全文获取类型
收费全文 | 1934篇 |
免费 | 95篇 |
国内免费 | 3篇 |
专业分类
化学 | 1289篇 |
晶体学 | 10篇 |
力学 | 60篇 |
数学 | 136篇 |
物理学 | 537篇 |
出版年
2023年 | 26篇 |
2022年 | 33篇 |
2021年 | 61篇 |
2020年 | 62篇 |
2019年 | 47篇 |
2018年 | 43篇 |
2017年 | 31篇 |
2016年 | 75篇 |
2015年 | 47篇 |
2014年 | 98篇 |
2013年 | 128篇 |
2012年 | 142篇 |
2011年 | 171篇 |
2010年 | 102篇 |
2009年 | 86篇 |
2008年 | 126篇 |
2007年 | 81篇 |
2006年 | 89篇 |
2005年 | 92篇 |
2004年 | 49篇 |
2003年 | 40篇 |
2002年 | 34篇 |
2001年 | 18篇 |
2000年 | 18篇 |
1999年 | 23篇 |
1998年 | 8篇 |
1997年 | 16篇 |
1996年 | 16篇 |
1995年 | 13篇 |
1994年 | 14篇 |
1993年 | 18篇 |
1992年 | 12篇 |
1991年 | 14篇 |
1990年 | 9篇 |
1989年 | 11篇 |
1988年 | 11篇 |
1987年 | 8篇 |
1986年 | 12篇 |
1985年 | 13篇 |
1984年 | 16篇 |
1983年 | 14篇 |
1982年 | 12篇 |
1981年 | 9篇 |
1979年 | 7篇 |
1978年 | 8篇 |
1977年 | 11篇 |
1976年 | 13篇 |
1975年 | 5篇 |
1974年 | 7篇 |
1973年 | 6篇 |
排序方式: 共有2032条查询结果,搜索用时 359 毫秒
71.
Chemistry of Heterocyclic Compounds - In recent years several important viral infections have emerged and antiviral chemotherapeutic agents are not sufficiently effective in clinic, leading to... 相似文献
72.
Julia Beerhues Maren Neubrand Dr. Sebastian Sobottka Dr. Nicolás I. Neuman Hannes Aberhan Shubhadeep Chandra Prof. Dr. Biprajit Sarkar 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(21):6557-6568
Carbene-based radicals are important for both fundamental and applied chemical research. Herein, extensive electrochemical investigations of nine different 1,2,3-triazolylidene selenium adducts are reported. It is found that the half-wave potentials of the first reduction of the selones correlate with their calculated LUMO levels and the LUMO levels of the corresponding triazolylidene-based mesoionic carbenes (MICs). Furthermore, unexpected quasi-reversibility of the reduction of two triazoline selones, exhibiting comparable reduction potentials, was discovered. Through UV/Vis/NIR and EPR spectroelectrochemical investigations supported by DFT calculations, the radical anion was unambiguously assigned to be triazoline centered. This electrochemical behavior was transferred to a triazolylidene-type MIC-gold phenyl complex resulting in a MIC-radical coordinated AuI species. Apart from UV-Vis-NIR and EPR spectroelectrochemical investigations of the reduction, the reduced gold-coordinated MIC radical complex was also formed in situ in the bulk through chemical reduction. This is the first report of a monodentate triazolylidene-based MIC ligand that can be reduced to its anion radical in a metal complex. The results presented here provide design principles for stabilizing radicals based on MICs. 相似文献
73.
Inside Cover: Ruthenium Complexes of Tripodal Ligands with Pyridine and Triazole Arms: Subtle Tuning of Thermal,Electrochemical, and Photochemical Reactivity (Chem. Eur. J. 3/2014)
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
74.
Highly Luminescent Colloidal Eu3+‐Doped KZnF3 Nanoparticles for the Selective and Sensitive Detection of CuII Ions
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Shyam Sarkar Manjunath Chatti Dr. Venkataramanan Mahalingam 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(12):3311-3316
This article describes a green synthetic approach to prepare water dispersible perovskite‐type Eu3+‐doped KZnF3 nanoparticles, carried out using environmentally friendly microwave irradiation at low temperature (85 °C) with water as a solvent. Incorporation of Eu3+ ions into the KZnF3 matrix is confirmed by strong red emission upon ultraviolet (UV) excitation of the nanoparticles. The nanoparticles are coated with poly(acrylic acid) (PAA), which enhances the dispersibility of the nanoparticles in hydrophilic solvents. The strong red emission from Eu3+ ions is selectively quenched upon addition of CuII ions, thus making the nanoparticles a potential CuII sensing material. This sensing ability is highly reversible by the addition of ethylenediaminetetraacetic acid (EDTA), with recovery of almost 90 % of the luminescence. If the nanoparticles are strongly attached to a positively charged surface, dipping the surface in a CuII solution leads to the quenching of Eu3+ luminescence, which can be recovered after dipping in an EDTA solution. This process can be repeated for more than five cycles with only a slight decrease in the sensing ability. In addition to sensing, the strong luminescence from Eu3+‐doped KZnF3 nanoparticles could be used as a tool for bioimaging. 相似文献
75.
Michael G. Sommer Petra Kureljak Dr. Damijana Urankar Dr. David Schweinfurth Nikolina Stojanović Dr. Martina Bubrin Dr. Martin Gazvoda Dr. Maja Osmak Prof. Dr. Biprajit Sarkar Prof. Dr. Janez Košmrlj 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(52):17296-17299
Azocarboxamide (azcH) has been combined for the first time with [Ru–Cym] to generate metal complexes with N,N‐ and N,O‐coordination mode, [(Cym)Ru(azc)Cl] and [(Cym)Ru(azcH)Cl]+[PF6]?. Geometric and electronic structures of the complexes are reported along with their in vitro activities against different tumour cell lines and preliminary results on solution chemistry. Compound [(Cym)Ru(azc)Cl] exhibited remarkable cytotoxic properties. It was cell‐type specific and had comparable IC50 values towards both cancer cells and their drug‐resistant subline. A tenfold increase in the sensitivity towards [(Cym)Ru(azc)Cl] was noted for the tumour cells with depleted intracellular glutathione (GSH) level, suggesting the essential role of GSH in cell response to this compound. 相似文献
76.
Redox‐Induced Spin‐State Switching and Mixed Valency in Quinonoid‐Bridged Dicobalt Complexes
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
David Schweinfurth Yvonne Rechkemmer Stephan Hohloch Naina Deibel Irina Peremykin Jan Fiedler Raphael Marx Dr. Petr Neugebauer Prof. Dr. Joris van Slageren Prof. Dr. Biprajit Sarkar 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(12):3475-3486
The complexes [{(tmpa)CoII}2(μ‐L1)2?]2+ ( 12+ ) and [{(tmpa)CoII}2(μ‐L2)2?]2+ ( 22+ ), with tmpa=tris(2‐pyridylmethyl)amine, H2L1=2,5‐di‐[2‐(methoxy)‐anilino]‐1,4‐benzoquinone, and H2L2=2,5‐di‐[2‐(trifluoromethyl)‐anilino]‐1,4‐benzoquinone, were synthesized and characterized. Structural analysis of 22+ revealed a distorted octahedral coordination around the cobalt centers, and cobalt–ligand bond lengths that match with high‐spin CoII centers. Superconducting quantum interference device (SQUID) magnetometric studies on 12+ and 22+ are consistent with the presence of two weakly exchange‐coupled high‐spin cobalt(II) ions, for which the nature of the coupling appears to depend on the substituents on the bridging ligand, being antiferromagnetic for 12+ and ferromagnetic for 22+ . Both complexes exhibit several one‐electron redox steps, and these were investigated with cyclic voltammetry and UV/Vis/near‐IR spectroelectrochemistry. For 12+ , it was possible to chemically isolate the pure forms of both the one‐electron oxidized mixed‐valent 13+ and the two‐electron oxidized isovalent 14+ forms, and characterize them structurally as well as magnetically. This series thus provided an opportunity to investigate the effect of reversible electron transfers on the total spin‐state of the molecule. In contrast to 22+ , for 14+ the metal–ligand distances and the distances within the quinonoid ligand point to the existence of two low‐spin CoIII centers, thus showing the innocence of the quintessential non‐innocent ligands L. Magnetic data corroborate these observations by showing the decrease of the magnetic moment by roughly half (neglecting spin exchange effects) on oxidizing the molecules with one electron, and the disappearance of a paramagnetic response upon two‐electron oxidation, which confirms the change in spin state associated with the electron‐transfer steps. 相似文献
77.
One‐Step Multicomponent Self‐Assembly of a First‐Generation Sierpiński Triangle: From Fractal Design to Chemical Reality
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Rajarshi Sarkar Kai Guo Dr. Charles N. Moorefield Prof. Mary Jane Saunders Prof. Chrys Wesdemiotis Prof. George R. Newkome 《Angewandte Chemie (International ed. in English)》2014,53(45):12182-12185
A novel terpyridine‐based architecture that mimics a first‐generation Sierpiński triangle has been synthesized by multicomponent assembly and features tpy? CdII? tpy connectivity (tpy=terpyridine). The key terpyridine ligands were synthesized by the Suzuki cross‐coupling reaction. Mixing two different terpyridine‐based ligands and CdII in a precise stoichiometric ratio (1:1:3) produced the desired fractal architecture in near‐quantitative yield. Characterization was accomplished by NMR spectroscopy, mass spectrometry, and transmission electron microscopy. 相似文献
78.
Amlan K. Roy 《Journal of mathematical chemistry》2014,52(5):1405-1413
Accurate low and high-lying bound states of Tietz–Hua oscillator potential are presented. The radial Schrödinger equation is solved efficiently by means of the generalized pseudospectral method that enables optimal spatial discreti zation. Both $\ell =0$ and rotational states are considered. Ro-vibrational levels of six diatomic molecules viz., H $_2$ , HF, N $_2$ , NO, O $_2$ , O $_2^+$ are obtained with good accuracy. Most of the states are reported here for the first time. A detailed analysis of variation of eigenvalues with $n, \ell $ quantum numbers is made. Results are compared with literature data, wherever possible. These are also briefly contrasted with the Morse potential results. 相似文献
79.
Souvik Sarkar Aritra Sarkar Prof. Dr. Subi J. George 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(45):20013-20017
Stereoselective and temporally controlled supramolecular polymerizations are ubiquitous in nature and are desirable attributes for the design of chiral, well-defined functional materials. Kinetically controlled, living supramolecular polymerization (LSP) has emerged recently for the synthesis of supramolecular polymers with controlled length and narrow dispersity. On the other hand, stringent design requirements for chiral-discriminating monomers precludes the stereoselective control of the supramolecular polymer structure. Herein, a synergetic stereo- and structural control of supramolecular polymerization by the realization of an unprecedented stereoselective seed-induced LSP is reported. Homochiral and seeded growth is demonstrated with bischromophoric naphthalene diimide (NDI) enantiomers with a chiral binaphthyl amine core, exhibiting strong self-recognition abilities and pathway complexity. 相似文献
80.
Dr. Sebastian Sobottka Maite Nößler Dr. Andrew L. Ostericher Dr. Gunter Hermann Noah Z. Subat Julia Beerhues Dr. Margarethe Behr-van der Meer Dr. Lisa Suntrup Dr. Uta Albold Dr. Stephan Hohloch Dr. Jean Christophe Tremblay Prof. Dr. Biprajit Sarkar 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(6):1314-1327
Asymmetric platinum donor–acceptor complexes [(pimp)Pt(Q2−)] are presented in this work, in which pimp=[(2,4,6-trimethylphenylimino)methyl]pyridine and Q2−=catecholate-type donor ligands. The properties of the complexes are evaluated as a function of the donor ligands, and correlations are drawn among electrochemical, optical, and theoretical data. Special focus has been put on the spectroelectrochemical investigation of the complexes featuring sulfonyl-substituted phenylendiamide ligands, which show redox-induced linkage isomerism upon oxidation. Time-dependent density functional theory (TD-DFT) as well as electron flux density analysis have been employed to rationalize the optical spectra of the complexes and their reactivity. Compound 1 ([(pimp)Pt(Q2−)] with Q2−=3,5-di-tert-butylcatecholate) was shown to be an efficient photosensitizer for molecular oxygen and was subsequently employed in photochemical cross-dehydrogenative coupling (CDC) reactions. The results thus display new avenues for donor–acceptor systems, including their role as photocatalysts for organic transformations, and the possibility to introduce redox-induced linkage isomerism in these compounds through the use of sulfonamide substituents on the donor ligands. 相似文献