全文获取类型
收费全文 | 97篇 |
免费 | 6篇 |
专业分类
化学 | 83篇 |
力学 | 1篇 |
数学 | 9篇 |
物理学 | 10篇 |
出版年
2023年 | 1篇 |
2022年 | 2篇 |
2021年 | 5篇 |
2020年 | 4篇 |
2019年 | 5篇 |
2018年 | 1篇 |
2016年 | 5篇 |
2015年 | 4篇 |
2014年 | 6篇 |
2013年 | 6篇 |
2012年 | 7篇 |
2011年 | 6篇 |
2010年 | 2篇 |
2009年 | 4篇 |
2008年 | 7篇 |
2007年 | 1篇 |
2006年 | 2篇 |
2005年 | 4篇 |
2004年 | 1篇 |
2003年 | 3篇 |
2002年 | 1篇 |
2001年 | 2篇 |
2000年 | 1篇 |
1999年 | 1篇 |
1998年 | 1篇 |
1997年 | 1篇 |
1996年 | 2篇 |
1994年 | 1篇 |
1992年 | 3篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 3篇 |
1981年 | 4篇 |
1977年 | 1篇 |
1959年 | 1篇 |
排序方式: 共有103条查询结果,搜索用时 31 毫秒
31.
Katharina Buddrus-Schiemann Martin Rieger Marlene Mühlbauer Maria Vittoria Barbarossa Christina Kuttler Burkhard A. Hense Michael Rothballer Jenny Uhl Juliano R. Fonseca Philippe Schmitt-Kopplin Michael Schmid Anton Hartmann 《Analytical and bioanalytical chemistry》2014,406(25):6373-6383
In this interdisciplinary approach, the dynamics of production and degradation of the quorum sensing signal 3-oxo-decanoylhomoserine lactone were studied for continuous cultures of Pseudomonas putida IsoF. The signal concentrations were quantified over time by use of monoclonal antibodies and ELISA. The results were verified by use of ultra-high-performance liquid chromatography. By use of a mathematical model we derived quantitative values for non-induced and induced signal production rate per cell. It is worthy of note that we found rather constant values for different rates of dilution in the chemostat, and the values seemed close to those reported for batch cultures. Thus, the quorum-sensing system in P. putida IsoF is remarkably stable under different environmental conditions. In all chemostat experiments, the signal concentration decreased strongly after a peak, because emerging lactonase activity led to a lower concentration under steady-state conditions. This lactonase activity probably is quorum sensing-regulated. The potential ecological implication of such unique regulation is discussed. 相似文献
32.
Reina MC Boese R Ge M Ulic SE Beckers H Willner H Della Védova CO 《The journal of physical chemistry. A》2008,112(34):7939-7946
Trichloromethanesulfenyl acetate, CCl 3SOC(O)CH 3, belongs to the family of sulfenic esters. This molecule has been characterized by vibrational spectroscopy. The conformational and geometrical properties of this species have been determined by IR and Raman spectroscopy, X-ray diffraction, and quantum chemical calculations. Geometry optimizations of the most stable forms were performed with ab initio (HF, MP2) and density functional theory (B3LYP) methods. According to our data, this compound results in a gauche-syn conformer with C 1 symmetry (gauche orientation around the S-O bond and syn orientation of the CO double bond with respect to the S-O single bond) for the most stable geometry, and trans-syn conformer with C s symmetry (trans orientation around the S-O bond and syn orientation of the CO double bond with respect to the S-O single bond) for the second stable conformer (1.1 and 0.53 kcal/mol higher in energy than the most stable C 1 form according to the matrix FTIR spectroscopy and MP2/6-31G* level of the theory, respectively). The crystalline solid (monoclinic, P2 1/ n, a = 8.0152(17) A, b = 5.7922(13) A, c = 17.429(4) A, alpha = gamma = 90 degrees , beta = 100.341(3) degrees ) consists exclusively of the main form. The geometrical parameters (X-ray diffraction) are d C-Cl = 1.767(19) A, d C-S = 1.797(2) A, d S-O = 1.663(14) A, d CO = 1.189(2) A, d O-C = 1.389(3) A, d C-C = 1.483(3) A, angles Cl-C-Cl = 110.3(11) degrees , Cl-C-S = 111.8(12) degrees , C-S-O = 97.4(8) degrees , S-O-C = 116.7(11) degrees , O-CO = 122.8(19) degrees , OC-C = 127.1(2) degrees , and the main torsion angles are delta(CSOC) = 105.9(15) degrees and delta(SOC(O)) = 7.6(3) degrees . The geometrical data calculated with B3LYP/6-31G++(3df,3pd), B3LYP/6-311G++(3df,3pd), B3LYP/aug-cc-pVTZ, and MP2/6-31G* are in good agreement with diffraction data. 相似文献
33.
34.
Nucleophilic Aromatic Substitution on Pentafluorophenyl‐Substituted Dipyrranes and Tetrapyrroles as a Route to Multifunctionalized Chromophores for Potential Application in Photodynamic Therapy
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Claudia S. Gutsche Marlene Ortwerth Dr. Susanna Gräfe Keith J. Flanagan Prof. Mathias O. Senge Prof. Hans‐Ulrich Reissig Prof. Nora Kulak Dr. Arno Wiehe 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(39):13953-13964
The application of porphyrinoids in biomedical fields, such as photodynamic therapy (PDT), requires the introduction of functional groups to tune their solubility for the biological environment and to allow a coupling to other active moieties or carrier systems. A valuable motif in this regard is the pentafluorophenyl (PFP) substituent, which can easily undergo a regiospecific nucleophilic replacement (SNAr) of its para‐fluorine atom by a number of nucleophiles. Here, it is shown that, instead of amino‐substitution on the final porphyrinoid or BODIPY (boron dipyrromethene), the precursor 5‐(PFP)‐dipyrrane can be modified with amines (or alcohols). These dipyrranes were transformed into amino‐substituted BODIPYs. Condensation of these dipyrranes with aldehydes gave access to trans‐A2B2‐porphyrins and trans‐A2B‐corroles. By using pentafluorobenzaldehyde, it was possible to introduce another para‐fluorine atom, which enabled the synthesis of multifunctionalized tetrapyrroles. Furthermore, alkoxy‐ and amino‐substituted dipyrranes were applied to the synthesis of A3B3‐hexaphyrins. The polar porphyrins that were prepared by using this method exhibited in vitro PDT activity against several tumor cell lines. 相似文献
35.
In this study the possibility of using liposomes as membrane mimetic systems was evaluated to estimate the antioxidant properties of oxicams and establish a relationship between the interactions of the drugs with the membrane and their consequent antioxidant activity. Different experiments were performed covering the study of the protective effect of oxicams in lipid peroxidation induced by the peroxyl radical (ROO) derived from 2,2′-azobis(2-amidinopropane) dihydrochloride (AAPH) and using two fluorescence probes with distinct lipophilic properties. Lipid peroxidation using the hydrophilic probe fluorescein was evaluated in lipid and aqueous media. Lipid systems labelled with the fluorescent probe diphenylhexatriene propionic acid (DPH-PA) were used to assess the effects of the drugs on membrane peroxidation simultaneously by fluorescence intensity decay and changes in membrane fluidity by steady-state anisotropy measurements. The use of different probes and liposomes as membrane mimetic systems allowed to conclude that membrane lipoperoxidation is related not only to the scavenging characteristics of the antioxidants but also to their ability to interact with the lipid bilayers. 相似文献
36.
Marlene J. CranStephen R. Gray John ScheirsStephen W. Bigger 《Polymer Degradation and Stability》2011,96(8):1497-1502
The depolymerisation of low molecular weight poly(ethylene oxide) (PEO) under mild conditions was studied using a linear temperature ramped non-isothermal technique and the results compared with those obtained from a conventional isothermal technique. The analysis of the non-isothermal kinetic (NIK) data was performed using an original computer program incorporating an algorithm that systematically minimizes the sum of the squares of the residuals between the experimental data and the calculated theoretical kinetic profile in order to extract the kinetic parameters. The results revealed that the depolymerisation of PEO proceeds in accordance with the Ekenstam model and follows the Arrhenius equation over the temperature range of ca. 40-130 °C. The NIK analysis resulted in a two-dimensional convergence to produce a unique solution set for the kinetic parameters of Ea = 89.4 kJ mol−1 and A = 9.6 × 106 h−1. These data are consistent with the results obtained from the isothermal experiments. It is proposed that NIK analysis is a quick and reliable means of obtaining kinetic parameters relevant to lifetime predictions in polymers whose degradation behaviour can be considered to be close to ideal. 相似文献
37.
A method of ultra-performance liquid chromatography combined with electrospray ionization triple quadrupole tandem mass spectrometry (UPLC-ESI-MS/MS) has been established for simultaneous determination of major disialoganglioside 3 (GD3) and monosialoganglioside 3 (GM3) in infant formulas and whey protein concentrates. Gangliosides were extracted by using the technique of Svennerholm and Fredman and then cleaned up with OASIS HLB solid-phase extraction (SPE) cartridges. The various molecular species of gangliosides were separated on an Acquity UPLC BEH C8 column and analyzed under the negative ion mode. GD3 and GM3 were rapidly quantified using internal standard (IS) method. The developed method was further validated by determining the linearity, average recovery, sensitivity (limit of quantification), and precision. The results presented high correlation coefficients (R(2) > 0.993) of the selected 16 gangliosides molecular species and provided the respective linear ranges. The limit of quantification was 0.325-0.734 mg/100 g for eight molecular species of GD3 and 0.008-0.312 mg/100 g for eight molecular species of GM3, respectively. The reasonable average recoveries (81-95%) and precision (relative standard deviation [RSD] ≤15%) were also demonstrated in three different spiked levels. This new method would be very useful in the quantitative determination of gangliosides in infant formulas and whey protein concentrates. 相似文献
38.
Xie X Scrinzi A Wickenhauser M Baltuska A Barth I Kitzler M 《Physical review letters》2008,101(3):033901
We numerically demonstrate so-far undescribed features in ionization and high harmonic generation from bound states with nonvanishing electronic angular momentum. The states' modified response to a strong laser pulse can be exploited for novel measurement and pulse production schemes. It is shown that angularly asymmetric tunneling from the states can be mapped onto variations of high harmonic intensities and that near-circularly polarized isolated attosecond extreme ultraviolet or x-ray pulses can be produced. 相似文献
39.
40.
A construction is described to encode an arbitrary graph uniquely as a block design. This demonstrates that describing whether two block designs (without repeated blocks) are isomorphic is polynomial time equivalent to solving graph isomorphism. This result supplies evidence for the claim that isomorphism testing for block designs is a hard subcase of graph isomorphism. 相似文献