全文获取类型
收费全文 | 2328篇 |
免费 | 64篇 |
国内免费 | 5篇 |
专业分类
化学 | 1504篇 |
晶体学 | 9篇 |
力学 | 54篇 |
数学 | 257篇 |
物理学 | 573篇 |
出版年
2023年 | 17篇 |
2022年 | 32篇 |
2021年 | 28篇 |
2020年 | 20篇 |
2019年 | 27篇 |
2018年 | 18篇 |
2017年 | 18篇 |
2016年 | 39篇 |
2015年 | 46篇 |
2014年 | 55篇 |
2013年 | 118篇 |
2012年 | 96篇 |
2011年 | 147篇 |
2010年 | 81篇 |
2009年 | 65篇 |
2008年 | 129篇 |
2007年 | 127篇 |
2006年 | 126篇 |
2005年 | 119篇 |
2004年 | 107篇 |
2003年 | 102篇 |
2002年 | 75篇 |
2001年 | 42篇 |
2000年 | 40篇 |
1999年 | 35篇 |
1998年 | 19篇 |
1997年 | 22篇 |
1996年 | 32篇 |
1995年 | 33篇 |
1994年 | 34篇 |
1993年 | 38篇 |
1992年 | 28篇 |
1991年 | 27篇 |
1990年 | 22篇 |
1989年 | 18篇 |
1988年 | 21篇 |
1987年 | 22篇 |
1986年 | 21篇 |
1985年 | 35篇 |
1984年 | 21篇 |
1983年 | 21篇 |
1982年 | 19篇 |
1981年 | 21篇 |
1980年 | 24篇 |
1979年 | 27篇 |
1978年 | 19篇 |
1977年 | 25篇 |
1976年 | 23篇 |
1974年 | 19篇 |
1973年 | 21篇 |
排序方式: 共有2397条查询结果,搜索用时 15 毫秒
81.
I M Johansson E C Huang J D Henion J Zweigenbaum 《Journal of chromatography. A》1991,554(1-2):311-327
On-line capillary electrophoresis (CE) separations are shown for a synthetic peptide mixture and a tryptic digest of human hemoglobin in an uncoated fused-silica capillary with detection using atmospheric pressure ionization mass spectrometry (API-MS). The CE system utilized a 1-m capillary column of either 75- or 100-microns I.D. These somewhat larger inside diameters allow higher sample capacities for MS detection and the 1-m length facilitates connecting the CE column to the liquid junction-ion spray interface and MS system. Low volatile buffer concentrations (15-20 mM) of ammonium acetate or ammonium formate, and high organic modifier content (5-50%) of methanol or acetonitrile facilitates ionization under electrospray conditions. This study shows that peptides separated by CE may be transferred to the API-MS system through a liquid junction coupling to the pneumatically assisted electrospray (ion spray) interface at low buffer pH when the electroosmotic flow is low (0-0.04 microliter/min). CE-MS as described herein is facilitated by features in modern CE instrumentation including robotic cleaning and pressurization of the capillary inlet. The latter is particularly useful for repetitive rinsing and conditioning of the capillary column between analyses in addition to continuous 'infusion' of sample to the mass spectrometer for tuning purposes. In addition to facile molecular weight determination, amino acid sequence information for peptides may be obtained by utilizing on-line tandem MS. After the tryptic digest sample components enter the API-MS system, the molecular ion species of individual peptides may be focussed and transmitted into the collision cell of the tandem triple quadrupole mass spectrometer. Collision-induced dissociation of protonated peptide molecules yielded structural information for their characterization following injection of 10 pmol of a tryptic digest from human hemoglobin. 相似文献
82.
The electrode reaction Zn(II)/Zn(Hg) in complex chloride, bromide, and iodide solutions with DMSO as solvent and ammonium perchlorate as supporting electrolyte has been studied at the equilibrium potential by the faradaic impedance method and a square-wave method. Furthermore, double-layer data have been determined by electrocapillary measurements. The results indicate that the zinc chloride and bromide complexes do not contribute noticeably to the exchange current density, while in the iodide system both the solvated zinc ion and the first complex take part in the charge transfer. From the dissimilar results valid for water and DMSO solutions the conclusion is made that probably ligand bridging at the amalgam by the halide ions is operative in water solutions, whereas in DMSO the larger solvent molecules adsorbed can form a steric hindrance to ligand bridging by chloride or bromide ions. 相似文献
83.
Six new divalent lanthanide complexes using triglyme (trigly) and tetraglyme (tetgly) as achiral ligands have been prepared, using a facile synthetic method, in search for enantioselective solid-state reagents. The crystal structures of cis-[SmI2(trigly)thf] (1), trans-[YbI2(trigly)thf] (2), trans-[SmI2(trigly)dme] (3), trans-[YbI2(tetgly)] (4), trans-[EuI2(tetgly)thf] (5), and [Sm(tetgly)2][SmI3(tetgly)]I (6) have been determined. All complexes, except 5, are chiral. The 10-coordinate cation in 6 displays a helical chirality since the two tetraglyme ligands are wrapped around the samarium ion. Since trans-[YbI2(tetgly)] (4), which has a chiral arrangement of terminal methyl groups, crystallizes as a conglomerate, preferential crystallization and consequent enantioselective reduction of acetophenone was attempted, but resulted in racemic products, possibly on account of racemic twinning in 4. 相似文献
84.
Johnston AM Scrimgeour CM Kennedy H Handley LL 《Rapid communications in mass spectrometry : RCM》2003,17(11):1099-1106
The conversion of ammonium (NH(4) (+)) to 1-sulfonato-iso-indole has been examined as a method for natural abundance measurement of delta(15)N of NH(4) (+). The reaction is complete within 2 h and is based on the derivatisation of NH(4) (+) by o-phthaldialdehyde and sodium sulfite at a high pH, 11.2. The product is readily concentrated from dilute solutions by reverse-phase solid-phase extraction (SPE). The method is compound-specific despite partial derivatisation of potentially interfering amino acids, as their derivatives are not extracted by SPE. delta(15)N values of NH(4) (+) in KCL soil extracts can be measured within 48 h by automated continuous-flow IRMS with a precision of 0.23 per thousand (1 SD). Parallel measurements of NH(4) (+) standards of known delta(15)N are made to allow correction for the isotopic dilution by non-sample NH(4) (+). The practicality of this method is demonstrated by measuring the changes in NH(4) (+) concentration and delta(15)N following the addition of urea as a nitrogen source to inorganic N-depleted soil. 相似文献
85.
Carrier solutions for stripping voltammetry in flow systems are deoxygenated by reaction with glucose added to the carrier. The reaction was catalyzed by glocuse oxidase and catalase co-immobilized in an enzyme reactor which was inserted before the injector. The oxygenated was removed at least as efficiently as with nitrogen purging and the voltametric behaviour of cadmium(II), lead(II) and zinc(II) was unaffected by the glucose/gluconic acid system. A particular advantage is the rapid start-up compared to the lengthy purging of carrier solution when nitrogen degassing is used. The enzyme reactor made from porous glass was effective for several months. 相似文献
86.
A field theoretical formulation is given for the method of different orbitals for different spins (DODS ). For an infinite system DODS describes an antiferromagnetic state and to account for this spin ordering a Gorkov-type of factorization is introduced. A corresponding gap equation is derived, where a non-zero solution indicates the presence of long-range order in the system. Actually the formulation given is general enough as to render DODS as a special case. As shown, we may also obtain a ferrimagnetic as well as a density wave state solution depending on the special characteristics of the system at hand. A related type of antiferromagnetism is described by the Overhauser spin density wave (SDW ) state and also this theory is formulated in a field theoretical language. The similarities and differences between DODS and SDW are discussed. The energy expressions for the two states are given within the Hartree-Fock approximation. It is proposed that the SDW state could be used to partly account for the correlation problem in molecules, as well as the method of DODS which has previously been employed for that purpose. 相似文献
87.
Adams RD Captain B Johansson M Smith JL 《Journal of the American Chemical Society》2005,127(2):488-489
The new rhenium-tin complex Re2(CO)8(mu-SnPh2)2, 1 was obtained in 52% yield from the reaction of Re2(CO)8(mu-H)[mu-C(H)C(H)Bu] with Ph3SnH. Compound 1 contains two SnPh2 groups bridging a long Re-Re single bond, Re-Re = 3.1971(4) A [3.1902(4) A], Re-Sn = 2.7429(4) A [2.7445(4) A], and 2.7675(4) [2.7682(5) A]. A bis-Pd(PBut3) adduct of 1, Pd2Re2(CO)8(mu-SnPh2)2(PBut3)2, 2 was obtained from the reaction of 1 with Pd(PBut3)2. Compound 2 contains Pd(PBut3) groups bridging two of its four Re-Sn bonds. The Re-Re bond and the unbridged Re-Sn bonds in 2 are significantly longer than those in 1, 3.245(1) A and 2.8167(14) A, respectively. Fenske-Hall molecular orbital calculations on 1 and 2 have been performed to explain the metal-metal bonding in these unusual mixed-metal polynuclear metal complexes. 相似文献
88.
Takeshita N Paradis LA Oner D McCarthy TJ Chen W 《Langmuir : the ACS journal of surfaces and colloids》2004,20(19):8131-8136
Wettability was controlled in a rational manner by individually and simultaneously manipulating surface topography and surface chemical structure. The first stage of this research involved the adsorption of charged submicrometer polystyrene latex particles to oppositely charged poly(ethylene terephthalate) (PET) film samples to form surfaces with different topographies/roughness; adsorption time, solution pH, solution ionic strength, latex particle size, and substrate charge density are external variables that were controlled. The introduction of discrete functional groups to smooth and rough surfaces through organic transformations was carried out in the second stage. Amine groups (-NH(2)) and alcohol groups (-OH) were introduced onto smooth PET surfaces by amidation with poly(allylamine) and adsorption with poly(vinyl alcohol) (PVOH), respectively. On latex particle adsorbed surfaces, a thin layer of gold was evaporated first to prevent particle redistribution before chemical transformation. Reactions with functionalized thiols and adsorption with PVOH on patterned gold surfaces successfully enhanced surface hydrophobicity and hydrophilicity. Particle size and biomodal particle size distribution affect both hydrophobicity and hydrophilicity. A very hydrophobic surface exhibiting water contact angles of 150 degrees /126 degrees (theta(A)/theta(R)) prepared by adsorption of 1-octadecanethiol and a hydrophilic surface with water contact angles of 18 degrees /8 degrees (theta(A)/theta(R)) prepared by adsorption of PVOH were prepared on gold-coated surfaces containing both 0.35 and 0.1 microm latex particles. The combination of surface topography and surface-chemical functionality permits wettability control over a wide range. 相似文献
89.
Thapper A Behrens A Fryxelius J Johansson MH Prestopino F Czaun M Rehder D Nordlander E 《Dalton transactions (Cambridge, England : 2003)》2005,(21):3566-3571
Reaction of the tetradentate ligand N-(2-hydroxybenzyl)-N,N-bis(2-pyridylmethyl)amine (L-OH) with MoO2Cl2 in methanol in the presence of NaOMe and PF6- results in the formation of [MoO2(L-O)]PF6. Similarly, the reaction of N-(2-mercaptobenzyl)-N,N-bis(2-pyridylmethyl)amine (L-SH) with MoO2(acac)2 leads to the formation of [MoO2(L-S)]+. The dioxo-molybdenum complex [MoO2(L-O)]+ reacts with phosphines in methanol to afford phosphine oxides and an air-sensitive molybdenum complex, tentatively identified as [Mo(IV)O(L-O)(OCH3)]. The latter complex is capable of reducing biological oxygen donors such as DMSO or nitrate, thereby mimicking the activity of DMSO reductase and nitrate reductase. Reaction of [MoO2(L-O)]PF6 with PPh3 in other solvents than methanol leads to the formation of the Mo(V) dimer [(L-O)OMo(micro-O)MoO(L-O)](PF6)2. The crystal structures of [MoO2(L-O)]PF6 and the micro-oxo bridged dimer are presented. 相似文献
90.
Determination of noscapine in plasma by liquid chromatography 总被引:1,自引:0,他引:1
A liquid chromatographic method has been developed for the determination of noscapine in plasma. Noscapine and the internal standard, papaverine, were extracted into methylene chloride by column extraction. The separation was performed on a straight-phase liquid chromatographic system using a mobile phase of hexane--methanol--chloroform--diethylamine. A high detection selectivity was obtained by UV detection at 310 nm. The precision of the method was 3.8% (standard deviation) at a level of 89 ng/ml and 9.5% (standard deviation) at 5.9 ng/ml. The selectivity of the analytical method was evaluated by comparing analytical results after isolation of extracts of plasma samples on reversed- and straight-phase liquid chromatographic systems. 相似文献