全文获取类型
收费全文 | 2455篇 |
免费 | 79篇 |
国内免费 | 23篇 |
专业分类
化学 | 1527篇 |
晶体学 | 7篇 |
力学 | 46篇 |
数学 | 407篇 |
物理学 | 570篇 |
出版年
2023年 | 10篇 |
2022年 | 27篇 |
2021年 | 28篇 |
2020年 | 38篇 |
2019年 | 30篇 |
2018年 | 30篇 |
2017年 | 36篇 |
2016年 | 62篇 |
2015年 | 60篇 |
2014年 | 63篇 |
2013年 | 126篇 |
2012年 | 187篇 |
2011年 | 180篇 |
2010年 | 123篇 |
2009年 | 111篇 |
2008年 | 159篇 |
2007年 | 167篇 |
2006年 | 174篇 |
2005年 | 211篇 |
2004年 | 142篇 |
2003年 | 126篇 |
2002年 | 119篇 |
2001年 | 19篇 |
2000年 | 25篇 |
1999年 | 19篇 |
1998年 | 15篇 |
1997年 | 16篇 |
1996年 | 34篇 |
1995年 | 19篇 |
1994年 | 17篇 |
1993年 | 21篇 |
1992年 | 13篇 |
1991年 | 6篇 |
1990年 | 8篇 |
1989年 | 13篇 |
1988年 | 7篇 |
1987年 | 4篇 |
1986年 | 8篇 |
1985年 | 12篇 |
1984年 | 11篇 |
1983年 | 11篇 |
1982年 | 12篇 |
1981年 | 10篇 |
1980年 | 5篇 |
1979年 | 8篇 |
1977年 | 5篇 |
1976年 | 3篇 |
1974年 | 4篇 |
1973年 | 6篇 |
1972年 | 4篇 |
排序方式: 共有2557条查询结果,搜索用时 12 毫秒
91.
The spectroscopic, electronic, and DNA-binding characteristics of two novel ruthenium complexes based on the dialkynyl ligands 2,3-bis(phenylethynyl)-1,4,8,9-tetraaza-triphenylene (bptt, 1) and 2,3-bis(4-tert-butyl-phenylethynyl)-1,4,8,9-tetraaza-triphenylene (tbptt, 2) have been investigated. Electronic structure calculations of bptt reveal that the frontier molecular orbitals are localized on the pyrazine-dialkynyl portion of the free ligand, a property that is reflected in a red shift of the lowest energy electronic transition (1: λ(max) = 393 nm) upon substitution at the terminal phenyl groups (2: λ(max) = 398 nm). Upon coordination to ruthenium, the low-energy ligand-centered transitions of 1 and 2 are retained, and metal-to-ligand charge transfer transitions (MLCT) centered at λ(max) = 450 nm are observed for [Ru(phen)(2)bptt](2+)(3) and [Ru(phen)(2)tbptt](2+)(4). The photophysical characteristics of 3 and 4 in ethanol closely parallel those observed for [Ru(bpy)(3)](2+) and [Ru(phen)(3)](2+), indicating that the MLCT excited state is primarily localized within the [Ru(phen)(3)](2+) manifold of 3 and 4, and is only sparingly affected by the extended conjugation of the bptt framework. In an aqueous environment, 3 and 4 possess notably small luminescence quantum yields (3: ?(H(2)O) = 0.005, 4: ?(H(2)O) = 0.011) and biexponential decay kinetics (3: τ(1) = 40 ns, τ(2) = 230 ns; 4: τ(1) ~ 26 ns, τ(2) = 150 ns). Addition of CT-DNA to an aqueous solution of 3 causes a significant increase in the luminescence quantum yield (?(DNA) = 0.045), while the quantum yield of 4 is relatively unaffected (?(DNA) = 0.013). The differential behavior demonstrates that tert-butyl substitution on the terminal phenyl groups inhibits the ability of 4 to intercalate with DNA. Such changes in intrinsic luminescence demonstrate that 3 binds to DNA via intercalation (K(b) = 3.3 × 10(4) M(-1)). The origin of this light switch behavior involves two competing (3)MLCT states similar to that of the extensively studied light switch molecule [Ru(phen)(2)dppz](2+). The solvent- and temperature-dependence of the luminescence of 3 reveal that the extended ligand aromaticity lowers the energy of the (3)ππ* excited state into competition with the emitting (3)MLCT state. Interconversion between these two states plays a significant role in the observed photophysics and is responsible for the dual emission in aqueous environments. 相似文献
92.
Popeney CS Setaro A Mutihac RC Bluemmel P Trappmann B Vonneman J Reich S Haag R 《Chemphyschem》2012,13(1):203-211
A series of nonionic amphiphiles derived from polyglycerol dendrons were studied for their ability to solubilize and isolate single-walled carbon nanotubes. The amphiphiles possessed differently sized polar head groups, hydrophobic tail units, and various aromatic and non-aromatic groups between the head and tail groups. Absorbance analysis revealed that amphiphiles with anchor groups derived from pyrene were far inferior to those that possessed simple linear aliphatic tail groups. Absorbance and near-infrared fluorescence analyses revealed a weak dependence on the dendron size of the head group, but a strong positive trend in suspended nanotube density and fluorescence intensity for amphiphiles with longer tail units. Variations in the moieties linking the head and tail groups led to a range of effects on the suspensions, with linkers imparting flexibility and a bent shape that gave improved performance overall. This was illustrated most dramatically by a pair of benzamide-containing amphiphiles, the para isomer of which showed evidence in the fluorescence data of increased nanotube aggregate formation when compared with the meta isomer. In addition, statistical AFM was used to illustrate more directly the microscopic differences between amphiphiles that were effective at nanotube bundle disruption and those that were not. 相似文献
93.
Adsorption of methylene blue (MB) on agar was investigated as a function of temperature (308-328 K), different concentrations of NaCl and HCl and various weight percentages of binary mixtures of ethanol with water. It was observed that the maximum experimental adsorption capacity, q m, exp, in water is up to 50 mg g-1 and decreases with increase in weight percentage of ethanol and NaCl and HCl concentration compared to that of water. Analysis of data using ARIAN model showed that MB adsorbs as monomer and dimer on the surface of agar. Binding constants of MB to agar were calculated using the Temkin isotherm. The process is exothermic in water and other solutions. The mean adsorption energy (E) value indicated binding of MB to agar is chemical adsorption. Kinetics of this interaction obeys from the pseudo-second-order model and diffusion of the MB molecules into the agar is the main rate-controlling step. 相似文献
94.
95.
Meiling Lu Xing‐Fang Li X. Chris Le Michael Weinfeld Hailin Wang 《Rapid communications in mass spectrometry : RCM》2010,24(11):1523-1532
We describe a method for probing surface‐exposed cysteines in proteins by selective labeling with p‐hydroxymercuribenzoate (PMB) combined with nano‐electrospray ionization mass spectrometric analysis (nanoESI‐MS). The rapid, stoichiometric, and specific labeling by PMB of surface‐exposed cysteines allows for characterization of the accessibility of the cysteines using a single MS analysis. Moreover, by taking advantage of the large mass shift of 321 Da, unique isotopic pattern, and enhanced MS signal of PMB‐labeled cysteine‐containing peptide fragments, the surface‐exposed cysteines in proteins can be accurately identified by peptide mapping. The number and sites of reactive cysteines on the surface of human and rat hemoglobins (hHb and rHb) were identified as examples. Collision‐induced dissociation tandem mass spectrometric (MS/MS) analysis of specific peptides further confirmed the selective labeling of PMB in hHb. The subtle difference between the different cysteine residues in rHb was also evaluated by multiple PMB titrations. The difference between the two cysteines in their environment may partially explain their reaction specificity. Cysteine 125 in the β unit of rHb is exposed on the surface, explaining its reactivity with glutathione. Cysteine 13 in the α subunit of rHb is much less exposed, and is located in a hydrophobic pocket, a conclusion that is consistent with the previous observation of its selective binding with dimethylarsinous acid, a reactive arsenic metabolite. The method is potentially useful for probing cysteines in other biologically important proteins and for studying proteins that are associated with conformational or structural changes induced by denaturing processes, protein modifications, protein‐protein interactions and protein assemblies. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
96.
This paper is motivated by the desire to formulate a relativistically covariant hidden-variable particle trajectory interpretation of the quantum theory of the vector field that is formulated in such a way as to allow the inclusion of gravity. We present a methodology for calculating the flows of rest energy and a conserved density for the massive vector field using the time-like eigenvectors and eigenvalues of the stress-energy-momentum tensor. Such flows may be used to define particle trajectories which follow the flow. This work extends our previous work which used a similar procedure for the scalar field. The massive, spin-one, complex vector field is discussed in detail and the flows of energy-momentum are illustrated in a simple example of standing waves in a plane. 相似文献
97.
Quan Chen Chris Boothroyd Andrew Mcintosh Soutar Xian Ting Zeng 《Journal of Sol-Gel Science and Technology》2010,53(1):115-120
The surface of commercial titania particles was coated by a layer of silica by a two-step process which involved a power ultrasound initiated sol–gel reaction. In the first step of this solution process, aminosilane, i.e. organosilane with amino functional group, was used to modify the surface of pristine nanoparticles. Subsequent silica nanocoating was initiated and sustained under power ultrasound agitation in a mixture of surface modified particles and epoxysilane. As a result, a homogenous coverage of silica on the nanoparticles’ surface, with thickness controllable from one to several nanometers, was obtained. Fourier transform infrared spectroscopy (FTIR), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and particle surface zeta potential measurements were employed to follow steps in the process and to confirm the reaction mechanism. 相似文献
98.
Lydia A. Panther Dr. Daniel P. Guest Dr. Andrew McGown Hugo Emerit Dr. Raysa Khan Tareque Dr. Arathy Jose Mr. Chris M. Dadswell Dr. Simon J. Coles Dr. Graham J. Tizzard Dr. Ramón González-Méndez Dr. Charles A. I. Goodall Prof. Mark C. Bagley Prof. John Spencer Dr. Barnaby W. Greenland 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(49):e202201444
Solvent-free synthesis by using a vibratory ball mill (VBM) offers the chance to access new chemical reactivity, whilst reducing solvent waste and minimising reaction times. Herein, we report the core functionalisation of N,N’-bis(2-ethylhexyl)-2,6-dibromo-1,4,5,8-naphthalenetetracarboxylic acid (Br2-NDI) by using Suzuki, Sonogashira and Buchwald–Hartwig coupling reactions. The products of these reactions are important building blocks in many areas of organic electronics including organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs) and organic photovoltaic cells (OPVCs). The reactions proceed in as little as 1 h, use commercially available palladium sources (frequently Pd(OAc)2) and are tolerant to air and atmospheric moisture. Furthermore, the real-world potential of this green VBM protocol is demonstrated by the double Suzuki coupling of a monobromo(NDI) residue to a bis(thiophene) pinacol ester. The resulting dimeric NDI species has been demonstrated to behave as an electron acceptor in functioning OPVCs. 相似文献
99.
Axel Ingendoh Jan Becher Helen Clausen Helle Chris Nielsen 《Tetrahedron letters》1985,26(9):1249-1252
The high reactivity of the -1-acyloxy-1,3-pentadiene-5-ols as dienes in intramolecular Diels-Alder reactions with maleic anhydride and fumaric acid ethylester monochloride is discussed. 相似文献
100.
Monir Uddin Antonis G. Hatzidimitriou Maria Lalia-Kantouri Chris Tsiamis 《Structural chemistry》1997,8(2):131-139
The infrared and electronic excitation spectra of a series of new nickel(II) chelates containing an-diimine (or nitrogenous base, enR) and the anion of a-dione (1,3-ketoenol or 1,3-ketoester,H) were obtained in the solid state and in solution. The composition and the overall structure of the new chelates in the solid state depends on ligand concentration, the substituents within the-dionato moiety and the counterion present. The IR and electronic excitation spectra of [Ni(enR)2
]NO3 and [Ni(enR)(O2NO)] indicate, in conjunction with other physicochemical measurements, bidentate coordination of the ligands, while the spectral shifts reveal replacement of the (O,O)nitrato group by basic solvents. The existence of the nickel(II) in an octahedral environment is confirmed by an X-ray structure analysis of [Ni(dpamH)2acac]NO3 · CH3OH (monoclinic, space groupP2l/n, a=17.296(1),b=7.462(1),c=21.604(3) å,=95.65(1),Z=4, R=0.0534,Rw=0.0600), where dpamH denotes the 2,2-dipyridylamine. 相似文献