全文获取类型
收费全文 | 372篇 |
免费 | 4篇 |
国内免费 | 2篇 |
专业分类
化学 | 161篇 |
力学 | 11篇 |
数学 | 69篇 |
物理学 | 137篇 |
出版年
2020年 | 3篇 |
2016年 | 3篇 |
2015年 | 4篇 |
2013年 | 11篇 |
2012年 | 7篇 |
2011年 | 18篇 |
2010年 | 3篇 |
2009年 | 4篇 |
2008年 | 17篇 |
2007年 | 12篇 |
2006年 | 18篇 |
2005年 | 12篇 |
2004年 | 17篇 |
2003年 | 11篇 |
2002年 | 12篇 |
2001年 | 6篇 |
2000年 | 8篇 |
1999年 | 10篇 |
1998年 | 4篇 |
1997年 | 4篇 |
1996年 | 11篇 |
1995年 | 7篇 |
1994年 | 10篇 |
1993年 | 8篇 |
1992年 | 14篇 |
1991年 | 8篇 |
1990年 | 6篇 |
1989年 | 5篇 |
1988年 | 3篇 |
1987年 | 4篇 |
1986年 | 6篇 |
1985年 | 4篇 |
1984年 | 4篇 |
1983年 | 6篇 |
1982年 | 10篇 |
1981年 | 6篇 |
1980年 | 4篇 |
1979年 | 8篇 |
1978年 | 12篇 |
1977年 | 6篇 |
1976年 | 8篇 |
1975年 | 4篇 |
1974年 | 3篇 |
1973年 | 7篇 |
1972年 | 4篇 |
1971年 | 3篇 |
1970年 | 3篇 |
1967年 | 2篇 |
1961年 | 2篇 |
1915年 | 2篇 |
排序方式: 共有378条查询结果,搜索用时 15 毫秒
71.
We present herein the composition of bacterial communities occurring in ground chicken and the changes which arise in these
populations based upon nonselective partitioning by commercially-available Dynal anti-Salmonella and anti-E. coli O157 immunomagnetic beads (IMB). Our enumeration and colony selection protocol was based upon a 6 × 6 drop plate method (n = 18 for each 25-g sub-sampling) using a dilution which resulted in ca. 4–8 colonies per drop. An average of 82 ± 13 colonies
were selected from three 25-g ground chicken subsamplings per batch, each of which was repeated seasonally for one year. DNA
was extracted from each colony and the composition of Eubacteria in each of these harvests was determined by sequence-based
identification of 16S rDNA amplicons. The Gram-positive bacteria Brochothrix thermosphacta and Carnobacterium maltaromticum were the most commonly found organisms in both the total chicken wash (PBS) and in the IMB-bound (PBS-washed) fractions.
The remaining background organisms which also adhered to varying degrees to commercial IMBs were: Pseudomonas oleovorans, Acinetobacter lwoffi, Serratia spp., and one Rahnella spp. A large number of the organisms were also cladistically evaluated based on rDNA basepair disparities: all Brochothrices
were monophyletic; twelve different Pseudomonads were found along with eight Carnobacteria, seven Acinetobacteres, four Serratiae,
and two Rahnellae. Carnobacterium alone showed an IMB-based concentration enhancement (ca. two to sixfold).
Any reference to a brand or firm name does not constitute endorsement of the US Department of Agriculture over others of a
similar nature not mentioned 相似文献
72.
Gung BW Zou Y Xu Z Amicangelo JC Irwin DG Ma S Zhou HC 《The Journal of organic chemistry》2008,73(2):689-693
Current models describe aromatic rings as polar groups based on the fact that benzene and hexafluorobenzene are known to have large and permanent quadrupole moments. This report describes a quantitative study of the interactions between oxygen lone pair and aromatic rings. We found that even electron-rich aromatic rings and oxygen lone pairs exhibit attractive interactions. Free energies of interactions are determined using the triptycene scaffold and the equilibrium constants were determined by low-temperature 1H NMR spectroscopy. An X-ray structure analysis for one of the model compounds confirms the close proximity between the oxygen and the center of the aromatic ring. Theoretical calculations at the MP2/aug-cc-pVTZ level corroborate the experimental results. The origin of attractive interactions was explored by using aromatic rings with a wide range of substituents. The interactions between an oxygen lone pair and an aromatic ring are attractive at van der Waals' distance even with electron-donating substituents. Electron-withdrawing groups increase the strength of the attractive interactions. The results from this study can be only partly rationalized by using the current models of aromatic system. Electrostatic-based models are consistent with the fact that stronger electron-withdrawing groups lead to stronger attractions, but fail to predict or rationalize the fact that weak attractions even exist between electron-rich arenes and oxygen lone pairs. The conclusion from this study is that aromatic rings cannot be treated as a simple quadrupolar functional group at van der Waals' distance. Dispersion forces and local dipole should also be considered. 相似文献
73.
Iridium(III) Complexes Bearing Pyrene‐Functionalized 1,10‐Phenanthroline Ligands as Highly Efficient Sensitizers for Triplet–Triplet Annihilation Upconversion 下载免费PDF全文
Yue Lu Junsi Wang Dr. Niamh McGoldrick Xiaoneng Cui Prof. Dr. Jianzhang Zhao Colin Caverly Dr. Brendan Twamley Dr. Gearoid M. Ó Máille Bryan Irwin Robert Conway‐Kenny Prof. Dr. Sylvia M. Draper 《Angewandte Chemie (International ed. in English)》2016,55(47):14688-14692
“Chemistry‐on‐the‐complex” synthetic methods have allowed the selective addition of 1‐ethynylpyrene appendages to the 3‐, 5‐, 3,8‐ and 5,6‐positions of IrIII‐coordinated 1,10‐phenanthroline via Sonogashira cross‐coupling. The resulting suite of complexes has given rise to the first rationalization of their absorption and emission properties as a function of the number and position of the pyrene moieties. Strong absorption in the visible region (e.g. 3,8‐substituted Ir‐3 : λabs=481 nm, ?=52 400 m ?1 cm?1) and long‐lived triplet excited states (e.g. 5‐substituted Ir‐2 : τT=367.7 μs) were observed for the complexes in deaerated CH2Cl2. On testing the series as triplet sensitizers for triplet–triplet annihilation upconversion, those IrIII complexes bearing pyrenyl appendages at the 3‐ and 3,8‐positions ( Ir‐1 , Ir‐3 ) were found to give optimal upconversion quantum yields (30.2 % and 31.6 % respectively). 相似文献
74.
Our previously published infrared and Raman spectra of 1,3-disilacyclobutane (13DSCB) and its 1,1,3,3-d4 isotopomer have been reexamined and partially reassigned on the basis of DFT and ab initio calculations. The calculations confirm previous microwave work that the CSiC angles in the ring are unexpectedly larger than the SiCSi angles. This may arise from the partial charges on the ring atoms. The calculations are in excellent agreement with the observed spectra in both frequency and intensity. They also demonstrate that this molecule has CH2 wagging and twisting vibrations with frequencies below 1000 cm-1, about 200 cm-1 lower than expected. These unprecedented low values can be explained by the decreased slope in the potential energy curves for these vibrations as the sideways motions of the CH2 groups result in attractive forces between the positively charged hydrogens on the carbon atoms and the negatively charged hydrogens on the silicon atoms. The theoretical calculations also confirm the previous conclusions that the individual molecules (vapor) have C2v symmetry whereas in the solid the molecules become planar with D2h symmetry. The vibrational coupling between the ring-angle bending mode and the SiH2 in-phase rocking, which is present for the C2v structure, is forbidden for D2h and hence disappears. 相似文献
75.
We have developed a program, ELECT++ (Effective LEssening of Conformations by Template molecules in C++), to speed up the conformational search for small flexible molecules using the similar property principle. We apply this principle to molecular shape and, importantly, to molecular flexibility. After molecules in a database are clustered according to flexibility and shape (FCLUST++), additional reagents are generated to screen the conformational space of molecules in each cluster (TEMPLATE++). We call these representative reagents of each cluster template reagents. Template reagents and clustered reagents produce, after reaction, template molecules and clustered molecules, respectively (tREACT++). The conformations of a template molecule are searched in the context of a macromolecular target. Acceptable conformational choices are then applied to all molecules in its cluster, thus effectively biasing conformational space to speed up conformational searches (tSEARCH++). In our incremental search method, it is necessary to calculate the root-mean-square deviations (RMSD) matrix of distances between different conformations of the same molecule to reduce the number of conformations. Instead of calculating the RMSD matrix for all molecules in a cluster, the RMSD matrix of a template molecule is chosen as a reference and applied to all the molecules in its cluster. We demonstrate that FCLUST++ clusters the primary amine reagents from the Available Chemicals Directory (ACD) successfully. The program tSEARCH++ was applied to dihydrofolate reductase with virtual molecules generated by tREACT++ using clustered primary amine reagents. The conformational search by the program tSEARCH++ was about 4.8 times faster than by SEARCH++, with an acceptable range of errors. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 1834–1852, 1998 相似文献
76.
Ladmiral V Mantovani G Clarkson GJ Cauet S Irwin JL Haddleton DM 《Journal of the American Chemical Society》2006,128(14):4823-4830
The synthesis of novel well-defined alkyne side chain functional polymers featuring narrow molecular weight distributions (PDI = 1.09-1.17) by living radical polymerization is described. Grafting of protected and unprotected carbohydrates is achieved via either a C-6 or an anomeric azide (alpha or beta) onto these polymers by Cu(I)-catalyzed "click chemistry", providing a simple and efficient route to synthetic glycopolymers. The strategy provides an extremely powerful tool for the synthesis of libraries of materials that differ only in the nature of the sugar moiety presented on a well-defined polymer scaffold. A library of multivalent ligands were then prepared following a "coclicking" synthetic protocol, and the reactivity of these glycopolymers in the presence of concanavalin A and Ricinus communis agglutinin, model lectins able to selectively bind appropriate mannose and galactose derivatives, respectively, was assessed. 相似文献
77.
Irwin Yousept 《Journal of Optimization Theory and Applications》2012,154(3):879-903
This paper is concerned with an optimal control problem governed by time-harmonic eddy current equations on a Lipschitz polyhedral domain. The controls are given by scalar functions entering in the coefficients of the curl-curl differential operator in the state equation. We present a mathematical analysis of the optimal control problem, including sensitivity analysis, regularity results, existence of an optimal control, and optimality conditions. Based on these results, we study the finite element analysis of the optimal control problem. Here, the state is discretized by the lowest order edge elements of Nédélec??s first family, and the control is discretized by continuous piecewise linear elements. Our main findings are convergence results of the finite element discretization (without a rate). 相似文献
78.
Journal of Statistical Physics - 相似文献
79.
80.
We construct essentially finitely indecomposable abelianp-groups that are not thick, i.e., admit a non-small homomorphism into a Σ-cyclicp-group.
Research partially supported by NSF grant DMS-8900350. 相似文献