全文获取类型
收费全文 | 845篇 |
免费 | 75篇 |
国内免费 | 3篇 |
学科分类
数理化 | 923篇 |
出版年
2024年 | 1篇 |
2023年 | 32篇 |
2022年 | 18篇 |
2021年 | 33篇 |
2020年 | 48篇 |
2019年 | 43篇 |
2018年 | 37篇 |
2017年 | 23篇 |
2016年 | 62篇 |
2015年 | 42篇 |
2014年 | 50篇 |
2013年 | 71篇 |
2012年 | 78篇 |
2011年 | 83篇 |
2010年 | 42篇 |
2009年 | 29篇 |
2008年 | 36篇 |
2007年 | 37篇 |
2006年 | 29篇 |
2005年 | 15篇 |
2004年 | 17篇 |
2003年 | 18篇 |
2002年 | 9篇 |
2001年 | 10篇 |
2000年 | 5篇 |
1999年 | 6篇 |
1998年 | 4篇 |
1996年 | 1篇 |
1995年 | 5篇 |
1994年 | 3篇 |
1993年 | 3篇 |
1992年 | 4篇 |
1991年 | 3篇 |
1989年 | 3篇 |
1988年 | 2篇 |
1987年 | 4篇 |
1986年 | 4篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1982年 | 4篇 |
1978年 | 2篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有923条查询结果,搜索用时 15 毫秒
1.
Ambarish Mondal Rajat K. Tripathy Parul Dutta Manas Kumar Santra Anvarhusein A. Isab Christopher W. Bielawski Hemanta K. Kisan Swapan K. Chandra Joydev Dinda 《应用有机金属化学》2019,33(1)
The syntheses, structures, and chemotherapeutic activities of Ag(I)‐, Au(I)‐, and Ru(II)‐complexes ligated to a novel N‐heterocyclic carbene ligand, 2‐(4‐nitrophenyl)imidazo[1,5‐a]pyridin‐2‐ylidene ( 1 ), are described. The corresponding complexes, [Ag( 1 )2][PF6], [Au( 1 )2][PF6] ( 3 ), and [Ru( 1 )(p‐cymene)Cl][PF6] ( 4 ), were prepared using convenient transmetallation chemistry and characterized using a range of spectroscopic and analytical techniques. X‐ray crystallography revealed that complexes 2 and 3 adopted linear structures whereas 4 exhibited a prototypical “piano‐stool”‐like geometry; the structural assignments were further supported by DFT calculations. A series of in vitro studies revealed that while the aforementioned Ag(I), Au(I) and Ru(II) complexes exhibited significant cytotoxicities against the human colon adenocarcinoma (HCT 116), lung cancer (A549), and breast cancer (MCF7) cell lines, the Ru derivative was most prominent. 相似文献
2.
Back Cover: Activation of Elemental Sulfur at a Two‐Coordinate Platinum(0) Center (Chem. Eur. J. 36/2016) 下载免费PDF全文
3.
4.
AbstractEnlightened by the Caputo fractional derivative, the present study deals with a novel mathematical model of generalized thermoelasticity to investigate the transient phenomena due to the influence of magnetic field and moving heat source in a rod in the context of three-phase lag (TPL) theory of thermoelasticity. Both ends of the rod are fixed and heat insulated. Employing Laplace transform as a tool, the problem has been transformed into the space-domain and solved analytically. Finally, solutions in the real-time domain are obtained by applying the inverse Laplace transform. Numerical calculation for stress, displacement, and temperature within the rod is carried out and displayed graphically. The effect of moving heat source speed on temperature, stress, and temperature is studied. It is found from the distributions that the temperature, thermally induced displacement and stress of the rod are found to decrease at large source speed. For the better understanding of the effect of moving heat source on all the distributions, three animations are added. 相似文献
5.
Dr. Siddhartha De Dr. Alexandrine Flambard Dr. Delphine Garnier Patrick Herson Dr. Frank H. Köhler Dr. Abhishake Mondal Dr. Karine Costuas Dr. Béatrice Gillon Prof. Rodrigue Lescouëzec Dr. Boris Le Guennic Dr. Frédéric Gendron 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(52):12120-12136
The local magnetic structure in the [FeIII(Tp)(CN)3]− building block was investigated by combining paramagnetic Nuclear Magnetic Resonance (pNMR) spectroscopy and polarized neutron diffraction (PND) with first-principle calculations. The use of the pNMR and PND experimental techniques revealed the extension of spin-density from the metal to the ligands, as well as the different spin mechanisms that take place in the cyanido ligands: Spin-polarization on the carbon atoms and spin-delocalization on the nitrogen atoms. The results of our combined density functional theory (DFT) and multireference calculations were found in good agreement with the PND results and the experimental NMR chemical shifts. Moreover, the ab-initio calculations allowed us to connect the experimental spin-density map characterized by PND and the suggested distribution of the spin-density on the ligands observed by NMR spectroscopy. Interestingly, significant differences were observed between the pseudo-contact contributions of the chemical shifts obtained by theoretical calculations and the values derived from NMR spectroscopy using a simple point-dipole model. These discrepancies underline the limitation of the point-dipole model and the need for more elaborate approaches to break down the experimental pNMR chemical shifts into contact and pseudo-contact contributions. 相似文献
6.
Shyam Sundar Mondal Namita Jaiswal Partha Sarathi Bera Ranjay K. Tiwari Jogendra Nath Behera Nripen Chanda Subhas Ghosal Tanmoy Kumar Saha 《应用有机金属化学》2021,35(1)
A series of copper (II) ( 1 and 3 ) and cobalt (II/III) ( 2 , 4 and 5 ) complexes comprising different imino‐phenolate ligands DCH , DTH and DBH 2 (where DCH = 2,4‐dichloro‐6‐((mesitylimino)methyl)phenol, DTH = 2,4‐di‐tert‐butyl‐6‐((mesitylimino)methyl) phenol and DBH 2 = 2,4‐dibromo‐6‐((mesitylimino)methyl)phenol) have been prepared with excellent yield and high purity. By utilizing different spectroscopic tools such as UV–visible, electrospray ionization (ESI)‐mass, Fourier‐transform infrared (FTIR) spectrometry and elemental analysis, the prepared complexes ( 1 – 5 ) were thoroughly characterized. The molecular structure of the synthesized complexes was ascertained by using single‐crystal X‐ray diffraction studies (SCXRDs). The experiment reveals that Complexes 1 – 5 bind to calf thymus DNA (CT‐DNA) through non‐intercalative way with good interacting abilities. However, 1 – 5 are excellent quenchers of the fluorescence intensity of bovine serum albumin (BSA) following the static pathway. Additionally, they had shown remarkable cytotoxic potential against MCF‐7 (mammary gland adenocarcinoma) and A549 (lung adenocarcinoma) cell lines. The IC50 values associated with these complexes were much lower than the conventional drug cisplatin. Apoptosis‐induced cell death was confirmed from the DNA fragmentation studies and Hoechst 33342 staining. The 2′,7′‐dichlorofluorescein diacetate (DCFDA) assay indicates that the complex mediated reactive oxygen species (ROS) generation is accountable for governing the apoptosis mechanism via oxidative cell distress. Apart from these studies, by carrying out density functional theory (DFT) method, highest occupied molecular orbital–lowest unoccupied molecular orbital (HOMO–LUMO) energy gap calculations and optimized structures of the synthesized complexes were accomplished. 相似文献
7.
8.
The chemical nature of the DNA bases is an important factor in sequence-mediated association of DNA molecules. Nucleotides are the fundamental DNA elements and the base identity impacts the molecular properties of nucleotide fragments. It is interesting to study the fundamental nature of nucleotides in DNA, on the basis of base-specific interactions, association, and modes of standard atomic or molecular interactions. With all-atom molecular dynamics simulations of model dinucleotide and tetranucleotide systems having single-stranded dinucleotide or tetranucleotide fragments of varying sequences, we show how the base identity and interactions between the different bases as well as water may affect the clustering properties of nucleotides fragments in an ionic solution. Sequence-dependent differential interactions between the nucleotide fragments, ionic concentration, and elevated temperature are found to influence the clustering properties and dynamics of association. Well-known epigenetic modification of DNA, that is, cytosine methylation also promotes dinucleotide clustering in solution. These observations point to one possible chemical nature of the DNA bases, as well as the importance of the base pairing, base stacking, and ionic interactions in DNA structure formation, and DNA sequence-mediated association. Sequence- and the ionic environment-mediated self-association properties of the dinucleotides indicate its great potential to develop biological nanomaterials for desired applications. 相似文献
9.
Sai Manoj N. V. T. Gorantla Harsha S. Karnamkkott Selvakumar Arumugam Sangita Mondal Kartik Chandra Mondal 《Journal of computational chemistry》2023,44(1):43-60
The factors/structural features which are responsible for the binding, activation and reduction of N2 to NH3 by FeMoco of nitrogenase have not been completely understood well. Several relevant model complexes by Holland et al. and Peters et al. have been synthesized, characterized and studied by theoretical calculations. For a matter of fact, those complexes are much different than real active N2-binding Fe-sites of FeMoco, which possesses a central C(4-) ion having an eight valence electrons as an μ6-bridge. Here, a series of [(S3C(0))Fe(II/I/0)-N2]n- complexes in different charged/spin states containing a coordinated σ- and π-donor C(0)-atom which possesses eight outer shell electrons [carbone, (Ph3P)2C(0); Ph3P→C(0)←PPh3] and three S-donor sites (i.e. -S-Ar), have been studied by DFT, QTAIM, and EDA-NOCV calculations. The effect of the weak field ligand on Fe-centres and the subsequent N2-binding has been studied by EDA-NOCV analysis. The role of the oxidation state of Fe and N2-binding in different charged and spin states of the complex have been investigated by EDA-NOCV analyses. The intrinsic interaction energies of the Fe−N2 bond are in the range from −42/−35 to −67 kcal/mol in their corresponding ground states. The S3C(0) donor set is argued here to be closer to the actual coordination environment of one of the six Fe-centres of nitrogenase. In comparison, the captivating model complexes reported by Holland et al. and Peter et al. possess a stronger π-acceptor C-ring (S2Cring donor, π-C donor) and stronger donor set like CP3 (σ-C donor) ligands, respectively. 相似文献
10.
Shivani Arora Tavinder Singh Umasankar Mondal Dr. Anand Singh 《European journal of organic chemistry》2023,26(30):e202300469
A visible light mediated protocol for the synthesis of polyhalogenated and deuterated δ- and γ-lactams from readily available alkyl halides is reported. The reaction involves the generation of haloalkyl radicals through halogen atom transfer (XAT) and subsequent arylalkylation of olefins to afford dihydroisoquinolinones and oxindoles. This new XAT protocol exhibits wide scope under mild conditions and enables access to new halogenated chemical space. 相似文献