全文获取类型
收费全文 | 675篇 |
免费 | 17篇 |
国内免费 | 4篇 |
专业分类
化学 | 407篇 |
晶体学 | 4篇 |
力学 | 26篇 |
数学 | 123篇 |
物理学 | 136篇 |
出版年
2023年 | 2篇 |
2022年 | 7篇 |
2021年 | 13篇 |
2020年 | 4篇 |
2019年 | 14篇 |
2018年 | 14篇 |
2017年 | 14篇 |
2016年 | 19篇 |
2015年 | 21篇 |
2014年 | 22篇 |
2013年 | 37篇 |
2012年 | 53篇 |
2011年 | 47篇 |
2010年 | 42篇 |
2009年 | 29篇 |
2008年 | 38篇 |
2007年 | 44篇 |
2006年 | 32篇 |
2005年 | 37篇 |
2004年 | 29篇 |
2003年 | 24篇 |
2002年 | 22篇 |
2001年 | 7篇 |
2000年 | 13篇 |
1999年 | 3篇 |
1998年 | 9篇 |
1997年 | 5篇 |
1996年 | 8篇 |
1995年 | 9篇 |
1994年 | 12篇 |
1993年 | 9篇 |
1992年 | 3篇 |
1991年 | 5篇 |
1990年 | 5篇 |
1989年 | 4篇 |
1988年 | 3篇 |
1986年 | 4篇 |
1985年 | 5篇 |
1984年 | 2篇 |
1980年 | 2篇 |
1978年 | 3篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1973年 | 2篇 |
1972年 | 1篇 |
1971年 | 2篇 |
1967年 | 1篇 |
1965年 | 1篇 |
1944年 | 2篇 |
1913年 | 2篇 |
排序方式: 共有696条查询结果,搜索用时 281 毫秒
1.
Periodica Mathematica Hungarica - We present a tight parametrical Hermite–Hadamard type inequality with probability measure, which yields a considerably closer upper bound for the mean value... 相似文献
2.
Harnack inequality for some classes of Markov processes 总被引:3,自引:0,他引:3
In this paper we establish a Harnack inequality for nonnegative harmonic functions of some classes of Markov processes with jumps.
Mathematics Subject Classification (2000): Primary 60J45, 60J75, Secondary 60J25.This work was completed while the authors were in the Research in Pairs program at the Mathematisches Forschungsinstitut Oberwolfach. We thank the Institute for the hospitality.The research of this author is supported in part by NSF Grant DMS-9803240.The research of this author is supported in part by MZT grant 0037107 of the Republic of Croatia. 相似文献
3.
Keith Vaughan Ronald J. LaFrance York Tang Donald L. Hooper 《Journal of heterocyclic chemistry》1991,28(7):1709-1713
3-Alkyl-4-arylazomethylene-3,4-dihydro-1,2,3-benzotriazines 5a and 5b undergo facile 1,4-addition of methanol or ethanol to afford stable crystalline hydrazones, 6 and 8 which have been characterised by spectroscopic analysis. In particular, the nmr spectrum of 8 shows novel features due to the diastereotopic nature of the CH2 protons in the two O-ethyl groups. Compound 5b shows a property unique to the compounds in this series; refluxing this arylazomethylenetriazine in ethanol affords a rearranged product, characterised as the 1-aryl-2-cinnolinylhydrazine ( 9 ). The formation of 9 is rationalised as a ring opening-ring closure process analogous to the Dimroth rearrangement. The cinnoline 9 displays some novel chemistry arising from the facility of the arylhydrazino substituent to react with acid to give a fragmentation product, 3-methylindazole ( 7 ). 相似文献
4.
The use of reagent concentration has resulted in increased rates for all stages of the REM resin synthesis of tertiary amines. These increases in rate translate into faster reaction times, higher yields and lower reagent consumption. Of the methods examined, the most successful was the use of perfluorous solvents, either alone or with a small amount of organic co-solvent. 相似文献
5.
Fe2O3--V2O5 catalysts doped with Cs2SO4 (molar ratio: V:Fe:Cs=1:0.74:0.06) were found to be a rather inhomogeneous mixture of various crystalline and amorphous iron
vanadate phases. After calcination in air the catalyst was divided into three different parts which were analyzed separately
revealing the formation of FeVO4 in the top and bottom fraction of the crucible and Fe2V4O13 in the middle fraction. As compared to the well crystallized FeVO4 reference sample, the quadrupole splittings of FeVO4 in the Cs-doped catalysts were larger pointing to more distorted iron sites which were assumed to be responsible for high
catalytic selectivities. In contrast, the quadrupole splittings of FeVO4 in the less selective K- and Rb-doped Fe2O3--V2O5 catalysts were smaller. Additional components in the bottom fraction were also α-Fe2O3 and Fe1-xS. As indicated by the CEMS spectra the latter is located preferentially on the surface of the catalyst particles.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
6.
7.
8.
Redox-active tyrosine residues play important roles in long-distance electron reactions in enzymes, including prostaglandin H synthase, galactose oxidase, ribonucleotide reductase, and photosystem II. Magnetic resonance and vibrational spectroscopy provide methods with which to study the structures of redox-active amino acids in proteins. In this report, ultraviolet photolysis was used to generate tyrosyl radicals from polycrystalline tyrosinate or dipeptides, and the structure of the radical was investigated with EPR and reaction-induced FT-IR spectroscopy at 77 K. Photolysis at 77 K is expected to generate a neutral tyrosyl radical through oxidation of the aromatic ring. EPR and FT-IR results obtained from (13)C-labeled tyrosine were consistent with that expectation. Surprisingly, labeling of the tyrosyl amino group with (15)N also resulted in isotope-shifted bands in the photolysis spectrum. The force constant of a NH deformation mode increased when the tyrosyl radical was generated. These data suggest an interaction between the pi system of the tyrosyl radical and the amino group. In spectra acquired from the dipeptides, evidence for a sequence-dependent interaction between the tyrosyl radical and the amide bond of the dipeptide was also obtained. We postulate that perturbation of the amino or the amide/imide groups may occur through a spin polarization mechanism, which is indirectly detected as a change in NH force constant. This conclusion is supported by density functional calculations, which suggest a conformationally sensitive delocalization of spin density onto the amino and carboxylate groups of the tyrosyl radical. These experiments provide a step toward a detailed spectral interpretation for protein-based tyrosyl radicals. 相似文献
9.
Thomas R. Gengenbach Zoran R. Vasic Sheng Li Ronald C. Chatelier Hans J. Griesser 《Plasmas and Polymers》1997,2(2):91-114
The properties and composition of plasma polymer surfaces stored in air can change considerably over time, especially as a
result of oxidative reactions. When plasma polymers contain an element other than O, it is possible to probe for mechanisms
in addition to oxidation that contribute to the aging of the surface. Plasma polymers containing N were fabricated from either
1,3-diaminopropane (DAP),n-heptylamine (nHA), or allylamine (AA), and studied by X-ray photo-electron spectroscopy (XPS) and air/water contact angles
(CA). For each of the plasma polymers, a multiexponential increase in the O/C ratio was observed over time using XPS. The
N/C ratios remained constant (AA) or decreased somewhat (nHA and DAP). In contrast, the trends in CA values differed, declining
for the nHA surfaces, rising for the AA, and changing little for the DAP. Surface roughness, assessed by scanning tunnelling
or atomic force microscopy, did not change over time. The diverse adjustments in the polarity of each surface and the similar
compositional changes between them are reconcilable if the aging of the plasma polymer surface is a manifestation of the superposition
of concurrent oxidative reactions and partial surface reorientation; the former introduce polar groups and the latter transports
then from the surface to deeper regions beyond the CA probe depth but within the XPS analysis depth. These processes vary
between different plasma polymers. Data for the alkylamine plasma polymers is also compared with that for two plasma polymers
fabricated from methanol. The change in composition, but not polarity, of the DAP surface after 4 days of storage demonstrates
the importance of using multiple techniques to characterize the aging of plasma polymer surfaces. 相似文献
10.
The conversion of phosphoenolpyruvate (PEP) to phosphonopyruvate (P-pyr) is catalyzed by PEP mutase via a dissociative mechanism. In this work, we investigate the uncatalyzed reaction using ab initio methods, density functional theory, and the semiempirical MNDO/d method. Comparisons of geometries and relative energies of stationary points (minima and transition states) with density functional results indicate that the semiempirical method is reasonably accurate. Solvent effects are examined using implicit solvent models, including the recently extended smooth conductor-like screening model. Due to the large negative charge carried by the system, solvation is found to drastically alter the location and energy of stationary points along the dissociative reaction pathways. The influence of substituting a nonbridging phosphoryl oxygen by sulfur (thio effects) was also investigated. Implications of these results for the enzymatic reaction are discussed. 相似文献