全文获取类型
收费全文 | 2001篇 |
免费 | 76篇 |
国内免费 | 8篇 |
专业分类
化学 | 1292篇 |
晶体学 | 27篇 |
力学 | 50篇 |
数学 | 196篇 |
物理学 | 520篇 |
出版年
2024年 | 7篇 |
2023年 | 25篇 |
2022年 | 31篇 |
2021年 | 37篇 |
2020年 | 56篇 |
2019年 | 51篇 |
2018年 | 31篇 |
2017年 | 30篇 |
2016年 | 59篇 |
2015年 | 56篇 |
2014年 | 79篇 |
2013年 | 160篇 |
2012年 | 114篇 |
2011年 | 152篇 |
2010年 | 79篇 |
2009年 | 76篇 |
2008年 | 119篇 |
2007年 | 131篇 |
2006年 | 72篇 |
2005年 | 70篇 |
2004年 | 61篇 |
2003年 | 35篇 |
2002年 | 32篇 |
2001年 | 29篇 |
2000年 | 17篇 |
1999年 | 9篇 |
1998年 | 13篇 |
1997年 | 11篇 |
1996年 | 17篇 |
1995年 | 19篇 |
1994年 | 23篇 |
1993年 | 26篇 |
1992年 | 17篇 |
1990年 | 10篇 |
1989年 | 12篇 |
1988年 | 16篇 |
1987年 | 16篇 |
1986年 | 17篇 |
1985年 | 19篇 |
1984年 | 13篇 |
1983年 | 19篇 |
1982年 | 19篇 |
1981年 | 18篇 |
1980年 | 17篇 |
1979年 | 17篇 |
1978年 | 20篇 |
1977年 | 13篇 |
1976年 | 19篇 |
1974年 | 16篇 |
1973年 | 12篇 |
排序方式: 共有2085条查询结果,搜索用时 140 毫秒
101.
Jena Sudipta Ray Asit Sahoo Ambika Kamila Pradeep Kumar Nayak Sanghamitra Panda Pratap Chandra 《Chemistry of Natural Compounds》2021,57(6):1147-1149
Chemistry of Natural Compounds - 相似文献
102.
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
103.
Phenothiazine–BODIPY–Fullerene Triads as Photosynthetic Reaction Center Models: Substitution and Solvent Polarity Effects on Photoinduced Charge Separation and Recombination 下载免费PDF全文
Chandra B. KC Gary N. Lim Dr. Vladimir N. Nesterov Prof. Dr. Paul A. Karr Prof. Dr. Francis D'Souza 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(51):17100-17112
Novel photosynthetic reaction center model compounds of the type donor2–donor1–acceptor, composed of phenothiazine, BF2‐chelated dipyrromethene (BODIPY), and fullerene, respectively, have been newly synthesized using multistep synthetic methods. X‐ray structures of three of the phenothiazine‐BODIPY intermediate compounds have been solved to visualize the substitution effect caused by the phenothiazine on the BODIPY macrocycle. Optical absorption and emission, computational, and differential pulse voltammetry studies were systematically performed to establish the molecular integrity of the triads. The N‐substituted phenothiazine was found to be easier to oxidize by 60 mV compared to the C‐substituted analogue. The geometry and electronic structures were obtained by B3LYP/6‐31G(dp) calculations (for H, B, N, and O) and B3LYP/6‐31G(df) calculations (for S) in vacuum, followed by a single‐point calculation in benzonitrile utilizing the polarizable continuum model (PCM). The HOMO?1, HOMO, and LUMO were, respectively, on the BODIPY, phenothiazine and fullerene entities, which agreed well with the site of electron transfer determined from electrochemical studies. The energy‐level diagram deduced from these data helped in elucidating the mechanistic details of the photochemical events. Excitation of BODIPY resulted in ultrafast electron transfer to produce PTZ–BODIPY.+–C60.?; subsequent hole shift resulted in PTZ.+–BODIPY–C60.? charge‐separated species. The return of the charge‐separated species was found to be solvent dependent. In nonpolar solvents the PTZ.+–BODIPY–C60.? species populated the 3C60* prior to returning to the ground state, while in polar solvent no such process was observed due to relative positioning of the energy levels. The 1BODIPY* generated radical ion‐pair in these triads persisted for few nanoseconds due to electron transfer/hole‐shift mechanism. 相似文献
104.
Shivanand M. Pudakalakatti Kousik Chandra Ravula Thirupathi Hanudatta S. Atreya 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(48):15719-15722
An NMR‐based approach for rapid characterization of translational diffusion of molecules has been developed. Unlike the conventional method of acquiring a series of 2D 13C and 1H spectra, the proposed approach involves a single 2D NMR spectrum, which can be acquired in minutes. Using this method, it was possible to detect the presence of intermediate oligomeric species of diphenylalanine in solution during the process of its self‐assembly to form nanotubular structures. 相似文献
105.
Dr. Chandra M. R. Volla Dr. Javier Mazuela Prof. Dr. Jan‐E. Bäckvall 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(25):7608-7612
A highly efficient oxidative carbocyclization–carbonylation reaction cascade of allenynes and enallenes has been developed using a PdII salt in low catalytic amounts under ambient temperature and pressure (1 atm of carbon monoxide). The use of DMSO as an additive was found to be important for an efficient reaction. A wide range of alcohols as trapping reagents were used to give the corresponding esters in good yields. 相似文献
106.
Dr. Koushik Chandra Dr. Tapta Kanchan Roy Dr. Deborah E. Shalev Prof. Abraham Loyter Prof. Chaim Gilon Prof. R. Benny Gerber Prof. Assaf Friedler 《Angewandte Chemie (International ed. in English)》2014,53(36):9450-9455
We present a new approach for peptide cyclization during solid phase synthesis under highly acidic conditions. Our approach involves simultaneous in situ deprotection, cyclization and trifluoroacetic acid (TFA) cleavage of the peptide, which is achieved by forming an amide bond between a lysine side chain and a succinic acid linker at the peptide N‐terminus. The reaction proceeds via a highly active succinimide intermediate, which was isolated and characterized. The structure of a model cyclic peptide was solved by NMR spectroscopy. Theoretical calculations support the proposed mechanism of cyclization. Our new methodology is applicable for the formation of macrocycles in solid‐phase synthesis of peptides and organic molecules. 相似文献
107.
Anirban Bhandari Saikat Mishra Dr. Ram Chandra Maji Akhilesh Kumar Prof. Dr. Marilyn M. Olmstead Prof. Dr. Apurba K. Patra 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(23):9262-9270
According to the well-accepted mechanism, methyl-coenzyme M reductase (MCR) involves Ni-mediated thiolate-to-disulfide conversion that sustains its catalytic cycle of methane formation in the energy saving pathways of methanotrophic microbes. Model complexes that illustrate Ni-ion mediated reversible thiolate/disulfide transformation are unknown. In this paper we report the synthesis, crystal structure, spectroscopic properties and redox interconversions of a set of NiII complexes comprising a tridentate N2S donor thiol and its analogous N4S2 donor disulfide ligands. These complexes demonstrate reversible NiII-thiolate/NiII-disulfide (both bound and unbound disulfide-S to NiII) transformations via thiyl and disulfide monoradical anions that resemble a primary step of MCR's catalytic cycle. 相似文献
108.
Ashutosh Kumar Buddhadev Purohit Kuldeep Mahato Sharmili Roy Ananya Srivastava Pranjal Chandra 《Electroanalysis》2020,32(1):59-69
We report for the first time sinapic acid (SA) sensing based on nanocomposite comprising electrochemically tuned gold nanoparticles (EAuNPs) and solvothermally reduced graphene oxide (rGO). The synthesized EAuNPs, rGO, and EAuNPs‐rGO nanocomposite were characterized using X‐ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), particle size analysis, and Raman spectroscopy. A proof‐of‐concept electrochemical sensor for SA was developed based on synthesized EAuNPs‐rGO nanocomposite, which was characterized by electrochemical techniques such as cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The developed sensor detected SA with a linear dynamic range (LDR) between 20 μM and 200 μM and detection limit (DL) of 33.43 (±0.21) nM (RSD<3.32 %). To show the useful purpose of the sensor probe in clinical applications, SA was detected in human urine samples, which showed the percentage recovery between 82.6 % and 92.8 %. Interferences due to various molecules such as L‐cystine, glycine, alanine, serum albumin, uric acid, citric acid, ascorbic acid, and urea were tested. Long‐term stability of the sensor probe was examined, which was found to be stable up to 6 weeks. The sensor fabricated using EAuNPs‐rGO nanocomposite has many attractive features such as; simplicity, rapidity, and label‐free detection; hence, it could be a method of choice for SA detection in various matrices. 相似文献
109.
110.
Yogendra K. Gautam Amit K. ChawlaRajan Walia R.D. AgrawalRamesh Chandra 《Applied Surface Science》2011,257(14):6291-6295
Structural and optical properties of pure Mg thin film coated with Pd have been investigated. Pd-capped Mg thin films had been prepared by DC magnetron sputtering. This work presents an ex situ study on hydrogenation and dehydrogenation kinetics of Pd/Mg films at different conditions using XRD, AFM and optical spectrophotometer. We have succeeded to load thin films of Mg to MgH2 at normal temperature and normal pressure of hydrogen gas. In hydrogenation, α-MgH2 phase of magnesium hydride was observed in hydrogenated films at 200 °C and γ-MgH2 at 250 °C respectively. The desorption kinetics in vacuum also revealed the phase transformation α-MgH2 to γ-MgH2. A reflectance change was observed in hydrogenated films in comparison of as deposited thin film. Hydrogenated (H loaded) samples were observed partially transparent in comparison of as deposited. 相似文献