Effect of chloride passivation on recombination dynamics in CdTe colloidal quantum dots

Colloidal quantum dots (CQDs) can be used in conjunction with organic charge‐transporting layers to produce light‐emitting diodes, solar cells and other devices. The efficacy of CQDs in these applications is reduced by the non‐radiative recombination associated with surface traps. Here we investigate the effect on the recombination dynamics in CdTe CQDs of the passivation of these surface traps by chloride ions. Radiative recombination dominates in these passivated CQDs, with the radiative lifetime scaling linearly with CQD volume over τr=20–55 ns. Before chloride passivation or after exposure to air, two non‐radiative components are also observed in the recombination transients, with sample‐dependent lifetimes typically of less than 1 ns and a few ns. The non‐radiative dynamics can be explained by Auger‐mediated trapping of holes and the lifetimes of this process calculated by an atomistic model are in agreement with experimental values if assuming surface oxidation of the CQDs

Field Theoretic Study of Bilayer Membrane Fusion III: Membranes with Leaves of Different Composition

We extend previous work on homogeneous bilayers to calculate the barriers to fusion of planar bilayers which contain two different amphiphiles, a lamellae-former and a hexagonal former, with different compositions of the twoin each leaf. Self-consistent field theory is employed, and both standard and alternative pathways are explored. We first calculate these barriers as the amount of hexagonal former is increased equally in both leaves to levels appropriate to the plasma membrane of human red blood cells. We follow these barriers as the composition of hexagonal-formers is then increased in the cis layer and decreased in the trans layer, again to an extent comparable to the biological system. We find that, while the fusion pathway exhibits two barriers in both the standard and alternative pathways, in both cases the magnitudes of these barriers are comparable to one another, and small, on the order of 13 kT. As a consequence, one expects that once the bilayers are brought sufficiently close to one another to initiate the process, fusion should occur rapidly.Comment: 9 figure

Field Theoretic Study of Bilayer Membrane Fusion: II. Mechanism of a Stalk-Hole Complex

We use self-consistent field theory to determine structural and energetic properties of intermediates and transition states involved in bilayer membrane fusion. In particular, we extend our original calculations from those of the standard hemifusion mechanism, which was studied in detail in the first paper of this series, to consider a possible alternative to it. This mechanism involves non-axial stalk expansion, in contrast to the axially symmetric evolution postulated in the classical mechanism. Elongation of the initial stalk facilitates the nucleation of holes and leads to destabilization of the fusing membranes via the formation of a stalk-hole complex. We study properties of this complex in detail, and show how transient leakage during fusion, previously predicted and recently observed in experiment, should vary with system architecture and tension. We also show that the barrier to fusion in the alternative mechanism is lower than that of the standard mechanism by a few $k_BT$ over most of the relevant region of system parameters, so that this alternative mechanism is a viable alternative to the standard pathway

Investigating Interactions of Biomembranes and Alcohols: A Multiscale Approach

We study the interaction of lipid bilayers with short chain alcohols using molecular dynamics on different length scales. We use detailed atomistic modeling and modeling on the length scale where an alcohol is just an amphiphilic dimer. Our strategy is to calibrate a coarse--grained model against the detailed model at selected state points at low alcohol concentration and then perform a wider range of simulations using the coarse--grained model. We get semiquantitative agreement with experiment for the major observables such as order parameter and area per molecule. We find a linear increase of area per molecule with alcohol concentration. The alcohol molecules in both system descriptions are in close contact with the glycerol backbone. Butanol molecules can enter the bilayer to some extent in contrast to the behavior of shorter alcohols. At very high alcohol concentrations we find clearly increased interdigitation between leaflets.Comment: 14 pages, 6 figure

Photocatalytic hydrogen production by biomimetic indium sulfide using Mimosa pudica leaves as template

Biomimetic sulfur-deficient indium sulfide (In2.77S4) was synthesized by a template-assisted hydrothermal method using leaves of Mimosa pudica as a template for the first time. The effect of this template in modifying the morphology of the semiconductor particles was determined by physicochemical characterization, revealing an increase in surface area, decrease in microsphere size and pore size and an increase in pore volume density in samples synthesized with the template. X-ray photoelectron spectroscopy (XPS) analysis showed the presence of organic sulfur (S O/S C/S H) and sulfur oxide species ( SO2, SO32−, SO42−) at the surface of the indium sulfide in samples synthesized with the template. Biomimetic indium sulfide also showed significant amounts of Fe introduced as a contaminant present on the Mimosa pudica leaves. The presence of these sulfur and iron species favors the photocatalytic activity for hydrogen production by their acting as a sacrificial reagent and promoting water oxidation on the surface of the templated particles, respectively. The photocatalytic hydrogen production rates over optimally-prepared biomimetic indium sulfide and indium sulfide synthesized without the organic template were 73 and 22 μmol g−1, respectively, indicating an improvement by a factor of three in the templated sample

Visualization of membrane loss during the shrinkage of giant vesicles under electropulsation

We study the effect of permeabilizing electric fields applied to two different types of giant unilamellar vesicles, the first formed from EggPC lipids and the second formed from DOPC lipids. Experiments on vesicles of both lipid types show a decrease in vesicle radius which is interpreted as being due to lipid loss during the permeabilization process. We show that the decrease in size can be qualitatively explained as a loss of lipid area which is proportional to the area of the vesicle which is permeabilized. Three possible mechanisms responsible for lipid loss were directly observed: pore formation, vesicle formation and tubule formation.Comment: Final published versio

The cooperative behaviour of antimicrobial peptides in model membranes

A systematic analysis of the hypothesis of the antimicrobial peptides' (AMPs) cooperative action is performed by means of full atomistic molecular dynamics simulations accompanied by circular dichroism experiments. Several AMPs from the aurein family (2.5,2.6, 3.1), have a similar sequence in the first ten amino acids, are investigated in different environments including aqueous solution, trifluoroethanol (TFE), palmitoyloleoylphosphatidylethanolamine (POPE), and palmitoyloleoylphosphatidylglycerol (POPG) lipid bilayers. It is found that the cooperative effect is stronger in aqueous solution and weaker in TFE. Moreover, in the presence of membranes, the cooperative effect plays an important role in the peptide/lipid bilayer interaction. The action of AMPs is a competition of the hydrophobic interactions between the side chains of the peptides and the hydrophobic region of lipid molecules, as well as the intra peptide interaction. The aureins 2.5-COOH and 2.6-COOH form a hydrophobic aggregate to minimize the interaction between the hydrophobic group and the water. Once that the peptides reach the water/lipid interface the hydrophobic aggregate becomes smaller and the peptides start to penetrate into the membrane. In contrast, aurein 3.1-COOH forms only a transient aggregate which disintegrates once the peptides reached the membrane, and it shows no cooperativity in membrane penetratio

Near-unity quantum yields from chloride treated CdTe colloidal quantum dots

Colloidal quantum dots (CQDs) are promising materials for novel light sources and solar energy conversion. However, trap states associated with the CQD surface can produce non‐radiative charge recombination that significantly reduces device performance. Here a facile post‐synthetic treatment of CdTe CQDs is demonstrated that uses chloride ions to achieve near‐complete suppression of surface trapping, resulting in an increase of photoluminescence (PL) quantum yield (QY) from ca. 5% to up to 97.2 ± 2.5%. The effect of the treatment is characterised by absorption and PL spectroscopy, PL decay, scanning transmission electron microscopy, X‐ray diffraction and X‐ray photoelectron spectroscopy. This process also dramatically improves the air‐stability of the CQDs: before treatment the PL is largely quenched after 1 hour of air‐exposure, whilst the treated samples showed a PL QY of nearly 50% after more than 12 hours