全文获取类型
收费全文 | 539篇 |
免费 | 30篇 |
国内免费 | 6篇 |
专业分类
化学 | 410篇 |
晶体学 | 1篇 |
力学 | 5篇 |
数学 | 88篇 |
物理学 | 71篇 |
出版年
2023年 | 2篇 |
2022年 | 1篇 |
2021年 | 13篇 |
2020年 | 7篇 |
2019年 | 13篇 |
2018年 | 11篇 |
2017年 | 2篇 |
2016年 | 30篇 |
2015年 | 20篇 |
2014年 | 22篇 |
2013年 | 30篇 |
2012年 | 51篇 |
2011年 | 48篇 |
2010年 | 28篇 |
2009年 | 19篇 |
2008年 | 33篇 |
2007年 | 30篇 |
2006年 | 38篇 |
2005年 | 38篇 |
2004年 | 27篇 |
2003年 | 16篇 |
2002年 | 9篇 |
2001年 | 8篇 |
2000年 | 6篇 |
1999年 | 3篇 |
1998年 | 10篇 |
1997年 | 4篇 |
1996年 | 2篇 |
1995年 | 4篇 |
1994年 | 1篇 |
1993年 | 4篇 |
1992年 | 4篇 |
1991年 | 3篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1986年 | 2篇 |
1985年 | 5篇 |
1984年 | 4篇 |
1983年 | 4篇 |
1982年 | 3篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1979年 | 4篇 |
1978年 | 3篇 |
1976年 | 2篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1972年 | 1篇 |
1931年 | 1篇 |
排序方式: 共有575条查询结果,搜索用时 22 毫秒
71.
72.
Benita Barton Eric C. Hosten Pieter L. Pohl 《Journal of inclusion phenomena and macrocyclic chemistry》2018,92(3-4):329-337
In this work, we reveal that the compound (?)-(2R,3R)-2,3-dimethoxy-1,1,4,4-tetraphenylbutane-1,4-diol (DMT) is a highly efficient host material for nitroaromatics o-nitrotoluene (o-NT), m-nitrotoluene (m-NT), p-nitrotoluene (p-NT) and nitrobenzene (NB). Each of these guests was included with a 2:1 host:guest ratio. The host displayed selectivity for p-NT and NB when these guests were mixed in equimolar proportions with any one of the other guest solvents, and the host recrystallized from this binary mixture. A selectivity order for the host in these conditions was thus noted to be NB?≈?p-NT?>?o-NT?>?m-NT. Furthermore, guests were also mixed in non-equimolar proportions and the host behaviour analysed, the results of which were in accordance with observations from the equimolar studies. Additionally, an equimolar quaternary experiment of all four guests provided a somewhat adjusted host selectivity order [p-NT (39.9%)?>?NB (30.2%)?>?m-NT (17.1%)?>?o-NT (12.8%)]. Single crystal diffraction analyses of all four complexes showed the crystals to share the same host packing, and comparable host–guest interactions were observed in each. However, thermal analyses, both DSC and TG, showed that the preferred guests p-NT and NB formed complexes with increased relative thermal stabilities, and this observation correlated with the selective behaviour of the host in competition experiments. 相似文献
73.
Back Cover: Integrated Transmission Electron and Single‐Molecule Fluorescence Microscopy Correlates Reactivity with Ultrastructure in a Single Catalyst Particle (Angew. Chem. Int. Ed. 1/2018) 下载免费PDF全文
74.
Integrated Transmission Electron and Single‐Molecule Fluorescence Microscopy Correlates Reactivity with Ultrastructure in a Single Catalyst Particle 下载免费PDF全文
Frank C. Hendriks Sajjad Mohammadian Dr. Zoran Ristanović Dr. Sam Kalirai Dr. Florian Meirer Prof. Dr. Eelco T. C. Vogt Dr. Pieter C. A. Bruijnincx Prof. Dr. Hans C. Gerritsen Prof. Dr. Bert M. Weckhuysen 《Angewandte Chemie (International ed. in English)》2018,57(1):257-261
Establishing structure–activity relationships in complex, hierarchically structured nanomaterials, such as fluid catalytic cracking (FCC) catalysts, requires characterization with complementary, correlated analysis techniques. An integrated setup has been developed to perform transmission electron microscopy (TEM) and single‐molecule fluorescence (SMF) microscopy on such nanostructured samples. Correlated structure–reactivity information was obtained for 100 nm thin, microtomed sections of a single FCC catalyst particle using this novel SMF‐TEM high‐resolution combination. High reactivity in a thiophene oligomerization probe reaction correlated well with TEM‐derived zeolite locations, while matrix components, such as clay and amorphous binder material, were found not to display activity. Differences in fluorescence intensity were also observed within and between distinct zeolite aggregate domains, indicating that not all zeolite domains are equally active. 相似文献
75.
Pieter F. W. Stouten Theo G. Prins Albert J. M. Duisenberg Jan A. Kanters Narinder S. Poonia 《Journal of chemical crystallography》1991,21(5):553-557
Na+ [C6H2(NO2)3O]– H2O,M
r=269.11, monoclinic,C2/m (No. 12),a=13.065(1),b=20.065(2),c=3.6957(4) Å,=90.75(1)°,V=968.7(1) Å3,Z=4,D
m=1.848 g cm–3 (by flotation),D
x=1.845 g cm–3, (CuK)=1.54184 Å,(CuK)=17.5 cm–1,F(000)=540,T=295 K,R=0.055,wR=0.060 for 879 observed reflections withI2.5(I). p]In the structure the picrate anion has exact twofold symmetry, the water molecule has exact mirror symmetry and the two sodium cations occupy special positions on inversion centers at (0, 1/2, 0) and (1/2, 1/2, 1/2). The phenyl ring together with the four substituent N and O atoms is strictly planar, but the phenyl ring is severely distorted from hexagonal symmetry, as is commonly observed in structures containing the picrate fragment. Both sodium ions are eight-coordinated with Na(1) and Na(2) in a cubic and distorted cubic arrangement, respectively. Na(1) coordinates to four charged phenoxide O atoms and four O atoms of nitro groups, and Na(2) to four O atoms of nitro groups and four water molecules. The water molecule donates two hydrogen bonds to symmetry-related O(2) atoms ofortho nitro groups. Two symmetry-related O(3) atoms ofortho nitro groups serve as acceptors in a very unusual asymmetric bifurcated C-HO hydrogen bond. 相似文献
76.
An analytical technique was developed to analyze light non-methane hydrocarbons (NMHC), including ethane, propane, iso-butane, n-butane, iso-pentane, n-pentane, n-hexane, isoprene, benzene and toluene from whole air samples collected in 2.5l-glass flasks used by the National Oceanic and Atmospheric Administration, Earth System Research Laboratory, Global Monitoring Division (NOAA ESRL GMD, Boulder, CO, USA) Cooperative Air Sampling Network. This method relies on utilizing the remaining air in these flasks (which is at below-ambient pressure at this stage) after the completion of all routine greenhouse gas measurements from these samples. NMHC in sample aliquots extracted from the flasks were preconcentrated with a custom-made, cryogen-free inlet system and analyzed by gas chromatography (GC) with flame ionization detection (FID). C2-C7 NMHC, depending on their ambient air mixing ratios, could be measured with accuracy and repeatability errors of generally < or =10-20%. Larger deviations were found for ethene and propene. Hexane was systematically overestimated due to a chromatographic co-elution problem. Saturated NMHC showed less than 5% changes in their mixing ratios in glass flask samples that were stored for up to 1 year. In the same experiment ethene and propene increased at approximately 30% yr(-1). A series of blank experiments showed negligible contamination from the sampling process and from storage (<10 pptv yr(-1)) of samples in these glass flasks. Results from flask NMHC analyses were compared to in-situ NMHC measurements at the Global Atmospheric Watch station in Hohenpeissenberg, Germany. This 9-months side-by-side comparison showed good agreement between both methods. More than 94% of all data comparisons for C2-C5 alkanes, isoprene, benzene and toluene fell within the combined accuracy and precision objectives of the World Meteorological Organization Global Atmosphere Watch (WMO-GAW) for NMHC measurements. 相似文献
77.
Erik Pieter van Geest Sina Katharina Götzfried David M. Klein Nadiya Salitra Sorraya Popal Yurii Husiev Corjan J. Van der Griend Xuequan Zhou Maxime A. Siegler Gregory F. Schneider Sylvestre Bonnet 《Photochemistry and photobiology》2023,99(2):777-786
Photosubstitutionally active ruthenium complexes show high potential as prodrugs for the photoactivated chemotherapy (PACT) treatment of tumors. One of the problems in PACT is that the localization of the ruthenium compound is hard to trace. Here, a ruthenium PACT prodrug, [Ru(3)(biq)(STF-31)](PF6)2 (where 3 = 3-(([2,2′:6′,2″-ter- pyridin]-4′-yloxy)propyl-4-(pyren-1-yl)butanoate) and biq = 2,2′-biquinoline), has been prepared, in which a pyrene tracker is attached via an ester bond. The proximity between the fluorophore and the ruthenium center leads to fluorescence quenching. Upon intracellular hydrolysis of the ester linkage, however, the fluorescence of the pyrene moiety is recovered, thus demonstrating prodrug cellular uptake. Further light irradiation of this molecule liberates by photosubstitution STF-31, a known cytotoxic nicotinamide phosphoribosyltransferase (NAMPT) inhibitor, as well as singlet oxygen via excitation of the free pyrene chromophore. The dark and light cytotoxicity of the prodrug, embedded in liposomes, as well as the appearance of blue emission upon uptake, were evaluated in A375 human skin melanoma cells. The cytotoxicity of the liposome-embedded prodrug was indeed increased by light irradiation. This work realizes an in vitro proof-of-concept of the lock-and-kill principle, which may ultimately be used to design strategies aimed at knowing where and when light irradiation should be realized in vivo. 相似文献
78.
Xianfeng Li Pieter Vandezande Ivo F.J. Vankelecom 《Journal of membrane science》2008,320(1-2):143-150
New solvent resistant nanofiltration (SRNF) membranes with polypyrrole (PPy) modified toplayer were prepared on different types support by in situ pyrrole polymerization. The morphology of the membranes was studied by SEM. The PPy modified membranes were applied in the filtration of organic solvents. All the PPy modified membranes showed a very high retention of the negatively charged RB in different solvent systems, comparable to those of the MPF-50 and STARMEM 122 commercial membranes, but at much higher flux. The extended filtration experiment in strong aprotic DMF of PPy modified membranes showed a clearly stable permeability and retention over 30 h. In addition, the PPy modified membranes showed a much higher flux in THF systems than for earlier reported crosslinked poly(imide) membranes. 相似文献
79.
Saveyn P Cocquyt J De Cuyper M Van der Meeren P 《Langmuir : the ACS journal of surfaces and colloids》2008,24(12):6007-6012
The interaction of the amine containing beta-receptor blocking agent propranolol (Ppn) with dimyristoylphosphatidylcholine (DMPC) vesicles was studied. Using a centrifugation assay, the protonated as well as unprotonated amount of the drug sorbed was verified, whereas the binding of the protonated Ppn was deduced from the surface charge density of the vesicles as calculated from electrophoretic mobility measurements. Assuming a 1:1 binding, a Langmuir model with only two parameters was found to be sufficient to fit all experimental data. Sensitivity analysis revealed that the estimated values of these parameters were reliable and independent from each other. These parameters were truly intrinsic, as electrostatic interactions were accounted for in the model. It was found that the pKa of Ppn shifted from 9.24, when dissolved in water, downward by 1.34 units upon sorption, indicating that the intrinsic partition coefficient of the unprotonated Ppn was about 22 times higher than that of the protonated analog. In addition, a significant increase in the affinity of both Ppn analogs with increasing salt concentration was found. Theoretical analysis revealed that the Langmuir sorption model may be considered as a partitioning model with decreasing partition coefficient as the sorbed amount increases. Thus, the Langmuir model provides a better fit than a simple partition model at conditions that induce a substantial amount of propranolol sorbed, such as high pH and high propranolol concentrations. 相似文献
80.
Bruijnincx PC Buurmans IL Gosiewska S Moelands MA Lutz M Spek AL van Koten G Klein Gebbink RJ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(4):1228-1237
The Rieske dioxygenases are a group of non-heme iron enzymes, which catalyze the stereospecific cis-dihydroxylation of its substrates. Herein, we report the iron(II) coordination chemistry of the ligands 3,3-bis(1-methylimidazol-2-yl)propionate (L1) and its neutral propyl ester analogue propyl 3,3-bis(1-methylimidazol-2-yl)propionate (PrL1). The molecular structures of two iron(II) complexes with PrL1 were determined and two different coordination modes of the ligand were observed. In [Fe(II)(PrL1)(2)](BPh(4))(2) (3) the ligand is facially coordinated to the metal with an N,N,O donor set, whereas in [Fe(II)(PrL1)(2)(MeOH)(2)](OTf)(2) (4) a bidentate N,N binding mode is found. In 4, the solvent molecules are in a cis arrangement with respect to each other. Complex 4 is a close structural mimic of the crystallographically characterized non-heme iron(II) enzyme apocarotenoid-15-15'-oxygenase (APO). The mechanistic features of APO are thought to be similar to those of the Rieske oxygenases, the original inspiration for this work. The non-heme iron complexes [Fe(II)(PrL1)(2)](OTf)(2) (2) and [Fe(II)(PrL1)(2)](BPh(4))(2) (3) were tested in olefin oxidation reactions with H(2)O(2) as the terminal oxidant. Whereas 2 was an active catalyst and both epoxide and cis-dihydroxylation products were observed, 3 showed negligible activity under the same conditions, illustrating the importance of the anion in the reaction. 相似文献