全文获取类型
收费全文 | 2549篇 |
免费 | 75篇 |
国内免费 | 8篇 |
专业分类
化学 | 2061篇 |
晶体学 | 39篇 |
力学 | 27篇 |
数学 | 199篇 |
物理学 | 306篇 |
出版年
2023年 | 12篇 |
2022年 | 18篇 |
2021年 | 22篇 |
2020年 | 35篇 |
2019年 | 45篇 |
2018年 | 21篇 |
2017年 | 28篇 |
2016年 | 51篇 |
2015年 | 51篇 |
2014年 | 59篇 |
2013年 | 121篇 |
2012年 | 136篇 |
2011年 | 147篇 |
2010年 | 77篇 |
2009年 | 87篇 |
2008年 | 153篇 |
2007年 | 160篇 |
2006年 | 146篇 |
2005年 | 133篇 |
2004年 | 141篇 |
2003年 | 116篇 |
2002年 | 98篇 |
2001年 | 43篇 |
2000年 | 48篇 |
1999年 | 23篇 |
1998年 | 38篇 |
1997年 | 37篇 |
1996年 | 31篇 |
1995年 | 17篇 |
1993年 | 16篇 |
1992年 | 26篇 |
1991年 | 24篇 |
1990年 | 24篇 |
1989年 | 16篇 |
1988年 | 22篇 |
1987年 | 25篇 |
1986年 | 15篇 |
1985年 | 23篇 |
1984年 | 29篇 |
1983年 | 25篇 |
1982年 | 29篇 |
1981年 | 29篇 |
1980年 | 44篇 |
1979年 | 26篇 |
1978年 | 23篇 |
1977年 | 19篇 |
1976年 | 24篇 |
1975年 | 18篇 |
1974年 | 18篇 |
1973年 | 19篇 |
排序方式: 共有2632条查询结果,搜索用时 0 毫秒
931.
Flame atomic emission and atomic absorption detection limits are compared on an absolute basis for the easily determined element, copper. Remarkably similar detection limits are obtained with a variety of atomization and sample introduction system combinations. Heated graphite atomizers offer significantly lower minimum detectable quantities. 相似文献
932.
933.
934.
Shinsaku Dobashi Masaharu Kira Ryuichiro Tanaka Yoshinori Izawa Yoshihiro Deguchi Takahiro Kubota Akihide Wada Michikazu Hara 《Analytical sciences》2005,21(9):1111-1115
LI-IT-TOFMS (laser ionization/ion-trap storage/time-of-flight mass spectrometry) is expected to be a powerful tool for environmental monitoring. In the research reported here, real-time LI-IT-TOFMS measurements were carried out on gaseous 2-4 chlorinated PCBs in order to evaluate the applicability of an environmental monitoring method. With respect to ion-trap storage for PCBs, we found that the effect was due to the driving RF voltage on the ring electrode in the ion trap. For PCBs ions produced by laser irradiation, we observed that it was more efficient to reach the center of the ion trap by using a gated RF voltage rather than by using a continuous RF voltage. The ion trajectories in the ion trap were simulated by SIMION 7.0. We found that the voltage of the exit end cap electrode affected both the number of ions trapped and the orbit of ions inside the trap cell. Optimization of this parameter was performed using both simulated and experimental results. The achievable PCBs sensitivity for real-time (1 min) measurement using the LI-IT-TOFMS method was found to be in the pptV range (<0.01 mg/m3N) by means of a comparison with the conventional gas sampling/GS-MS method. A satisfactory proportional relationship was confirmed between the laser-based and conventional results. 相似文献
935.
Kazuhiko Tsukagoshi Yukihiro Shikata Riichiro Nakajima Masaharu Murata Mizuo Maeda 《Analytical sciences》2002,18(11):1195-1198
We developed capillary electrophoresis with a chemiluminescence detector using a polymer solution as the separation medium for the analysis of biopolymers, such as DNA and protein. A peroxyoxalate chemiluminescence reagent of bis(2,4,6-trichlorophenyl)oxalate was used together with fluorescein-labeling reagent. When a migration buffer solution containing carboxylmethylcellulose was used, the flow-type chemiluminescence detection cell was found to give a better resolution than the batch-type one. Fluorescein-labeled adenosine triphosphate of 1.0 x 10(-4) M was examined by means of capillary electrophoresis with absorption (260 nm), fluorescence (ex. 496 nm and em. 517 nm), and chemiluminescence detectors. The chemiluminescence detection showed the highest sensitivity among them; the S/N ratios obtained by absorption, fluorescence, and chemiluminescence detections were 4, 38, and 130, respectively. Fluorescein-labeled DNA was prepared through a polymerase chain reaction using fluorescein-labeled deoxyadenosine triphosphate. A mixture of the labeled DNA fragments (500, 600, 700, 800, 900, and 993 bp) was successfully separated and detected by the present system. A mixture of proteins (lysozyme, cytochrome C, and ribonuclease A) which were labeled with fluorescein isothiocyanate was also separated and detected. 相似文献
936.
Fukamizu K Miyake Y Nishibayashi Y 《Journal of the American Chemical Society》2008,130(32):10498-10499
Our previously disclosed ruthenium-catalyzed carbon-carbon bond forming reactions between propargylic alcohols and alkenes via an allenylidene-ene type pathway have been successfully applied to an enantioselective intramolecular cyclization for a variety of chiral heterocycles such as chromane, thiochromane, and 1,2,3,4-tetrahydroquinoline derivatives (up to 99% ee) by use of a suitable optically active diruthenium complex as a catalyst. The methodology described in this paper becomes a novel synthetic approach to chiral heterocycles, the structures of which are widely found in many natural and biologically active compounds. 相似文献
937.
Whitener KE Frunzi M Iwamatsu S Murata S Cross RJ Saunders M 《Journal of the American Chemical Society》2008,130(42):13996-13999
We put ammonia into an open-cage fullerene with a 20-membered ring ( 1) as the orifice and examined the properties of the complex using NMR and MALDI-TOF mass spectroscopy. The proton NMR shows a broad resonance corresponding to endohedral NH 3 at delta H = -12.3 ppm relative to TMS. This resonance was seen to narrow when a (14)N decoupling frequency was applied. MALDI spectroscopy confirmed the presence of both 1 ( m/ z = 1172) and 1 + NH 3 ( m/ z = 1189), and integrated intensities of MALDI peak trains and NMR resonances indicate an incorporation fraction of 35-50% under our experimental conditions. NMR observations showed a diminished incorporation fraction after 6 months of storage at -10 degrees C, which indicates that ammonia slowly escapes from the open-cage fullerene. 相似文献
938.
Kasai Y Matsumori N Umegawa Y Matsuoka S Ueno H Ikeuchi H Oishi T Murata M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(4):1178-1185
Amphotericin B (AmB) is thought to exert its pharmacological effects by forming a barrel-stave assembly with ergosterol in fungal membranes. To examine the interaction between AmB and ergosterol (Erg) or cholesterol (Cho), (13)C- and (19)F-labelled covalent conjugates were prepared as reported previously (N. Matsumori et al. Chem. Biol. 2004, 11, 673-679). The CD spectra of the conjugates in a membrane-bound form suggested that the distance between the heptaene moieties of the ergosterol conjugates AmB-C(2)-(6-F)Erg 2 and AmB-C(2)-Erg 3 is similar to that of AmB in ergosterol-containing membranes, but significantly larger than that of AmB in nonsterol or cholesterol-containing membranes. These observations suggest that, as is the case with ergosterol-containing membranes, the conjugated sterol moiety prevents the close contact between the heptaene moieties within the membrane that would reduce channel conductivity of the AmB assemblies. To further investigate this bimolecular interaction, we recorded the solid-state NMR spectra of conjugates 2 and AmB-C(2)-(6-F)Cho 4, which are composed of uniformly (13)C-labelled AmB and 6-fluorinated ergosterol or cholesterol; the conjugates were expected to facilitate the estimation of distances between the fluorine and carbon atoms. By using rotor-synchronous double resonance (rotational echo double resonance of X cluster; RDX) experiments, we deduced the distance between the fluorine atom and its nearest carbon atom in the heptaene moiety of 2 to be less than 8.6 A. This indicates that the B ring of ergosterol comes close to the AmB polyene moiety. A conformational search of the AmB-ergosterol conjugate by using distance constraints derived from the RDX results suggested that ergosterol molecules possibly surround the AmB assembly, which is in contrast with the conventional image in which ergosterol is inserted into AmB molecules. 相似文献
939.
Takebayashi Y Mashimo Y Koike D Yoda S Furuya T Sagisaka M Otake K Sakai H Abe M 《The journal of physical chemistry. B》2008,112(30):8943-8949
Fourier transform infrared (FT-IR) spectrum of water-in-supercritical CO(2) microemulsion was measured at 60 degrees C and 30.0 MPa over a wide range of water/CO(2) ratio from 0.0 to 1.2 wt % to study the distribution of water into CO(2), interfacial area around surfactant headgroup, and core water pool. The microemulsion was stabilized by sodium bis(1H,1H,2H, 2H-heptadecafluorodecyl)-2-sulfosuccinate [8FS(EO)(2)] equimolarly mixed with sodium 1-oxo-1-[4-(tridecafluorohexyl)phenyl]-2-hexanesulfonate [FC6HC4] or with poly(ethylene glycol) 2,6,8-trimethyl-4-nonyl ether [TMN-6]. The signal area of the O-H stretching band of water suggested that the number of water molecules in the microemulsion increases linearly with the water/CO(2) ratio, except for a slow initial increase below 0.4 wt % due to a part of water dissolved in CO(2). The amount of water in CO(2) was evaluated by decomposing the bending band of water into two components, one at lower frequency ascribed to water in CO(2) and the other at higher frequency to water in the microemulsion. The decomposition confirmed that CO(2) is saturated with water at the water content of 0.4 wt %. It was also revealed, from the symmetric SO stretching frequency of the surfactant, that the sulfonate headgroup is completely hydrated at the water/CO(2) ratio of 0.4-0.5 wt %. The results demonstrated that water is introduced preferentially into CO(2) and the interfacial area at small water content, and then is loaded into the micelle core after the saturation of CO(2) with water and the full hydration of the surfactant headgroup. 相似文献
940.
The development of retention prediction models for the seven ginsenosides Rf, Rg1, Rd, Re, Rc, Rb2, and Rb1 on a polyamine-bonded stationary phase in hydrophilic interaction chromatography (HILIC) is presented. The models were derived using multiple linear regression (MLR) and artificial neural network (ANN) using the logarithm of the retention factor (log k) as the dependent variable for four temperature conditions (0, 10, 25, and 40 degrees C). Using stepwise MLR, the retention of the analytes in all the temperature conditions was satisfactorily described by a two-predictor model wherein the predictors were the percentage of ACN (%ACN) in the mobile phase and local dipole index (LDI) of the compounds. These predictors account for the contribution of the solute-related variable (LDI) and the influence of the mobile phase composition (%ACN) on the retention behavior of the ginsenosides. A comparison of the models derived from both MLR and ANN revealed that the trained ANNs showed better predictive abilities than the MLR models in all temperature conditions as demonstrated by their higher R(2) values for both training and test sets and lower average percentage deviation of the predicted log k from the observed log k of the test compounds. The ANN models also showed excellent performance when applied to the prediction of the seven ginsenosides in different sample matrices. 相似文献