全文获取类型
收费全文 | 7388篇 |
免费 | 1043篇 |
国内免费 | 1145篇 |
专业分类
化学 | 6188篇 |
晶体学 | 120篇 |
力学 | 308篇 |
综合类 | 91篇 |
数学 | 806篇 |
物理学 | 2063篇 |
出版年
2024年 | 12篇 |
2023年 | 82篇 |
2022年 | 164篇 |
2021年 | 214篇 |
2020年 | 258篇 |
2019年 | 259篇 |
2018年 | 205篇 |
2017年 | 240篇 |
2016年 | 350篇 |
2015年 | 376篇 |
2014年 | 428篇 |
2013年 | 520篇 |
2012年 | 638篇 |
2011年 | 722篇 |
2010年 | 511篇 |
2009年 | 464篇 |
2008年 | 568篇 |
2007年 | 471篇 |
2006年 | 453篇 |
2005年 | 410篇 |
2004年 | 333篇 |
2003年 | 313篇 |
2002年 | 339篇 |
2001年 | 239篇 |
2000年 | 180篇 |
1999年 | 169篇 |
1998年 | 109篇 |
1997年 | 94篇 |
1996年 | 58篇 |
1995年 | 57篇 |
1994年 | 38篇 |
1993年 | 38篇 |
1992年 | 38篇 |
1991年 | 40篇 |
1990年 | 27篇 |
1989年 | 16篇 |
1988年 | 26篇 |
1987年 | 18篇 |
1986年 | 20篇 |
1985年 | 16篇 |
1984年 | 12篇 |
1983年 | 8篇 |
1982年 | 11篇 |
1981年 | 4篇 |
1980年 | 4篇 |
1979年 | 4篇 |
1978年 | 4篇 |
1977年 | 3篇 |
1975年 | 4篇 |
1936年 | 2篇 |
排序方式: 共有9576条查询结果,搜索用时 15 毫秒
121.
A thin film of manganese hexacyanoferrate (MnHCF) was electrochemically formed on a glassy carbon (GC) electrode to prepare a chemically modified electrode (CME). The mechanism of film formation of MnHCF and its growth process were investigated in detail by cyclic voltammetry. The results show that the stoichiometric composition of MnHCF is Mn^ⅢFe^Ⅲ(CN)6, an analogue of prussian yellow. There exist three clear-cut stages in the whole modification process and the last stage is indispensable to the fabrication of homogenized, stable MnHCF film and must last for an appropriate time. The surface morphology of MnHCF/GC electrode was characterized by scanning electron microscopy (SEM), which further verified the effective deposition of MnHCF film on GC. The kinetic constants of MnHCF/GC electrode process were also evaluated. The resulting MnHCF film modified electrode presented good stability and high electrocatalytic activity toward the oxidation of H2O2, indicating that MnHCF film possesses function of catalase and can be expected for analytical purposes. 相似文献
122.
Kohli BM Eng JK Nitsch RM Konietzko U 《Rapid communications in mass spectrometry : RCM》2005,19(5):589-596
In liquid chromatography/tandem mass spectrometry (LC/MS/MS) analyses of complex peptide mixtures, dynamic exclusion functions are used to minimize repeat selections of identical precursors for collision induced dissociation (CID). We describe a new algorithm for the dynamic exclusion of m/z values during LC/MS/MS. Full-scan based peak exclusion (Fulspec) uses a simplified model of chromatographic peak formation to detect and exclude contaminants present throughout the run or that lead to broad peaks. Therefore, instead of excluding peptides from fragment analysis according to a rigidly predefined time window, the chromatographic properties of the detected analytes are used. The algorithm was tested on two datasets derived from previously published experiments. Fulspec achieves a distribution of CID spectra with minimal tailing on the retention time axis, without resorting to rigid exclusion of m/z values. The procedure further excludes intensities with a bias towards low-quality CID spectra. This combination frees up valuable analytical capacity. The underlying intensity vs. quality analyses challenge the assumption that abundant precursors automatically give the best identifications. Further validation of the algorithm will require its incorporation by equipment manufacturers into the instrument control programs. 相似文献
123.
Lee JS Zhang MH Yun EK Geum D Kim K Kim TH Lim YS Seo JS 《Experimental & molecular medicine》2005,37(5):427-435
Vimentin is an intermediate filament that regulates cell attachment and subcellular organization. In this study, vimentin filaments were morphologically altered, and its soluble subunits were rapidly reduced via cadmium chloride treatment. Cadmium chloride stimulated three major mitogen-activated protein kinases (MAPKs): extracellular signal-regulated kinase (ERK), c-Jun N-terminal kinase (JNK), and p38, and led apoptotic pathway via caspase-9 and caspase-3 activations. In order to determine whether MAPKs were involved in this cadmium-induced soluble vimentin disappearance, we applied MAPK-specific inhibitors (PD98059, SP600125, SB203580). These inhibitors did not abolish the cadmium-induced soluble vimentin disappearance. Caspase and proteosome degradation pathway were also not involved in soluble vimentin disappearance. When we observed vimentin levels in soluble and insoluble fractions, soluble vimentin subunits shifted to an insoluble fraction. As we discovered that heat-shock protein 27 (HSP27) was colocalized and physically associated with vimentin in unstressed cells, the roles of HSP27 with regard to vimentin were assessed. HSP27-overexpressing cells prevented morphological alterations of the vimentin filaments, as well as reductions of soluble vimentin, in the cadmium-treated cells. Moreover, HSP27 antisense oligonucleotide augmented these cadmium-induced changes in vimentin. These findings indicate that HSP27 prevents disruption of the vimentin intermediate filament networks and soluble vimentin disappearance, by virtue of its physical interaction with vimentin in cadmium-treated SK-N-SH cells. 相似文献
124.
Seo YJ Jeon MH Lee JH Lee YJ Youn HJ Ko JH Lee JH 《Experimental & molecular medicine》2005,37(6):624-630
Bis (Bag-3, CAIR), a Bcl-2-interacting protein, promotes the anti-apoptotic activity of Bcl-2 and increased levels of Bis have been observed in several disease models. The involvement of Bcl-2 and some Bcl-2-binding proteins in differentiation has recently been reported. However, the relevance of Bis to cellular differentiation remains unknown. The findings herein show that Bis expression is up-regulated during the differentiation of HL-60 cells. To investigate the effect of Bis expression on differentiation, we established Bis-overexpressing HL-60 cells (HL-60-bis). HL-60-bis cells have a low nuclear: cytoplasmic ratio and indented nucleus in Wright- Giemsa staining, and an increased expression of CD11b in immunofluorescence study, indicating the promotion of differentiation. The overexpression of Bis also resulted in a retarded cell growth rate, accompanied by the accumulation of HL-60 cells at the G0/G1 phase of the cell cycle, which was sustained during the differentiation process. Western blot analysis revealed that the expression of p27, a representative inducer of cell cycle arrest at the G1 phase, was increased 2.5-fold in HL-60-bis cells compared to HL-60-neo cells. These results suggest that the Bis induced growth inhibition of HL-60 cells promotes G0/G1 phase arrest via up-regulation of p27, which seems to be a prerequisite for differentiation. Further studies will be required to define the exact roles of Bis on cellular differentiation more precisely. 相似文献
125.
Effects of double substitution on the thermodynamic stabilities of nitrogen radicals 总被引:1,自引:0,他引:1
Studiesonkineticsofradicalreactions[1]andonCHbonddissociationenergies(BDE)[2]haveshownthatcarbonradicalsarestabilizedbyeitheranelectrondonatinggroup(EDG)oranelectronwithdrawinggroup(EWG),andthatifacarbonradicalissubstitutedwithbothanEDGandanEWGatthesamecen… 相似文献
126.
ZrO2在Cu-ZnO-ZrO2甲醇水蒸汽重整制氢催化剂中的作用 总被引:2,自引:0,他引:2
通过对一系列Cu-ZnO-ZrO2甲醇水蒸汽重整(SRM)催化剂的XRD、TEM和BET表征及催化性能测定,研究催化剂中ZrO2对催化剂粒径、比表面以及对SRM反应性能的影响.结果表明,ZrO2的加入,使催化剂的粒径从15 nm降至10 nm(其中CuO和ZnO的平均粒径分别从7.7和10.4 nm降至3.9和8.7 nm),BET比表面从60 m2•g-1增至78 m2•g-1.随着催化剂含ZrO2量不同,甲醇的转化率和H2、CO2的选择性均产生变化,当催化剂中Zr含量为24.0%(w),反应温度为220 ℃,水、醇摩尔比为1.3时,甲醇的转化率达到51.6%, H2和CO2的选择性达到100%(CO和CH4在产物气体中的体积分数小于10-4),这一结果对甲醇燃料电池甲醇重整器的应用具有重要的意义. 相似文献
127.
A method is described for the determination of aldicarb and its metabolites (the sulphoxide and sulphone) in urine by gas chromatography with flame photometric detection (GC-FPD). The sample was concentrated with a column containing activated charcoal and Florisil, and then eluted with dichloromethane-acetone (1:1, v/v). The aldicarb and aldicarb sulphoxide in the eluate solution were oxidized to aldicarb sulphone and the total sulphone concentration was determined by GC-FPD after extraction with dichloromethane and clean-up with an activated charcoal column. The detection limit was 0.0024 mg/l. The mean recoveries from spiked urine in the range 0.04-0.12 mg/l were 90.9%, 86.6%, 92.6% for aldicarb, aldicarb sulphoxide and aldicarb sulphone, respectively. 相似文献
128.
A Novel Dihydroflavone from the Roots of Uvaria Macrophylla 总被引:1,自引:0,他引:1
A new dihydroflavone (1), named macrophyllol A, was isolated from the roots of Uvaria macrophylla. Its structure was elucidated on the basis of spectroscopic evidence. 相似文献
129.
Novel synthesis of a strained para-cyclophane derivative 总被引:1,自引:0,他引:1
Zhi Hao Shi Yun Yang Wei 《中国化学快报》2007,18(4):397-399
A [P. Rajakumar, A.M.A. Rasheed, Tetrahedron 61(22) (2005) 5351] para-cyclophane derivative was synthesized via intramolecular esterification of a dipeptide surrogate containing asparagine to form tetrahydropyrimidinone ring. The structures of the product and intermediates were characterized by 1H NMR, 13C NMR and mass spectrum. 相似文献
130.
R.-L. Yun Y.-M. Chang C.-H. Lin K.-H. Hu C.-M. Shu 《Journal of Thermal Analysis and Calorimetry》2006,85(1):107-113
In industrial processes, information
on the safety property of chemicals is essentially crucial for safe handling
during unit operations. Ensuring the safe use of combustible or flammable
substances in processes is unlikely without detailed investigations of their
flammability characteristics and related hazards. We studied 3-methyl pyridine
(3-picoline), e.g., flammability limits (LFL/UFL), maximum explosion pressure
(P
max), maximum
explosion pressure rise (dP/dt)max, minimum oxygen concentration
(MOC), vapor deflagration index (K
g),
and characterized the influence of inert steam (H2O)
on critical parameters for 3-picoline/water mixtures at 270°C, 1 atm,
various oxygen concentrations, and vapor mixing ratios (100/0, 30/70, 10/90
and 5/95 vol.%) with a 20-L-Apparatus in simulated conditions, respectively.
The results showed that the flammability characteristics
of 3-picoline(aq) all increased with the oxygen concentration.
However, as the composition of inert steam increased, the flammability parameters
and the degree of fire and explosion hazards were significantly reduced, instead.
This study elucidated the flammability properties of 3-picoline mixed with
inert steam. The conclusions could be applied to proactively prevent the relevant
processes from incurring fire and explosion accidents. 相似文献