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1.
2.
One influential parameter which mediates interactions between many types of molecules and biological membranes stems from
the lumped contributions of the transmembrane potential, dipole potential and the difference in the surface potentials on
both sides of a membrane. With relevance to cell physiology, such electrical features of a biomembrane are prone to undergoing
changes as a result of interactions with the aqueous surrounding. Among the most useful tools devoted to exploring changes
of electrical parameters of a lipid membrane induced by certain extracellular ions, lipid composition, and embedded membrane
peptides and proteins, are spectroscopic imaging and the inner field compensation (IFC) method. In this work we layout the
principles of a fully computerized version of the IFC method, which makes it more readily available to users. As a direct
application, we deployed this improved version of the IFC method to time-resolve changes induced by alamethicin monomers upon
membrane dipole potential, following their aggregation within an artificial lipid membrane. Intriguingly, even prior crossing
the membrane core, the membrane-bound alamethicin monomers are shown to significantly increase the dipole potential of the
monolayer they reside in. Such data further emphasize the yet less-explored interplay between membrane-based protein and peptides,
and the membrane dipole potential. 相似文献
3.
Loredana Protesescu Joaquín Calbo Kristopher Williams William Tisdale Aron Walsh Mircea Dinc 《Chemical science》2021,12(17):6129
The development of synthetic routes to access stable, ultra-small (i.e. <5 nm) lead halide perovskite (LHP) quantum dots (QDs) is of fundamental and technological interest. The considerable challenges include the high solubility of the ionic LHPs in polar solvents and aggregation to form larger particles. Here, we demonstrate a simple and effective host–guest strategy for preparing ultra-small lead bromide perovskite QDs through the use of nano-sized MOFs that function as nucleating and host sites. Cr3O(OH)(H2O)2(terephthalate)3 (Cr-MIL-101), made of large mesopore-sized pseudo-spherical cages, allows fast and efficient diffusion of perovskite precursors within its pores, and promotes the formation of stable, ∼3 nm-wide lead bromide perovskite QDs. CsPbBr3, MAPbBr3 (MA+ = methylammonium), and (FA)PbBr3 (FA+ = formamidinium) QDs exhibit significantly blue-shifted emission maxima at 440 nm, 446 nm, and 450 nm, respectively, as expected for strongly confined perovskite QDs. Optical characterization and composite modelling confirm that the APbBr3 (A = Cs, MA, FA) QDs owe their stability within the MIL-101 nanocrystals to both short- and long-range interfacial interactions with the MOF pore walls.We demonstrate a simple and effective host–guest strategy for preparing ultra-small lead bromide perovskite QDs through the use of nano-sized MOFs that function as nucleating and host sites. 相似文献
4.
Benzene is known to be toxic and carcinogenic: therefore, in case of exposure to benzene vapours, a reliable biological monitoring procedure is needed, particularly in the field of occupational hygiene. The determination of the concentration of benzene in the exhaled air 8 h after the exposure has been demonstrated to be a significant biomarker, even for low concentrations of airborne benzene vapours. This work presents a sampling and analysis method that optimizes previously described procedures: in the sampling phase, a double-step sample collection in Tedlar bags is used, in order to remove the breath moisture and to standardise the sample volumes. The analytical phase uses a cryogenic trap for the concentration of the air samples to be injected in the GC-MS, without the need for trapping materials, significantly reducing time and costs of the analysis and improving sensitivity. The presented method has been successfully applied to the biological monitoring of a mixed population (occupationally exposed and not exposed subjects, smokers and non-smokers), with a lower detection limit of 1.5 ng of benzene per litre of exhaled air, that is 1/200 of the biological exposure index recommended by the American Conference of Governmental Hygienists. 相似文献
5.
Correa NM Zorzan DH D'Anteo L Lasta E Chiarini M Cerichelli G 《The Journal of organic chemistry》2004,69(24):8231-8238
Kinetics of the reduction of 3-chloroacetophenone (CAF) with sodium borohydride (NaBH(4)) were followed by UV-vis spectroscopy at 27.0 degrees C in different reverse micellar media, toluene/BHDC/water and toluene/AOT/water, and compared with results in an isooctane/AOT/water reverse micellar system. AOT is sodium 1,4-bis-2-ethylhexylsulfosuccinate, and BHDC is benzyl-n-hexadecyl dimethylammonium chloride. The kinetic profiles were investigated as a function of variables such as surfactant and NaBH(4) concentration and the amount of water dispersed in the reverse micelles, W(0) = [H(2)O]/[surfactant]. In all cases, the first-order rate constant, k(obs), increases with the concentration of surfactant as a consequence of incorporating the substrate into the interface of the reverse micelles where the reaction takes place. The reaction is faster at the cationic interface than at the anionic one probably because the negative ion BH(4)(-) is part of the cationic interface. The effect of the external solvent on the reaction shows that reduction is favored in the isooctane/AOT/water reverse micellar system than that with an aromatic solvent. This is probably due to BH(4)(-) being more in the water pool of the toluene/AOT/water reverse micellar system. The kinetic profile upon water addition depends largely on the type of interface. In the BHDC system, k(obs) increases with W(0) in the whole range studied while in AOT the kinetic profile has a maximum at W(0) approximately 5, probably reflecting the fact that BH(4)(-) is part of the cationic interface while, in the anionic one, there is a strong interaction between water and the polar headgroup of AOT below W(0) = 5 and, above that, BH(4)(-) is repelled from the interface once the water pool has formed. Application of a kinetic model based on the pseudophase formalism, which considers the distribution of the ketone between the continuous medium and the interface and assumes that reaction takes place only at the interface, has enabled us to estimate rate constants at the interface of the reverse micellar systems. At W(0) < 10, it was considered that NaBH(4) is wholly at the interface and, at W(0) >/= 10, where there are free water molecules, also the partitioning between the interface and the water pool was taken into account. The results were used to evaluate CAF and NaBH(4) distribution constants between the different pseudophases as well as the second-order reaction rate constant of the reduction reaction in the micellar interface. 相似文献
6.
Giampaolo Primofiore Anna Maria Marini Federico Da Settimo Silvia Salerno Daniele Bertini Lisa Dalla Via Sebastiano Marciani Magno 《Journal of heterocyclic chemistry》2003,40(5):783-788
The synthesis of new planar derivatives characterized by the presence of a pyridothiopyranopyrazole or pyridothiopyranopyrimidine nucleus, carrying a substituted aryl group, is reported. The novel 1,4‐dihydropyrido[3′,2′:5,6]thiopyrano[4,3‐c]pyrazole derivatives were obtained by condensation of 2,3‐dihydro‐3‐hydroxymethylenethiopyrano[2,3‐b]pyridin‐4(4H)‐ones with appropriate hydrazines. The preparation of 2‐substituted pyrido[3′,2′:5,6]thiopyrano[4,3‐d]pyrimidines was accomplished from the intermediate 2,3‐dihy‐dro‐3‐dimethylaminomethylenethiopyrano[2,3‐b]pyridin‐4(4H)‐ones by reaction with the appropriate binucleophile amidines. The antiproliferative activity of some new products was tested by an in vitro assay on human tumour cell lines (HL‐60 and HeLa), but none of them showed any significant effects in the tests performed. Accordingly, linear flow dichroism measurements indicated their inability to form a molecular complex with DNA. 相似文献
7.
Dalpozzo R De Nino A Maiuolo L Procopio A Tagarelli A Sindona G Bartoli G 《The Journal of organic chemistry》2002,67(25):9093-9095
A new and chemoselective method for the cleavage of alkyl and cyclic acetals and ketals at room temperature in wet nitromethane by using catalytic cerium(III) trifluoromethane sulfonate is presented. The high yields, the observed selectivity, the very gentle reaction conditions, and the almost neutral pH make this procedure particularly attractive for multistep synthesis. 相似文献
8.
The thermal behaviour of (n-CaH2n+1NH2)2ZnCl2 complexes with n = 6, 8, … 16 has been investigated by DSC and by temperature variable IR and X-ray powder diffraction techniques. Complexes with n = 12,14,16 show solid—solid phase transition which are “melting” transitions of the hydrocarbon regions of the structure. The crystal structure of both the low and the high temperature polymorphs is characterized by the piling of sandwiches, each formed by an “inorganic” layer sandwiched between two alkylammonium layers. 相似文献
9.
Soran Loredana Coman Virginia Soran Albert Silvestru Cristian 《Central European Journal of Chemistry》2004,2(4):563-572
2-(Diethylaminomethyl)phenyl bromide and 1,3-bis(dimethylaminomethyl)-benzene, useful ligands for the synthesis of hypervalent
organometallic compounds, were prepared and characterized by NMR (1H, 13C, 2D experiments) spectroscopy. Their synthesis was monitored by the HPLC method. The compounds were eluted on a Nucleosil
120 Si column (5 μm, 25×0.4 cm) with n-hexane at room temperature using a 1.0 ml/min flow-rate. The maximum values of absorbance for the studied compounds, excepting
the diethylamine, were located in a narrow range around 212 nm, the wavelength used for their UV detection. The diethylamine
was detected at 190 nm. The calibration curves are straight lines with correlation factors r>0.995. The HPLC data are in good
agreement with those provided by NMR spectroscopy. 相似文献
10.
Dr. Giuseppe Ferrauto Dr. Daniela Delli Castelli Dr. Loredana Leone Prof. Mauro Botta Prof. Silvio Aime Dr. Zsolt Baranyai Prof. Lorenzo Tei 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(16):4184-4193
The new ligand HPDO3MA [(R,R,R,R)-10-(2-hydroxypropyl)-α,α′,α′′-trimethyl-1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid] was designed to combine and optimize the chemical properties of the macrocyclic ligands HPDO3A and DOTMA. The presence of the methyl groups on the acetic pendant arms of HPDO3A is expected to rigidify the structure of the ligand and favor an increase of the kinetic inertness of the Ln complexes. 1H NMR spectra of Eu(HPDO3MA) displayed the presence of two pairs of diastereoisomers: SAP (square antiprismatic) and TSAP (twisted square antiprismatic) isomers (56 and 44 %, respectively). In addition, 1H and 17O relaxometric NMR studies of Gd(HPDO3MA) showed approximately a 10 % increase in relaxivity and a faster water exchange rate with respect to Gd(HPDO3A). Moreover, a detailed chemical exchange saturation transfer (CEST) characterization of Yb(HPDO3MA) displayed a sensitivity about two times larger than that of Yb(HPDO3A) both in phantom and in cell labeling experiments. Finally, the kinetic inertness of Yb(HPDO3MA) was measured to be twice as high as that of Yb(HPDO3A), with a dissociation half-life at physiological pH of about 2500 years. 相似文献