210 research outputs found
Time-resolved imaging of non-diffusive carrier transport in long-lifetime halide perovskite thin films
Owing to their exceptional semiconducting properties, hybrid
inorganic-organic perovskites show great promise as photovoltaic absorbers. In
these materials, long-range diffusion of charge carriers allows for most of the
photogenerated carriers to contribute to the photovoltaic efficiency. Here,
time-resolved photoluminescence (PL) microscopy is used to directly probe
ambipolar carrier diffusion and recombination kinetics in hybrid perovskites.
This technique is applied to thin films of methylammonium lead tri-iodide
MAPbI obtained with two different fabrication routes, methylammonium lead
tribromide (MAPbBr), and an alloy of formamidinium lead tri-iodide
(FAPbI) and methylammonium lead bromide
FAMAPb(IBr_). Average diffusion
coefficients in the films leading to the highest device efficiencies and
longest lifetimes, i.e., in FAMAPb(IBr)
and acetonitrile-processed MAPbI, are found to be several orders of
magnitude lower than in the other films. Further examination of the
time-dependence shows strong evidence for non-diffusive transport. In
particular, acetonitrile-processed MAPbI shows distinct diffusion regimes
on short and long timescales with an effective diffusion constant varying over
2 orders of magnitude. Our results also highlight the fact that increases in
carrier lifetime in this class of materials are not necessarily concomitant
with increased diffusion lengths and that the PL quantum efficiency under solar
cell operating conditions is a greater indication of material, and ultimately
device, quality
(3E,5E)-1-Benzyl-3,5-bis(2-fluorobenzylidene)piperidin-4-one
The inversion-related molecules of the title compound, C26H21F2NO, associate into closed dimeric subunits via co-operative C—H⋯π interactions. Two non-classical C—H⋯O and one C—H⋯N intramolecular hydrogen bonds are also found in the crystal structure. The piperidin-4-one ring adopts a sofa conforamtion with the 1-benzyl group in the equatorial position, and the equiplanar fluorophenyl substituents in the 3- and 5-positions stretched out on either side. The 1-benzyl group is disposed towards the substituent in the 6th position of the piperidin-4-one ring. The 3,5-diene units possess E configurations
(3E,5E)-3,5-Bis(4-allyloxybenzylidene)-1-benzylpiperidin-4-one
In the title compound C32H31NO3, the allyloxy groups on either side of the piperidin-4-one ring are conformationally disordered. The contribution of major and minor components of the allyloxy group at the 3rd position of the ring are 0.576 (4) and 0.424 (4), respectively, and those at the 5th position are 0.885 (3) and 0.115 (3), respectively. The six-membered piperidin-4-one ring adopts a sofa conformation with the benzyl group occupying an equatorial position and the olefinic double bonds possessing an E configuration. Flanking phenyl substituents are stretched out on either side of the six-membered ring. π–π interactions with a centroid–centroid distance of 3.885 (1) Å give rise to molecular dimers and short C—H⋯π contacts lead to chains along the c axis
(3E,5E)-1-Benzyl-3,5-dibenzylidenepiperidin-4-one
In the title compound, C26H23NO, C—H⋯O hydrogen bonds generate a ribbon structure along the a axis. These ribbons further assemble into a one-dimensional sheet parallel to the ac plane via C—H⋯π interactions. The piperidin-4-one ring adopts a sofa conformation with the 1-benzyl group in the equatorial position, and the 3- and 5-phenyl substituents stretched out on either side. The benzylidene units adopt E configurations and the 1-benzyl group is disposed towards the 3- substituent of the piperidin-4-one ring
Novel adjuvants from seaweed impede autophagy signaling in therapy-resistant residual pancreatic cancer
The DLV System for Knowledge Representation and Reasoning
This paper presents the DLV system, which is widely considered the
state-of-the-art implementation of disjunctive logic programming, and addresses
several aspects. As for problem solving, we provide a formal definition of its
kernel language, function-free disjunctive logic programs (also known as
disjunctive datalog), extended by weak constraints, which are a powerful tool
to express optimization problems. We then illustrate the usage of DLV as a tool
for knowledge representation and reasoning, describing a new declarative
programming methodology which allows one to encode complex problems (up to
-complete problems) in a declarative fashion. On the foundational
side, we provide a detailed analysis of the computational complexity of the
language of DLV, and by deriving new complexity results we chart a complete
picture of the complexity of this language and important fragments thereof.
Furthermore, we illustrate the general architecture of the DLV system which
has been influenced by these results. As for applications, we overview
application front-ends which have been developed on top of DLV to solve
specific knowledge representation tasks, and we briefly describe the main
international projects investigating the potential of the system for industrial
exploitation. Finally, we report about thorough experimentation and
benchmarking, which has been carried out to assess the efficiency of the
system. The experimental results confirm the solidity of DLV and highlight its
potential for emerging application areas like knowledge management and
information integration.Comment: 56 pages, 9 figures, 6 table
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Distribution of lipids in the grain of wheat (cv Hereward) determined by lipidomic analysis of milling and pearling fractions
Lipidomic analyses of milling and pearling fractions from wheat grain were carried out to determine differences in composition which could relate to the spatial distribution of lipids in the grain. Free fatty acids and triacylglycerols were major components in all fractions, but the relative contents of polar lipids varied, particularly lysophosphatidyl choline and digalactosyldiglyceride, which were enriched in flour fractions. By contrast, minor phospholipids were enriched in bran and offal fractions. The most abundant fatty acids in the analysed acyl lipids were C16:0 and C18:2 and their combinations, including C36:4 and C34:2. Phospholipids and galactolipids have been reported to have beneficial properties for bread making, while free fatty acids and triacylglycerols are considered detrimental. The subtle differences in the compositions of fractions determined in the present study could therefore underpin the production of flour fractions with optimised compositions for different end uses
Spoligotype Diversity of Mycobacterium tuberculosis over Two Decades from Tiruvallur, South India
Chitosan-Graft-Branched Polyethylenimine Copolymers: Influence of Degree of Grafting on Transfection Behavior
BACKGROUND: Successful non-viral gene delivery currently requires compromises to achieve useful transfection levels while minimizing toxicity. Despite high molecular weight (MW) branched polyethylenimine (bPEI) is considered the gold standard polymeric transfectant, it suffers from high cytotoxicity. Inversely, its low MW counterpart is less toxic and effective in transfection. Moreover, chitosan is a highly biocompatible and biodegradable polymer but characterized by very low transfection efficiency. In this scenario, a straightforward approach widely exploited to develop effective transfectants relies on the synthesis of chitosan-graft-low MW bPEIs (Chi-g-bPEI(x)) but, despite the vast amount of work that has been done in developing promising polymeric assemblies, the possible influence of the degree of grafting on the overall behavior of copolymers for gene delivery has been largely overlooked. METHODOLOGY/PRINCIPAL FINDINGS: With the aim of providing a comprehensive evaluation of the pivotal role of the degree of grafting in modulating the overall transfection effectiveness of copolymeric vectors, we have synthesized seven Chi-g-bPEI(x) derivatives with a variable amount of bPEI grafts (minimum: 0.6%; maximum: 8.8%). Along the Chi-g-bPEI(x) series, the higher the degree of grafting, the greater the ζ-potential and the cytotoxicity of the resulting polyplexes. Most important, in all cell lines tested the intermediate degree of grafting of 2.7% conferred low cytotoxicity and higher transfection efficiency compared to other Chi-g-bPEI(x) copolymers. We emphasize that, in transfection experiments carried out in primary articular chondrocytes, Chi-g-bPEI(2.7%) was as effective as and less cytotoxic than the gold standard 25 kDa bPEI. CONCLUSIONS/SIGNIFICANCE: This work underlines for the first time the pivotal role of the degree of grafting in modulating the overall transfection effectiveness of Chi-g-bPEI(x) copolymers. Crucially, we have demonstrated that, along the copolymer series, the fine tuning of the degree of grafting directly affected the overall charge of polyplexes and, altogether, had a direct effect on cytotoxicity
Structural basis for native agonist and synthetic inhibitor recognition by the Pseudomonas aeruginosa quorum sensing regulator PqsR (MvfR)
Bacterial populations co-ordinate gene expression collectively through quorum sensing (QS), a cell-to-cell communication mechanism employing diffusible signal molecules. The LysR-type transcriptional regulator (LTTR) protein PqsR (MvfR) is a key component of alkyl-quinolone (AQ)-dependent QS in Pseudomonas aeruginosa. PqsR is activated by 2-alkyl-4-quinolones including the Pseudomonas quinolone signal (PQS; 2-heptyl-3-hydroxy-4(1H)-quinolone), its precursor 2-heptyl-4- hydroxyquinoline (HHQ) and their C9 congeners, 2-nonyl-3-hydroxy-4(1H)-quinolone (C9-PQS) and 2-nonyl-4-hydroxyquinoline (NHQ). These drive the autoinduction of AQ biosynthesis and the up-regulation of key virulence determinants as a function of bacterial population density. Consequently, PqsR constitutes a potential target for novel antibacterial agents which attenuate infection through the blockade of virulence. Here we present the crystal structures of the PqsR co-inducer binding domain (CBD) and a complex with the native agonist NHQ. We show that the structure of the PqsR CBD has an unusually large ligand-binding pocket in which a native AQ agonist is stabilized entirely by hydrophobic interactions. Through a ligand-based design strategy we synthesized and evaluated a series of 50 AQ and novel quinazolinone (QZN) analogues and measured the impact on AQ biosynthesis, virulence gene expression and biofilm development. The simple exchange of two isosteres (OH for NH2) switches a QZN agonist to an antagonist with a concomitant impact on the induction of bacterial virulence factor production. We also determined the complex crystal structure of a QZN antagonist bound to PqsR revealing a similar orientation in the ligand binding pocket to the native agonist NHQ. This structure represents the first description of an LTTR-antagonist complex. Overall these studies present novel insights into LTTR ligand binding and ligand-based drug design and provide a chemical scaffold for further anti-P. aeruginosa virulence drug development by targeting the AQ receptor PqsR
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