylphenyl methacrylates (DMMA) was carried out in benzene at 60°C. PMA, 2,6-DNMA, and MDNMA did not undergo radical homopolymerization, while 2,4-DNMA and DMMA did. The results suggest that the growing radical readily attacks the oxygen atom of the nitro group at the 2 position of the terminal phenyl group due to the steric effect of the substituent at the 6 position, resulting in chain termination. PMA formed a charge-transfer complex with 2-naphthyl methacrylate (NMA). The stoichiometric composition of this complex was shown to be 1:1 molar complex. PMA was readily copolymerized with NMA. The amount of solvent affected the composition of the copolymer obtained at a given same mole fraction in feed. The results suggest that charge-transfer interaction between the ester groups affects the copolymerization mechanism. 相似文献
70.
The development of a water-soluble and small molecular weight fluorescent probe, 3-(4-methoxyphenyl)-4-(methylsulfanyl)-6-(pyridin-2-yl)pyridin-2(1H)-one (3), for detecting Zn2+ based on pyridine-pyridone skeleton is reported. We observed a clear chelation enhanced fluorescence effect of 3 in the presence of Zn2+. Other fluorescent properties of 3 are discussed. 相似文献