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81.
Abstract The phosphonium salts have been prepared by the reaction of triphenylphosphine with the corresponding halomethanes (eq. (1)) and bromine (eq.(2)), respectively. 相似文献
82.
H. Vogt V. Kolleck L. Riesel 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4)
Abstract Carbonyl compounds react with CBr2F2 in the presence of phosphanes, RP (R = Ph, NR;), and metals (M = Zn, Cd, Pb) forming geminal difluoroolefins (eq. 1)1. R′CHO + CBr2F2 + R3P + M → R′CH=CF2 + MBr2 + R3PO (1) Without any doubt this reaction has to occur via the intermediate formation of difluoromethylene phosphoranes, which then undergo the Wittig reaction with carbonyl compounds (eq. 2). R3P=CF2 + R′CHO → R3PO + R′CH=CF2 (2). 相似文献
83.
Paolo Dapporto Paola Paoli Carla Bazzicalupi Andrea Bencini Nicoletta Nardi Barbara Valtancoli 《Supramolecular chemistry》2013,25(3):195-200
Abstract In preceding works, which have dealt with the synthesis and characterisation of a series of macrobicyclic compounds with five donor atoms, the unusually high basicity constants of these polyaminic cage-like molecules have been ascribed to the inclusion of the proton inside the macrobicyclic cavity which results in a very efficient hydrogen-bond network. The present paper, based on previously reported X-ray crystal structures regarding five-atoms bridging units and on molecular modelling studies shows that the disposition of the five donor atoms in the monoprotonated species is related to the protonation site. Precisely, if the protonation occurs on a bridge-head nitrogen the resulting geometry of the donors is a trigonal bipyramid, whereas it is square pyramidal when the proton is bound to a nitrogen belonging to a macrobicyclic chain. For what concerns the geometrical array of the donor atoms in the free amines, the favoured array seems to be the trigonal bipyramidal. 相似文献
84.
Dr. Annalisa Mancini Dr. M. Carla Aragoni Dr. Neil Bricklebank Dr. Carlo Castellano Prof. Francesco Demartin Prof. Francesco Isaia Prof. Vito Lippolis Dr. Anna Pintus Dr. Massimiliano Arca 《化学:亚洲杂志》2013,8(3):639-647
The reactions of 4,5,6,7‐tetrathiocino‐[1,2‐b:3,4‐b′]‐1,3,8,10‐tetrasubstituted‐diimidazolyl‐2,9‐dithiones (R2,R′2‐todit; 1 : R=R′=Et; 2 : R=R′=Ph; 3 : R=Et, R′=Ph) with Br2 exclusively afforded 1:1 and 1:2 “T‐shaped” adducts, as established by FT‐Raman spectroscopy and single‐crystal X‐ray diffraction in the case of complex 1? 2 Br2. On the other hand, the reactions of compounds 1 – 3 with molecular I2 provided charge‐transfer (CT) “spoke” adducts, among which the solvated species 3? 2 I2 ? (1?x)I2 ? x CH2Cl2 (x=0.94) and ( 3 )2 ? 7 I2 ? x CH2Cl2, (x=0.66) were structurally characterized. The nature of all of the reaction products was elucidated based on elemental analysis and FT‐Raman spectroscopy and supported by theoretical calculations at the DFT level. 相似文献
85.
(2Z,1S)-1,3-diphenyl-2-propenol (3) is obtained from the chiral 5,6-dihydro-1,4-dithiin 1b in two steps and 60% enantiomeric excess. Combining our previously reported stereoselective double bond formation and this 1,4 asymmetric induction introduces a new route to chiral allylic alcohols with cis geometry from simple aldehydes and methyl ketones. 相似文献
86.
Dr. Alessandro Barge Marina Caporaso Prof. Giancarlo Cravotto Dr. Katia Martina Dr. Paolo Tosco Prof. Silvio Aime Dr. Carla Carrera Dr. Eliana Gianolio Dr. Giorgio Pariani Dr. Davide Corpillo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(36):12086-12092
We report the synthesis and characterization of a water‐soluble, star‐shaped macromolecular platform consisting of eight β‐cyclodextrin (β‐CD) units anchored to the narrower rim of a γ‐CD core through bis(triazolyl)alkyl spacers. The efficient synthetic protocol is based on the microwave (MW)‐promoted Cu‐catalyzed 1,3‐dipolar cycloaddition of CD monoazides to CD monoacetylenes. The ligand‐hosting capability of the construct has been assessed by relaxometric titration and nuclear magnetic relaxation dispersion (NMRD) profiling, which showed it to be good, and this was supported by molecular dynamics simulations. To demonstrate the feasibility of obtaining supramolecular structures with high hosting ability, we designed a dimeric platform, formed by joining two nonamers through the γ‐CD cores through a bis(lithocholic acid) linker. With a view to the potential biological applications, cytotoxicity and extent of binding to human serum albumin were assessed. The properties of this dendrimeric multicarrier make it suitable for pharmaceutical and diagnostic purposes, ranging from targeted drug delivery to molecular imaging. 相似文献
87.
Carla Sirtori Ana Agüera Irene Carra José A. Sanchéz Pérez 《Analytical and bioanalytical chemistry》2014,406(11):2549-2558
This work allowed the identification of major transformation products (TPs) of acetamiprid (ACTM) during Fenton process. Acetamiprid is a chloronicotinoid insecticide widely used around the world for its characteristics (high insecticidal activity, good systemic properties, suitable field stability, etc.). The degradation of the parent molecule and the identification of the main TPs were evaluated in different water matrices (demineralized water and real agro-food industrial wastewater). TPs of acetamiprid generated by Fenton experiments were monitored and identified by liquid chromatography quadrupole time-of-flight tandem mass spectrometry (LC–QTOF–MS/MS). Up to 14 TPs were characterized based on the accurate mass of the molecular ion and fragment ions obtained in both full-scan and MS/MS modes. Most of them were eliminated after 75 min of treatment time in demineralized water. However, in real agro-food industrial wastewater, most of them were eliminated at 90 min of treatment time, demonstrating the influence of the matrix composition on the studied compound degradation. 相似文献
88.
Poly(lactic acid) (PLA) is a biodegradable polymer that has a variety of applications, one of which is as biomaterial in surgery or as functional layers on implants, due to its compatibility with living tissue. This paper reports the possibilities of quantification of poly(lactic acid) (PLA) in a polymer matrix such as poly(methyl methacrylate) (PMMA) by micro Raman spectroscopy (MRS). Blends of amorphous poly(DL‐lactic acid) with poly(methyl methacrylate) were prepared by the procedure of dissolution/precipitation. Thermal properties of the blends such as the glass transition temperature (Tg) were characterized by differential scanning calorimetry (DSC). The PLA/PMMA blends exhibited only a single glass transition region, indicating that this system is miscible. The PLA/PMMA system obeys the Gordon–Taylor equation (Tg versus PLA content). Various concentration ratios of PLA blends were prepared to use as a basis for quantitative analysis by MRS. Intensities of the characteristic bands at 813 cm−1 (νCOC of PMMA) and 873 cm−1 (νC―COO of PLA) were used for the calculation. The calibration graph showed a good linear correlation with an R2 value of 0.9985. On the basis of the calibration curve obtained, the determined content of several PLA/PMMA blends was in good agreement when compared with nominal contents. The limit of detection (LOD) and quantification (LOQ) were calculated by the calibration data set as signal‐to‐noise method. The relative standard deviation of this method was lower than 10% and the accuracy better than 4%. This study demonstrated that Raman spectroscopy provides an alternative non destructive method for quantitative analysis of PLA in a PMMA matrix. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
89.
Paola Taddei Carla Boga Gabriele Micheletti Barbara Ballarin 《Journal of Raman spectroscopy : JRS》2015,46(1):100-108
Raman and IR spectroscopy were used to investigate the changes induced in yak hair keratin by the straightening treatment based on glyoxylic acid. The amino acidic residues that appeared involved in the reaction with glyoxylic acid were serine and lysine; the involvement of the latter was deduced by the spectroscopic detection of iminic species, resulting from the reaction between the aminic group of lysine and the carbonyl group of glyoxylic acid. The reaction with glyoxylic acid induced conformational rearrangements that mainly involved the fibre bulk rather than the cuticle. Changes in the average tyrosine environment and its hydrogen‐bonding state were detected: at increasing glyoxylic acid incorporation, the tyrosine residues appeared more exposed, probably because of H‐bond interactions with the COOH group. The distribution of the disulfide bridge conformation was also affected, although no cleavage of the S–S bond was detected, in agreement with the shiny and healthy appearance of the fibres. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
90.
Gennara Cavallaro Carla Sardo Emanuela Fabiola Craparo Gaetano Giammona 《Molecules (Basel, Switzerland)》2021,26(6)
Here, a novel strategy of formulating efficient polymeric carriers based on the already described INU-IMI-DETA for gene material whose structural, functional, and biological properties can be modulated and improved was successfully investigated. In particular, two novel derivatives of INU-IMI-DETA graft copolymer were synthesized by chemical functionalisation with epidermal growth factor (EGF) or polyethylenglycol (PEG), named INU-IMI-DETA-EGF and INU-IMI-DETA-PEG, respectively, in order to improve the performance of already described “inulin complex nanoaggregates” (ICONs). The latter were thus prepared by appropriately mixing the two copolymers, by varying each component from 0 to 100 wt% on the total mixture, named EP-ICONs. It was seen that the ability of the INU-IMI-DETA-EGF/INU-IMI-DETA-PEG polymeric mixture to complex siGL3 increases with the increase in the EGF-based component in the EP-ICONs and, for each sample, with the increase in the copolymer:siRNA weight ratio (R). On the other hand, the susceptibility of loaded siRNA towards RNase decreases with the increase in the pegylated component in the polymeric mixture. At all R values, the average size and the zeta potential values are suitable for escaping from the RES system and suitable for prolonged intravenous circulation. By means of biological characterisation, it was shown that MCF-7 cells are able to internalize mainly the siRNA-loaded into EGF-decorated complexes, with a significant difference from ICONs, confirming its targeting function. The targeting effect of EGF on EP-ICONs was further demonstrated by a competitive cell uptake study, i.e., after cell pre-treatment with EGF. Finally, it was shown that the complexes containing both EGF and PEG are capable of promoting the internalisation and therefore the transfection of siSUR, a siRNA acting against surviving mRNA, and to increase the sensitivity to an anticancer agent, such as doxorubicin. 相似文献