首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   480篇
  免费   22篇
  国内免费   1篇
化学   301篇
晶体学   4篇
力学   2篇
数学   13篇
物理学   183篇
  2023年   7篇
  2022年   7篇
  2021年   13篇
  2020年   8篇
  2019年   17篇
  2018年   9篇
  2017年   6篇
  2016年   10篇
  2015年   13篇
  2014年   24篇
  2013年   32篇
  2012年   36篇
  2011年   37篇
  2010年   26篇
  2009年   13篇
  2008年   39篇
  2007年   37篇
  2006年   29篇
  2005年   25篇
  2004年   19篇
  2003年   11篇
  2002年   9篇
  2001年   5篇
  2000年   7篇
  1999年   3篇
  1998年   3篇
  1997年   8篇
  1996年   11篇
  1995年   6篇
  1994年   2篇
  1993年   7篇
  1992年   6篇
  1991年   1篇
  1990年   2篇
  1989年   5篇
  1986年   1篇
  1985年   1篇
  1982年   1篇
  1981年   1篇
  1975年   2篇
  1972年   3篇
  1968年   1篇
排序方式: 共有503条查询结果,搜索用时 15 毫秒
81.
Here, we report the extracellular biosynthesis of silver nanoparticles (AgNPs) and determination of their antibacterial and anticancer properties. We also explore the efficacy of bioAgNPs incorporated in cellulose nanocrystals (CNCs) and alginate (Alg) for the formation of an antibacterial hydrogel film. Streptomyces sp. PBD-311B was used for the biosynthesis of AgNPs. The synthesized bioAgNPs were characterized using UV-Vis spectroscopy, TEM, XRD, and FTIR analysis. Then, the bioAgNPs’ antibacterial and anticancer properties were determined using TEMA and cytotoxicity analysis. To form the antibacterial hydrogel film, bioAgNPs were mixed with a CNC and Alg solution and further characterized using FTIR analysis and a disc diffusion test. The average size of the synthesized bioAgNPs is around 69 ± 2 nm with a spherical shape. XRD analysis confirmed the formation of silver nanocrystals. FTIR analysis showed the presence of protein capping at the bioAgNP surface and could be attributed to the extracellular protein binding to bioAgNPs. The MIC value of bioAgNPs against P. aeruginosa USM-AR2 and MRSA was 6.25 mg/mL and 3.13 mg/mL, respectively. In addition, the bioAgNPs displayed cytotoxicity effects against cancer cells (DBTRG-0.5MG and MCF-7) and showed minimal effects against normal cells (SVG-p12 and MCF-10A), conferring selective toxicity. Interestingly, the bioAgNPs still exhibited inhibition activity when incorporated into CNC/Alg, which implies that the hydrogel film has antibacterial properties. It was also found that bioAgNP-CNC/Alg displayed a minimal or slow release of bioAgNPs owing to the intermolecular interaction and the hydrogel’s properties. Overall, bioAgNP-CNC/Alg is a promising antibacterial hydrogel film that showed inhibition against the pathogenic bacteria P. aeruginosa and MRSA and its application can be further evaluated for the inhibition of cancer cells. It showed benefits for surgical resection of a tumor to avoid post-operative wound infection and tumor recurrence at the surgical site.  相似文献   
82.
采用时间依赖的量子波包法研究14N14N16O、14N15N16O、15N14N16O、15N15N16O、14N14N17O和14N14相似文献   
83.
11B (I=3/2) MAS NMR in the binary glass system xV2O5–B2O3 (x=0.053, 0.43) and the ternary glass system xV2O5–B2O3–PbO (0.1x1.5) has been investigated at room temperature. In the xV2O5–B2O3 glasses, one NMR line due to BO3 unit was observed. Meanwhile in the xV2O5–B2O3–PbO, two NMR lines which arise from BO3 and BO4 units were detected, where the appearance of BO4 units is produced by the presence of PbO. From the computer-simulation of the 11B NMR central transition line (m=−1/2↔1/2), the quadrupole parameters (e2qQ/h and η) for BO3 units in xV2O5–B2O3, and those for BO3 and BO4 units in xV2O5–B2O3–PbO were obtained as a function of x. As the V2O5 content increases in xV2O5–B2O3–PbO, the e2qQ/h and η values of the BO3 associated resonance are found to slightly decrease and increase, respectively. Meanwhile, the e2qQ/h and η values of BO4 associated resonance in xV2O5–B2O3–PbO are found to slightly increase and decrease, respectively. By comparing the intensities of the total transitions (m=−3/2↔−1/2,m=−1/2↔1/2, and 1/2↔3/2) for the 11B NMR line of BO3 and BO4 units contained in xV2O5–B2O3–PbO with those of respective standard samples of 0.053V2O5–B2O3 and NaBH4, the quantitative fractions of BO3 and BO4 in xV2O5–B2O3–PbO were obtained as a function of x.  相似文献   
84.
85.
The new dinuclear half-sandwich complexes of titanium with xylene bridge, [Ti(η5-cyclopentadienyl)Cl2L]2[CH2-C6H4-CH2] (L = Cl (3), L = O-2,6-iPr2C6H3 (4), L = N(SiMe3)(2,6-Me2C6H3) (5)), have been synthesized. The complexes 4 and 5 have been prepared by the reaction of the complex 3 with the corresponding lithium salts of aryloxy and anilide. Structure of these complexes has been characterized by 1H and 13C NMR. The change of substituent from chloride, 3, to anilide, 5, at titanium resulted in chemical shift change of cyclopentadienyl protons from 6.92 and 6.79 to 6.13 and 5.95 ppm probably due to the positive electron density delivery from the anilide group. It was found that all three half-titanocenes were effective catalyst for the generation of SPS (syndiotactic polystyrene). Xylene bridged dinuclear catalyst (4) with aryloxy substituent exhibited very high activity (458 kg of SPS/(mol of [Ti])h), at 40 °C, whereas the analogous hexamethylene bridged dinuclear half-titanocene catalyst (7) showed a lower activity (80.7 kg of SPS/(mol of [Ti])h) under the same conditions. While the catalyst 3 was the most active catalyst among three complexes less than 40 °C the catalyst 5 exhibited the highest activity at 70 °C. Xylene linkage was suggested to be too stiff to permit any kind of intramolecular interaction between two active centers. Lack of steric disturbance due to the rigidity of the xylene bridge might give rise to the similar properties of dinuclear metallocene to the corresponding mononuclear metallocene to result in not only the facile coordination of monomer at the active center to lead high activity but also the easier β-H elimination comparing to the dinuclear catalysts with the flexible bridge to result in the formation of lower molecular weight polymer.  相似文献   
86.
A full dimensional time‐dependent quantum wavepacket approach is used to study the photodissociation dynamics of nitrous oxide for the X → 2 bound–bound transition based on new highly accurate potential energy and transition dipole moment surfaces. The computed 2 absorption spectra at room temperature are characterized by sharp vibrational structures that contribute slightly to the diffuse vibrational structures around the maximum peak at 180 nm of the first ultraviolet absorption band (from the contribution of 2 , 1 , and 2 states) of N2O. Transitions from different initial rovibrational states reveal that the sharp structures arise mainly from N2? O bending vibrations, whereas, at higher temperatures, the N2? O and N? NO stretching vibrations are responsible for enhancing the intensity of the structures. At absorption wavelengths 166 nm and 179 nm, vibrational quantum state distributions of N2 product fragments decrease monotonically with increasing vibrational quantum number v = 0, 1, 2. At 166 nm, rotational quantum state distributions of N2 at fixed v = 0 and v = 1 display multimodal profiles with maximum peaks at j = 77 and j = 75, respectively, whereas, the distributions at the 179 nm absorption wavelength display bimodal profiles with maximum peaks at j = 73 and j = 71, respectively. Accordingly, the presence of rotationally hot N2 from previous experimental and theoretical works in the first band strongly implies a significant influence of the 2 state in determining the final dissociation pathway of N2 + O. © 2016 Wiley Periodicals, Inc.  相似文献   
87.
A mononuclear nonheme cobalt(III) complex of a tetradentate ligand containing two deprotonated amide moieties, [Co(bpc)Cl(2)][Et(4)N] (1; H(2)bpc = 4,5-dichloro-1,2-bis(2-pyridine-2-carboxamido)benzene), was prepared and then characterized by elemental analysis, IR, UV/Vis, and EPR spectroscopy, and X-ray crystallography. This nonheme Co(III) complex catalyzes olefin epoxidation upon treatment with meta-chloroperbenzoic acid. It is proposed that complex 1 shows partitioning between the heterolytic and homolytic cleavage of an O-O bond to afford Co(V)=O (3) and Co(IV)=O (4) intermediates, proposed to be responsible for the stereospecific olefin epoxidation and radical-type oxidations, respectively. Moreover, under extreme conditions, in which the concentration of an active substrate is very high, the Co-OOC(O)R (2) species is a possible reactive species for epoxidation. Furthermore, partitioning between heterolysis and homolysis of the O-O bond of the intermediate 2 might be very sensitive to the nature of the solvent, and the O-O bond of the Co-OOC(O)R species might proceed predominantly by heterolytic cleavage, even in the presence of small amounts of protic solvent, to produce a discrete Co(V) ?O intermediate as the dominant reactive species. Evidence for these multiple active oxidants was derived from product analysis, the use of peroxyphenylacetic acid as the peracid, and EPR measurements. The results suggest that a less accessible Co(V)=O moiety can form in a system in which the supporting chelate ligand comprises a mixture of neutral and anionic nitrogen donors.  相似文献   
88.
We developed a method for the simultaneous quantification of aceclofenac and its three major metabolites in rat plasma. After protein precipitation with acetonitrile including flufenamic acid as an internal standard (IS), aceclofenac, diclofenac, 4'-hydroxyaceclofenac, 4'-hydroxydiclofenac, and the IS were chromatographed on a reverse-phase C18 analytical column. The isocratic mobile phase of acetonitrile/0.1% formic acid (aq; 9:1 [v/v]) was eluted at 0.3 mL/min. Quantification was performed on a triple-quadrupole mass spectrometer using electrospray ionization, and the ion transitions were monitored in selective reaction-monitoring mode. The coefficient of variation in the assay precision was less than 8%, and the accuracy was 92-103%. This method was successfully used to measure the concentrations of aceclofenac and its three major metabolites in rat plasma following the oral administration of a single 20 mg/kg oral dose of aceclofenac.  相似文献   
89.
The mixing of Ag ion-doped poly(ethyleneimine) (PEI) and poly(acrylic acid) (PAA) produced Ag ion-doped polyelectrolyte complex particles (PECs) in solution. Positively charged Ag ion-doped PECs (Ag ion PECs) with a spherical shape were deposited alternatively with PAA to form a multilayer assembly. The multilayered film containing Ag ion PECs was reduced to generate a composite nanostructure. Metal nanoparticle (NP)-enriched nanocomposite films were formed by an additional process of the postadsorption of precursors on PECs within the nanocomposite films, which resulted in the enhancement of the catalytic and electrical properties of the composite films. Because the films contain PECs that are responsive to changes in pH and most of the NPs are embedded in the PECs, interesting catalytic properties, which are unexpected in a particle-type catalyst, were observed upon pH changes. As a result of the reversible structural changes of the films and the immobilization of the NPs within the films, the film-type catalysts showed enhanced performance and stability during catalytic reactions under various pH conditions, compared to particle-type catalysts.  相似文献   
90.
We present a theoretical and experimental study of self-rotation of incident elliptically polarized light on a rubidium atomic vapor. We construct density matrix equations, which are then solved numerically, and further averaged over atomic transit times and a Maxwell-Boltzmann velocity distribution. We calculate the rotation angle as a function of detuning for various laser intensities and polarizations. We compare the calculated results with experimental results and find good agreement between them.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号