全文获取类型
收费全文 | 776篇 |
免费 | 37篇 |
国内免费 | 1篇 |
专业分类
化学 | 519篇 |
晶体学 | 14篇 |
力学 | 11篇 |
数学 | 107篇 |
物理学 | 163篇 |
出版年
2023年 | 12篇 |
2022年 | 8篇 |
2021年 | 16篇 |
2020年 | 33篇 |
2019年 | 30篇 |
2018年 | 12篇 |
2017年 | 12篇 |
2016年 | 26篇 |
2015年 | 24篇 |
2014年 | 39篇 |
2013年 | 43篇 |
2012年 | 45篇 |
2011年 | 52篇 |
2010年 | 16篇 |
2009年 | 15篇 |
2008年 | 34篇 |
2007年 | 31篇 |
2006年 | 34篇 |
2005年 | 18篇 |
2004年 | 17篇 |
2003年 | 12篇 |
2002年 | 5篇 |
2000年 | 10篇 |
1999年 | 7篇 |
1997年 | 9篇 |
1993年 | 7篇 |
1992年 | 6篇 |
1986年 | 6篇 |
1984年 | 5篇 |
1979年 | 5篇 |
1978年 | 8篇 |
1976年 | 6篇 |
1975年 | 6篇 |
1949年 | 6篇 |
1937年 | 6篇 |
1931年 | 4篇 |
1928年 | 6篇 |
1927年 | 9篇 |
1925年 | 10篇 |
1924年 | 8篇 |
1923年 | 6篇 |
1921年 | 4篇 |
1913年 | 6篇 |
1912年 | 6篇 |
1909年 | 5篇 |
1908年 | 4篇 |
1907年 | 10篇 |
1906年 | 4篇 |
1904年 | 4篇 |
1883年 | 4篇 |
排序方式: 共有814条查询结果,搜索用时 241 毫秒
1.
Designs, Codes and Cryptography - We study security functions which can serve to establish semantic security for the two central problems of information-theoretic security: the wiretap channel, and... 相似文献
2.
Dr. Liat Avram Dr. Václav Havel Ronit Shusterman-Krush Dr. Mark A. Iron Dr. Moritz Zaiss Prof. Vladimír Šindelář Dr. Amnon Bar-Shir 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(7):1687-1690
The accumulated knowledge regarding molecular architectures is based on established, reliable, and accessible analytical tools that provide robust structural and functional information on assemblies. However, both the dynamicity and low population of noncovalently interacting moieties within studied molecular systems limit the efficiency and accuracy of traditional methods. Herein, the use of a saturation transfer-based NMR approach to study the dynamic binding characteristics of an anion to a series of synthetic receptors derived from bambusuril macrocycles is demonstrated. The exchange rates of BF4− are mediated by the side chains on the receptor (100 s−1<kex<5000 s−1), which play a critical role in receptor-anion binding dynamics. The signal amplification obtained with this approach allows for the identification of different types of intermolecular interactions between the receptor and the anion, something that could not have been detected by techniques hitherto used to study molecular assemblies. These findings, which are supported by a computational molecular dynamic study, demonstrate the uniqueness and added value of this NMR method. 相似文献
3.
S. B. Ellis S. J. Kiehl W. S. Hughes K. Schwabe W. C. Gardiner H. L. Sanders H. Yoshimura Hanna Jablezynska-Jedrzewska J. Domański W. A. Dorfman P. Nylén Barbara Stone F. Hovorka W. C. Dearing E. Biilmann W. Kordatzki P. Wulff G. Florence A. Drilhon P. Szigeti O. Tomiček F. Poupě O. Redlich W. Stricks 《Analytical and bioanalytical chemistry》1937,111(2-4):94-104
4.
Moritz Kohn 《Monatshefte für Chemie / Chemical Monthly》1923,43(5):373-376
Ohne ZusammenfassungHerrn Ingenieur E. Hofmann danke ich fÜr seine bewährte UnterstÜtzung. 相似文献
5.
C. Mahr H. Bergmann P. Zuman J. Sunkel K. -J. Range K. -H. König W. Schermann G. Manecke A. Sippel E. Best K. Hartl J. Volke H. Kübler P. Moritz H. H. Pfeiffer E. Knickmann H. Lüken 《Colloid and polymer science》1967,218(2):158-171
Ohne Zusammenfassung 相似文献
6.
Coordination of dinitrogen to Sellmann-type iron (II) complexes in a sulfur-dominated coordination sphere, which emulates
the environment of iron centers in the FeMo-cofactor of nitrogenase, is analyzed with respect to spin states, spin barriers,
and the effect of trans-ligands. Such detailed investigations became only recently feasible when the reliability of density functional methods, which
are the only quantum chemical methods capable of describing large transition metal complexes, could significantly be improved
for the calculation of energies for states of different spin. It is found that the actual binding energy of dinitrogen is
of sufficient magnitude for a reasonably strong fixation of N2 by Sellmann-type coordination compounds. However, potential fixation is determined by additional factors which reduce the
binding energy. One factor is the change in spin state of the N2-free metal fragment, which lowers the total energy and quenches the thermodynamic stabilization effect of the binding energy.
In addition, the metal fragment rearranges and gains even more stabilization energy for the un-coordinated state. Apart from
these thermodynamical effects, the existence of spin barriers, which must be overcome upon binding of dinitrogen, leads to
kinetical effects, which cannot be neglected. 相似文献
7.
Dimethyl bromomethylmalonate (IV) reacts with vitamin B12s in aqueous solution yielding a relatively unstable carbon-cobalt bonded adduct V, which shows visible spectra in good accord with expectation. The adduct V was allowed to decompose in water, in the dark, at room temperature and at physiological pH. Three products: succinic acid (VI), methylmalonic acid (VIII) and malonic acid (VII) were formed in 3, 18, and 13% yields respectively. Isolation of the succinic acid rearrangement product provides support for the intermediacy of the carbon-cobalt bond in the coenzyme B12 dependent enzymic carbon-skeleton rearrangement of methylmalonyl-SCoA to succinyl-SCoA. 相似文献
8.
Stephan?HaiberEmail author Xingtao?Ai Henning?Bubert Moritz?Heintze Volker?Brüser Waltraut?Brandl Gabriela?Marginean 《Analytical and bioanalytical chemistry》2003,375(7):875-883
Plasma chemically modified carbon nanofibers were characterized by X-ray photoelectron spectroscopy with regard to the content of carbon, oxygen, and nitrogen and the contribution of carboxylic groups or ester, carbonyl and hydroxylic groups or ether on the surface. Unfortunately, X-ray photoelectron spectroscopy only provides an average value of the first 10 to 15 molecular layers. For comparison, depth profiles were measured and wet chemical methods were applied to estimate the thickness of the functionalized layer and the distribution of oxygen-containing functional groups within the near-surface layers. The results indicate that the fiber surface is covered by a monomolecular oxygen-containing layer and that plasma treatment allows a complete oxygen functionalization of the uppermost surface layer. The best conditions for plasma treatment found within the set of parameters applied to generate complete functionalization are: plasma gas O(2)/Ar ratio 1:1, gas pressure 1-1.5 hPa, plasma power 80 W, treatment time >or= 5 min. Additionally, three quick and easy methods are presented to estimate the efficiency of plasma treatment with regard to surface functionalization: pyrolysis, contact angle measurements, and light permeability measurements of aqueous carbon nanofiber suspensions. 相似文献
9.
Henrik Land Alina Sekretareva Ping Huang Holly J. Redman Brigitta Nmeth Nakia Polidori Lívia S. Mszros Moritz Senger Sven T. Stripp Gustav Berggren 《Chemical science》2020,11(47):12789
[FeFe]-hydrogenases are known for their high rates of hydrogen turnover, and are intensively studied in the context of biotechnological applications. Evolution has generated a plethora of different subclasses with widely different characteristics. The M2e subclass is phylogenetically distinct from previously characterized members of this enzyme family and its biological role is unknown. It features significant differences in domain- and active site architecture, and is most closely related to the putative sensory [FeFe]-hydrogenases. Here we report the first comprehensive biochemical and spectroscopical characterization of an M2e enzyme, derived from Thermoanaerobacter mathranii. As compared to other [FeFe]-hydrogenases characterized to-date, this enzyme displays an increased H2 affinity, higher activation enthalpies for H+/H2 interconversion, and unusual reactivity towards known hydrogenase inhibitors. These properties are related to differences in active site architecture between the M2e [FeFe]-hydrogenase and “prototypical” [FeFe]-hydrogenases. Thus, this study provides new insight into the role of this subclass in hydrogen metabolism and the influence of the active site pocket on the chemistry of the H-cluster.Characterization of a group D putative sensory [FeFe]-hydrogenase reveals how the active site can be tuned to decrease CO inhibition and increase stability of a reduced H-cluster while retaining the ability to catalyze H+/H2 interconversion. 相似文献
10.
Otto Funk Lothar Schwabe Karl-Heinz Frömming 《Journal of inclusion phenomena and macrocyclic chemistry》1993,16(4):299-314
The purpose of the study was to examine the formation of inclusion compounds in the freeze-dried products obtained from aqueous solutions of nicotinic acid and -cyclodextrin (-CD), or heptakis (2,6-0-dimethyl)--cyclodextrin (DIMEB). The molar ratios used were 1:1 and 2:1. In addition two freezing temperatures (–40 and –196°C) and different secondary drying temperatures (+50 and +80°C) were used. Freeze-dried products with -CD obtained after low temperature freezing are of the same crystallographic structure as seen in a pure inclusion compound prepared by coprecipitation. Amorphous products were formed after fast freezing. The molar ratios of included nicotinic acid in the freeze-dried products vary — dependent on the preparation conditions — between 0.75:1 and 1:1. A factorial design proves that the included drug amount can be increased by enhancement of the amount of nicotinic acid used, by faster freezing, and by the combination of these two factors. The proof of inclusion formation was given by a combination of X-ray diffractography, differential scanning calorimetry, thermogravimetry and thermofractography.The freeze-dried preparations obtained with DIMEB were amorphous mixtures of the two components. No proof for inclusion of the nicotinic acid in the cyclodextrin cavity could be given. Higher (–40°C) or lower (–196°C) freezing temperatures and the running of the secondary drying process could not influence these results. The very low stability constant of the complex and steric reasons are responsible for this behavior. 相似文献