全文获取类型
收费全文 | 1011篇 |
免费 | 57篇 |
国内免费 | 1篇 |
专业分类
化学 | 695篇 |
晶体学 | 2篇 |
力学 | 53篇 |
数学 | 152篇 |
物理学 | 167篇 |
出版年
2024年 | 4篇 |
2023年 | 9篇 |
2022年 | 22篇 |
2021年 | 50篇 |
2020年 | 39篇 |
2019年 | 27篇 |
2018年 | 28篇 |
2017年 | 20篇 |
2016年 | 71篇 |
2015年 | 40篇 |
2014年 | 42篇 |
2013年 | 69篇 |
2012年 | 82篇 |
2011年 | 113篇 |
2010年 | 53篇 |
2009年 | 34篇 |
2008年 | 50篇 |
2007年 | 57篇 |
2006年 | 53篇 |
2005年 | 55篇 |
2004年 | 30篇 |
2003年 | 33篇 |
2002年 | 23篇 |
2001年 | 5篇 |
2000年 | 11篇 |
1999年 | 4篇 |
1998年 | 1篇 |
1997年 | 2篇 |
1996年 | 7篇 |
1995年 | 5篇 |
1994年 | 1篇 |
1993年 | 2篇 |
1991年 | 3篇 |
1990年 | 2篇 |
1989年 | 6篇 |
1988年 | 1篇 |
1987年 | 2篇 |
1985年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1979年 | 1篇 |
1976年 | 1篇 |
1970年 | 1篇 |
1961年 | 1篇 |
1948年 | 1篇 |
1938年 | 1篇 |
1937年 | 1篇 |
1918年 | 1篇 |
1916年 | 1篇 |
排序方式: 共有1069条查询结果,搜索用时 265 毫秒
991.
Pineider F Mannini M Sessoli R Caneschi A Barreca D Armelao L Cornia A Tondello E Gatteschi D 《Langmuir : the ACS journal of surfaces and colloids》2007,23(23):11836-11843
A sulfur-containing single molecule magnet, [Mn12O12(O2CC6H4SCH3)16(H2O)4], was assembled from solution on a Au(111) surface affording both submonolayer and monolayer coverages. The adsorbate morphology and the degree of coverage were inspected by scanning tunneling microscopy (STM), while X-ray photoelectron spectroscopy (XPS) allowed the determination of the chemical nature of the adsorbate on a qualitative and quantitative basis. The properties of the adsorbates were found to be strongly dependent on the solvent used to dissolve the magnetic complex. In particular, systems prepared from tetrahydrofuran solutions gave arrays of isolated and partially ordered clusters on the gold substrate, while samples prepared from dichloromethane exhibited a homogeneous monolayer coverage of the whole Au(111) surface. These findings are relevant to the optimization of magnetic addressing of single molecule magnets on surfaces. 相似文献
992.
Ferri D Behzadi B Kappenberger P Hauert R Ernst KH Baiker A 《Langmuir : the ACS journal of surfaces and colloids》2007,23(3):1203-1208
Bimetallic Pd-Au and Pt-Au and monometallic Pd, Pt, and Au films were prepared by physical vapor deposition. The resulting surfaces were characterized by means of XPS, AFM, and CO adsorption from the liquid phase (CH2Cl2) monitored by ATR-IR spectroscopy. CO adsorption combined with ATR-IR proved to be a very sensitive method for probing the degree of interdiffusion occurring at the interfaces whose properties were altered by variation of the Pd and Pt film thickness from 0.2 to 2 nm. Because no CO adsorption was observed on Au, the evaporation of Pt-group metals on Au allowed us to study the effect of dilution on the adsorption properties of the surfaces. At equivalent Pd film thickness, the evaporation of Au reduced the amount of adsorbed CO and caused the formation of 2-fold bridging CO, which was almost absent in monometallic surfaces. Additionally, the average particle size on Pd-Au surfaces was smaller than that on monometallic Pd surfaces. The results indicate that a Pd/Au diffuse interface is formed that affects the Pd particle size even more drastically than the simple decrease in Pd film thickness in monometallic surfaces. Pt-Au surfaces were less sensitive to CO adsorption, indicating that the two metals do not mix to a significant extent. The difference in the interfacial behavior of Pd and Pt in the bimetallic gold films is traced to the largely different Pd-Au and Pt-Au miscibility gaps. 相似文献
993.
We performed molecular dynamics simulations of diluted solutions of calcium carbonate in water. To this end, we combined and tested previous polarizable models. The carbonate anion forms long-living hydrogen bonds with water and shows an amphiphilic character, in which the water molecules are expelled in a region close to its C(3) symmetry axis. The calcium cation forms a strongly bound ion pair with the carbonate. The first hydration shell around the CaCO(3) pair is found to be very similar to the location of the water molecules surrounding CaCO(3) in ikaite, the hydrated mineral. 相似文献
994.
Tamburro D Fredolini C Espina V Douglas TA Ranganathan A Ilag L Zhou W Russo P Espina BH Muto G Petricoin EF Liotta LA Luchini A 《Journal of the American Chemical Society》2011,133(47):19178-19188
Many low-abundance biomarkers for early detection of cancer and other diseases are invisible to mass spectrometry because they exist in body fluids in very low concentrations, are masked by high-abundance proteins such as albumin and immunoglobulins, and are very labile. To overcome these barriers, we created porous, buoyant, core-shell hydrogel nanoparticles containing novel high affinity reactive chemical baits for protein and peptide harvesting, concentration, and preservation in body fluids. Poly(N-isopropylacrylamide-co-acrylic acid) nanoparticles were functionalized with amino-containing dyes via zero-length cross-linking amidation reactions. Nanoparticles functionalized in the core with 17 different (12 chemically novel) molecular baits showed preferential high affinities (K(D) < 10(-11) M) for specific low-abundance protein analytes. A poly(N-isopropylacrylamide-co-vinylsulfonic acid) shell was added to the core particles. This shell chemistry selectively prevented unwanted entry of all size peptides derived from albumin without hindering the penetration of non-albumin small proteins and peptides. Proteins and peptides entered the core to be captured with high affinity by baits immobilized in the core. Nanoparticles effectively protected interleukin-6 from enzymatic degradation in sweat and increased the effective detection sensitivity of human growth hormone in human urine using multiple reaction monitoring analysis. Used in whole blood as a one-step, in-solution preprocessing step, the nanoparticles greatly enriched the concentration of low-molecular weight proteins and peptides while excluding albumin and other proteins above 30 kDa; this achieved a 10,000-fold effective amplification of the analyte concentration, enabling mass spectrometry (MS) discovery of candidate biomarkers that were previously undetectable. 相似文献
995.
Kondo A Kajiro H Noguchi H Carlucci L Proserpio DM Ciani G Kato K Takata M Seki H Sakamoto M Hattori Y Okino F Maeda K Ohba T Kaneko K Kanoh H 《Journal of the American Chemical Society》2011,133(27):10512-10522
Selective synthetic routes to coordination polymers [Cu(bpy)(2)(OTf)(2)](n) (bpy = 4,4'-bipyridine, OTf = trifluoromethanesulfonate) with 2- and 3-dimensionalities of the frameworks were established by properly choosing each different solvent-solution system. They show a quite similar local coordination environment around the Cu(II) centers, but these assemble in a different way leading to the 2D and 3D building-up structures. Although the two kinds of porous coordination polymers (PCPs) both have flexible frameworks, the 2D shows more marked flexibility than the 3D, giving rise to different flexibility-associated gas adsorption behaviors. All adsorption isotherms for N(2), CO(2), and Ar on the 3D PCP are of type I, whereas the 2D PCP has stepwise gas adsorption isotherms, also for CH(4) and water, in addition to these gases. The 3D structure, having hydrophilic and hydrophobic pores, shows the size-selective and quadrupole-surface electrical field interaction dependent adsorption. Remarkably, the 2D structure can accommodate greater amounts of gas molecules than that corresponding to the inherent crystallographic void volume through framework structural changes. In alcohol adsorption isotherms, however, the 2D PCP changes its framework structure through the guest accommodation, leading to no stepwise adsorption isotherms. The structural diversity of the 2D PCP stems from the breathing phenomenon and expansion/shrinkage modulation. 相似文献
996.
Fantauzzi M Licheri C Atzei D Loi G Elsener B Rossi G Rossi A 《Analytical and bioanalytical chemistry》2011,401(7):2237-2248
In this work, a multi-technical bulk and surface analytical approach was used to investigate the bioleaching of a pyrite and
arsenopyrite flotation concentrate with a mixed microflora mainly consisting of Acidithiobacillus ferrooxidans. X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and X-ray-induced Auger electron spectroscopy mineral surfaces
investigations, along with inductively coupled plasma-atomic emission spectroscopy and carbon, hydrogen, nitrogen and sulphur
determination (CHNS) analyses, were carried out prior and after bioleaching. The flotation concentrate was a mixture of pyrite
(FeS2) and arsenopyrite (FeAsS); after bioleaching, 95% of the initial content of pyrite and 85% of arsenopyrite were dissolved.
The chemical state of the main elements (Fe, As and S) at the surface of the bioreactor feed particles and of the residue
after bioleaching was investigated by X-ray photoelectron and X-ray excited Auger electron spectroscopy. After bioleaching,
no signals of iron, arsenic and sulphur originating from pyrite and arsenopyrite were detected, confirming a strong oxidation
and the dissolution of the particles. On the surfaces of the mineral residue particles, elemental sulphur as reaction intermediate
of the leaching process and precipitated secondary phases (Fe–OOH and jarosite), together with adsorbed arsenates, was detected.
Evidence of microbial cells adhesion at mineral surfaces was also produced: carbon and nitrogen were revealed by CHNS, and
nitrogen was also detected on the bioleached surfaces by XPS. This was attributed to the deposition, on the mineral surfaces,
of the remnants of a bio-film consisting of an extra-cellular polymer layer that had favoured the bacterial action. 相似文献
997.
998.
Luparia M Oliveira MT Audisio D Frébault F Goddard R Maulide N 《Angewandte Chemie (International ed. in English)》2011,50(52):12631-12635
Your wish is my command: Deracemization is a powerful strategy wherein a racemate is converted into a 100?% yield of a single enantiopure product. A new concept in catalytic deracemization is presented, in which a racemate with n?stereogenic elements can be selectively converted into each one of 2(m) (m = number of chiral centers of the product) different enantiopure products, by simple tuning of the reaction conditions. 相似文献
999.
Homogeneous ice nucleation from supercooled water was studied in the temperature range of 220-240 K through combining the forward flux sampling method (Allen et al., J. Chem. Phys., 2006, 124, 024102) with molecular dynamics simulations (FFS/MD), based on a recently developed coarse-grained water model (mW) (Molinero et al., J. Phys. Chem. B, 2009, 113, 4008). The calculated ice nucleation rates display a strong temperature dependence, ranging from 2.148 ± 0.635 × 10(25) m(-3) s(-1) at 220 K to 1.672 ± 0.970 × 10(-7) m(-3) s(-1) at 240 K. These rates can be fitted according to the classical nucleation theory, yielding an estimate of the effective ice-water interface energy γ(ls) of 31.01 ± 0.21 mJ m(-2) for the mW water model. Compared to experiments, our calculation underestimates the homogeneous ice nucleation rate by a few orders of magnitude. Possible reasons for the discrepancy are discussed. The nucleating ice embryo contains both cubic ice Ic and hexagonal ice Ih, with the fraction of each structure being roughly 50% when the critical size is reached. In particular, a novel defect structure containing nearly five-fold twin boundaries is identified in the ice clusters formed during nucleation. The way such defect structure is formed is found to be different from mechanisms proposed for the formation of the same defect in metallic nanoparticles and thin film. The quasi five-fold twin boundary structure found here is expected to occur in the crystallization of a wide range of materials with the diamond cubic structure, including ice. 相似文献
1000.
Lorenzo Bertini Alberto De Sole Davide Gabrielli Giovanni Jona‐Lasinio Claudio Landim 《纯数学与应用数学通讯》2011,64(5):649-696
Consider the viscous Burgers equation ut + f(u)x = εuxx on the interval [0,1] with the inhomogeneous Dirichlet boundary conditions u(t,0) = ρ0, u(t,1) = ρ1. The flux f is the function f(u) = u(1 − u), ε > 0 is the viscosity, and the boundary data satisfy 0 < ρ0 < ρ1 < 1. We examine the quasi‐potential corresponding to an action functional arising from nonequilibrium statistical mechanical models associated with the above equation. We provide a static variational formula for the quasi‐potential and characterize the optimal paths for the dynamical problem. In contrast with previous cases, for small enough viscosity, the variational problem defining the quasi‐potential admits more than one minimizer. This phenomenon is interpreted as a nonequilibrium phase transition and corresponds to points where the superdifferential of the quasi‐potential is not a singleton. © 2011 Wiley Periodicals, Inc. 相似文献