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21.
In the presence of BF3*Et2O, alkynyltungsten complexes underwent [3 + 2] cycloaddition with tethered epoxides to give bicyclic -lactones efficiently. Only one diastereomeric product was formed despite the presence of three stereogenic centers. A mechanism is proposed that involves formation of a tungsten-vinylidenium species via an SN2 attack of the epoxide carbon by an alkynyltungsten group to give a tungsten-enol ether species via counterattack at the central tungsten-vinylidenium carbon by the OBF3- terminus. Most of the tungsten enol ether species were too unstable for isolation and underwent hydrolysis to give only cis-fused -bicyclic lactones. This cyclization works for both cis- and trans-epoxides and tolerates various functional groups. In the case of trans-phenyl epoxide, the reaction led to an addition product via a 6-endo attack of epoxide by the tungsten fragment. This method provides a simple enantiospecific synthesis of complex bicyclic lactones if a chiral epoxide is used in the cyclization. It is also applicable to the one-pot synthesis of bicyclic unsaturated gamma-lactones if a suitable alkynyltungsten functionality is used.  相似文献   
22.
Herein, we present results from MD simulations of the Michaelis complex formed between the dizinc beta-lactamase from B. fragilis and imipenem. We considered two catalytically important configurations, which differ in the presence or absence of a hydroxide bridge connecting the two zinc ions in the active site. The structural and dynamical effects induced by substrate binding, the specific roles of the conserved residues and the zinc-bound water molecules, the near attack conformers of the Michaelis complex, and so forth, are discussed in detail. The relative stability of the two configurations was estimated from QM linear scaling calculations on the enzyme-substrate complex combined with Poisson-Boltzmann electrostatic calculations and normal mode calculations. Importantly, we find that the two configurations have similar energies, indicating that these two structures could readily be interchanged, thereby facilitating catalysis. The configuration with the hydroxide bound to the two zinc ions is predicted to be the resting form of the enzyme, while the configuration without the bridge is the reactive form that was found to place the hydroxide in position to attack the carbonyl of the beta-lactam ring. Thus, we propose that the enzyme initiates catalysis by converting from the hydroxide bridge form into the configuration that lacks the hydroxide bridge. This interconversion increases the nucleophilicity of the hydroxide ion and exposes it to the beta-lactam carbonyl, which ultimately facilitates nucleophilic attack. The implications of the observed modes of binding, the possible influence of mutating the Lys184 and Asn193 residues on substrate binding, and the reaction mechanism are also discussed in detail.  相似文献   
23.
A series of trialkylsilyl esters were deprotected or transesterificated into their corresponding carboxylic acids or methyl esters under a catalytic amount of CBr4 in alcohol reaction system. This method enables to desilylate secondary sp3-carbon, sp2-carbon, sp-carbon and aryl tethered trialkylsilyl esters to carboxylic acids, whereas primary sp3-carbon tethered trialkylsilyl esters were further converted into their methyl esters under CBr4/MeOH reaction conditions. The highly chemoselective deprotections can be modulated and achieved by the introduced protecting trialkylsilyl groups and the used alcohols such as MeOH and EtOH under this photochemically-induced reaction conditions.  相似文献   
24.
Morphological effects in luminescence properties of a representative semiconducting polymer, poly(2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV), has recently attracted much attention. Previous studies indicated that short-term heat treatment of solution-cast MEH-PPV films may result in the formation of mesomorphic order that is responsible for the "red" emission around 640 nm, in contrast to the single-chromophore "yellow" emission near 590 nm from the disordered matrix. On the basis of microscopic and spectroscopic evidence for films cast from freshly prepared and aged solutions, here we show that prolonged storage of MEHyellowPPV solutions at room temperature or lower may result in retardation of the thermally induced mesophase formation in the subsequently cast films. According to small-angle neutron scattering and differential scanning calorimetric observations over aged MEH-PPV/toluene solutions, we propose that the suppressed transformation into mesomorphic order is due to further development of nanocrystalline aggregates that serve as physical cross-links among MEH-PPV chains in the solution state upon long-term storage. These solvent-induced nanocrystalline aggregates, however, do not exhibit new spectroscopic features beyond the suppression of "red" emission at 640 nm from the mesomorphic phase.  相似文献   
25.
We report here porphodilactol derivatives and their corresponding metal complexes. These systems show promise as “all-in-one” phototheranostics and are predicated on a design strategy that involves controlling the relationship between intersystem crossing (ISC) and photothermal conversion efficiency following photoexcitation. The requisite balance was achieved by tuning the aromaticity of these porphyrinoid derivatives and forming complexes with one of two lanthanide cations, namely Gd3+ and Lu3+. The net result led to a metalloporphodilactol system, Gd-trans-2, with seemingly optimal ISC efficiency, photothermal conversion efficiency and fluorescence properties, as well as good chemical stability. Encapsulation of Gd-trans-2 within mesoporous silica nanoparticles (MSN) allowed its evaluation for tumour diagnosis and therapy. It was found to be effective as an “all-in-one” phototheranostic that allowed for NIR fluorescence/photoacoustic dual-modal imaging while providing an excellent combined PTT/PDT therapeutic efficacy in vitro and in vivo in 4T1-tumour-bearing mice.

We report here porphodilactol derivatives and their corresponding metal complexes as “all-in-one” phototheranostics by controlling the relationship between intersystem crossing (ISC) and photothermal conversion efficiency following photoexcitation.  相似文献   
26.
27.
The combination of attenuated total reflectance-fourier transform mid-infrared spectrometry (ATR-FTMIR) and multivariate pattern recognition is presented as a fast and convenient methodology to ascertain the source product an oil slick comes from and to evaluate the extent of its weathering. Different types of hydrocarbons (including crude oils, several heavy distillates and the Prestige's heavy fuel oil) were spilled on metallic containers designed ad hoc and their fate monitored by ATR-FTMIR. Not only environmental conditions were considered for weathering but artificial IR- and UV-irradiation. Pattern-recognition studies revealed that the different hydrocarbons clustered at different locations on the score plots and that the samples corresponding to each oil became ordered according to the extent of their weathering. Among them, fuel oil samples coming from the recent disaster of the Prestige tanker off the Galician shoreline showed a distinctive behaviour. Comparison of natural-, IR- and UV-weathering of a crude oil showed that IR solar radiation can be important in oil-weathering, in addition to broadly-reported UV degradation.  相似文献   
28.
The electrospray ionisation (ESI) in negative mode of the pharmacologically significant 3,5-disubstituted tetrahydro-2H-1,3,5-thiadiazin-2-thiones, and their subsequent fragmentations using an ion-trap mass spectrometer, have been investigated. Experiments on sequential product ion fragmentations (MS(n)) were performed in order to elucidate the degradation pathways for these compounds. The data presented show that the fragmentation of the even-electron [M - H](-) ions could proceed through an internal nucleophilic substitution displacement. Decarboxylation and extrusion of carbon disulfide are other fragmentations observed.  相似文献   
29.
Summary Plots of capacity factor and retention time vs. elution solvent composition were proved to be useful to interpret the retention behavior of Kepone and its metabolites in a reversed-phase solid-phase extraction and to optimize the elution solvent. The percent recovery of Kepone was largely improved when the solvent was optimized. The standard deviations of the results of extractions were also improved upon the optimization of the solvent.  相似文献   
30.
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