Tuning Electronic and Structural Properties of Lead-Free Metal Halide Perovskites: A Comparative Study of 2D Ruddlesden-Popper and 3D Compositions.

In recent decades, two-dimensional (2D) perovskites have emerged as promising semiconductors for next-generation photovoltaics, showing notable advancements in solar energy conversion. Herein, we explore the impact of alternative inorganic lattice BX-based compositions (B=Ge or Sn, X=Br or I) on the energy gap and stability. Our investigation encompasses BA2Man-1BnX3n+1 2D Ruddlesden-Popper perovskites (for n=1-5 layers) and 3D bulk (MA)BX3 systems, employing first-principles calculations with spin-orbit coupling (SOC), DFT-1/2 quasiparticle, and D3 dispersion corrections. The study unveils how atoms with smaller ionic radii induce anisotropic internal and external distortions within the inorganic and organic lattices. Introducing the spacers in the low-layer regime reduces local distortions but widens band gaps. Our calculation protocol provides deeper insights into the physics and chemistry underlying 2D perovskite materials, paving the way for optimizing environmentally friendly alternatives that can efficiently replace with sustainable materials.

How cation nature controls the bandgap and bulk Rashba splitting of halide perovskites.

Because of instability issues presented by metal halide perovskites based on methylammonium (MA), its replacement to Cs has emerged as an alternative to improve the materials' durability. However, the impact of this replacement on electronic properties, especially gap energy and bulk Rashba splitting remains unclear since electrostatic interactions from organic cations can play a crucial role. Through first-principles calculations, we investigated how organic/inorganic cations impact the electronic properties of MAPbI 3 and CsPbI 3 perovskites. Although at high temperatures the organic cation can assume spherical-like configurations due to its rotation into the cages, our results provide a complete electronic mechanism to show, from a chemical perspective based on ab initio calculations at 0 K , how the MA dipoles suppression can reduce the MAPbI 3 gap energy by promoting a degeneracy breaking in the electronic states from the PbI 3 framework, while the dipole moment reinforcement is crucial to align theory ↔ experiment, increasing the bulk Rashba splitting through higher Pb off-centering motifs. The lack of permanent dipole moment in Cs results in CsPbI 3 polymorphs with a pronounced Pb on-centering-like feature, which causes suppression in their respective bulk Rashba effect.

Determination of specific and non-specific protein-protein interactions for beta-lactoglobulin by analytical ultracentrifugation and membrane osmometry experiments.

Protein-protein interactions are essential for the understanding of biological processes. Specific protein aggregation is an important aspect for many biological systems. In particular, electrostatic interactions play the key role for protein-protein interactions, as many amino acids have pH-dependent charge states. Moreover, protein dissociation is directly related to the solution pH, ionic strength, temperature and protein concentration. The subtle interplay between different specific and non-specific interactions is demonstrated for beta-lactoglobulin (BLG) with a focus on low salt concentrations, thus mimicking technically relevant processing conditions. BLG is a well-characterized model system, proven to attain its monomer-dimer equilibrium strongly dependent upon the pH of the solution. In this manuscript, we present a unique combination of analytical ultracentrifugation and membrane osmometry experiments, which quantifies specific and non-specific interactions, i.e. in terms of the dimer dissociation constants and the second osmotic virial coefficient, at pH 3 and 7 and sodium chloride concentrations of 10 mM and 100 mM. This provides direct insight to protein-protein interactions for a system with a concentration-dependent monomer-dimer equilibrium. Moreover, using a coarse-grained extended DLVO model in combination with molecular dynamics simulations, we quantify non-specific monomer-monomer, monomer-dimer and dimer-dimer interactions as well as the binding free energy of BLG dimerization from theoretical calculations. The experimentally determined interactions are shown to be mainly governed by electrostatic interactions and further agree with free energy calculations. Our experimental protocol aims to determine non-specific and specific interactions for a dynamically interacting system and provides an understanding of protein-protein interactions for BLG at low salt concentrations.

Revealing the impact of organic spacers and cavity cations on quasi-2D perovskites via computational simulations.

Two-dimensional hybrid lead iodide perovskites based on methylammonium (MA) cation and butylammonium (BA) organic spacer-such as [Formula: see text]-are one of the most explored 2D hybrid perovskites in recent years. Correlating the atomistic profile of these systems with their optoelectronic properties is a challenge for theoretical approaches. Here, we employed first-principles calculations via density functional theory to show how the cation partially canceled dipole moments through the [Formula: see text] terminal impact the structural/electronic properties of the [Formula: see text] sublattices. Even though it is known that at high temperatures, the organic cation assumes a spherical-like configuration due to the rotation of the cations inside the cage, our results discuss the correct relative orientation according to the dipole moments for ab initio simulations at 0 K, correlating well structural and electronic properties with experiments. Based on the combination of relativistic quasiparticle correction and spin-orbit coupling, we found that the MA horizontal-like configuration concerning the inorganic sublattice surface leads to the best relationship between calculated and experimental gap energy throughout n = 1, 2, 3, 4, and 5 number of layers. Conversely, the dipole moments cancellation (as in BA-MA aligned-like configuration) promotes the closing of the gap energies through an electron depletion mechanism. We found that the anisotropy [Formula: see text] isotropy optical absorption conversion (as a bulk convergence) is achieved only for the MA horizontal-like configuration, which suggests that this configuration contribution is the majority in a scenario under temperature effects.

Unveiling oxygen vacancy impact on lizardite thermo and mechanical properties.

Here, we performed a systematic DFT study assisted by the workflow framework SimStack for the mechanical and thermodynamic properties of the clay mineral lizardite in pristine and six different types of O vacancies configurations. In most cases, the defect caused a structural phase transition in the lizardite from the trigonal (pristine) to the triclinic phase. The results show that oxygen vacancies in lizardite significantly reduce the lattice thermal conductivity, accompanied by an elastic moduli reduction and an anisotropy index increase. Through the P-V relation, an increase in compressibility was evidenced for vacancy configurations. Except for the vacancy with the same crystalline structure as pristine lizardite, the sound velocities of the other vacancy configurations produce a decrease in these velocities, and it is essential to highlight high values for the Grüneisen parameter. We emphasize the great relevance of the punctual-defects introduction, such as O vacancies, in lizardite, since this microstructural design is responsible for the decrease of the lattice thermal conductivity in comparison with the pristine system by decreasing the heat transfer ability, turning lizardite into a promising candidate for thermoelectric materials.

SIMONA 1.0: an efficient and versatile framework for stochastic simulations of molecular and nanoscale systems.

Molecular simulation methods have increasingly contributed to our understanding of molecular and nanoscale systems. However, the family of Monte Carlo techniques has taken a backseat to molecular dynamics based methods, which is also reflected in the number of available simulation packages. Here, we report the development of a generic, versatile simulation package for stochastic simulations and demonstrate its application to protein conformational change, protein-protein association, small-molecule protein docking, and simulation of the growth of nanoscale clusters of organic molecules. Simulation of molecular and nanoscale systems (SIMONA) is easy to use for standard simulations via a graphical user interface and highly parallel both via MPI and the use of graphical processors. It is also extendable to many additional simulations types. Being freely available to academic users, we hope it will enable a large community of researchers in the life- and materials-sciences to use and extend SIMONA in the future. SIMONA is available for download under http://int.kit.edu/nanosim/simona.

Receptor flexibility for large-scale in silico ligand screens: chances and challenges.

An important contribution to today's computer-aided drug design is the automated screening of large compound databases against structurally resolved protein receptors targets. The introduction of ligand flexibility has, by now, become a standardized procedure. In contrast, a general approach to treat target degrees of freedom is still to be found, a consequence of the extreme increase of computational complexity, which comes along with the relaxation of protein degrees of freedom. In this chapter, we discuss in some detail both benefits and present limitations of target flexibility for high-throughput in silico database screens. Among the benefits are an improved diversity of binding modes, which allows one to identify a wider class of drug candidates. The limitations are related to a diminishing docking accuracy and an increased number of false hits. Using the thymidine kinase receptor and ten known inhibitors as an example, we describe in detail how target flexibility was implemented and how it affected the screening performance.

Conformational dependence of DNA ballistic conductivity.

With the atomistic Kubo-Verges method we calculate the ballistic conductance of various conformers of DNA (A,B,Z), as well as intermediate and composite conformations, using experimental structures and model complexes. For duplexes with 6 and 15 base pairs, we find that the valence band conductivity near the Fermi edge varies dramatically between the different conformations, most notably for the B-to-Z transition. The latter conductivity differences are largely unchanged both in the presence and in the absence of trimethylthiol linkers between DNA and gold electrodes in vacuo, but become much less drastic when explicit molecular dynamics and water-counterion surrounding of B- and Z-DNA are taken into account. Based on atomistic structural models, we argue that changes in the electrostatic energy in the presence of an applied external electric field can induce conformational switching that may be exploited in novel DNA-based memory devices of high packing density.

Search for the rare decay B-->pil+ l-.

We have performed a search for the flavor-changing neutral-current decays B-->pil+ l-, where l+ l- is either e+ e- or mu+ mu-, using a sample of 230 x 10(6) Upsilon(4S)-->BB decays collected with the BABAR detector. We observe no evidence of a signal and measure the upper limit on the isospin-averaged branching fraction to be B(B-->pil+ l-)<9.1 x 10(-8) at 90% confidence level. We also search for the lepton-flavor-violating decays B-->pie+/- mu-/+ and measure an upper limit on the isospin-averaged branching fraction of B(B-->pie+/- mu-/+)<9.2 x 10(-8) at 90% confidence level.

Heavy metal accumulation in trees growing on contaminated sites in Central Europe.

Metal-accumulating woody species have been considered for phytoextraction of metal-contaminated sites. We investigated Zn and Cd accumulation in tissues of adult trees and associated herbaceous species collected from contaminated areas in Central Europe. We found considerable Cd and Zn accumulation in various willow, poplar and birch species with up to 116mgCdkg(-1) and 4680mgZnkg(-1) in leaves of Salix caprea. Annual variation of Cd and Zn concentrations in leaves of Salix caprea were small, indicating that data obtained in different years can be compared. Metal concentrations in leaves were not related to total (aqua regia) or labile (1M NH(4)NO(3) extract) concentrations in soil but the accumulation factors (leaf concentration: soil concentration) for Cd and Zn followed an inverse log type function. Metal partitioning between tissues showed a minimum in the wood, with increasing concentrations of Cd and Zn towards the leaves and fine roots.

Predicting phosphorus availability from chemically diverse conventional and recycling fertilizers.

Fertilizers produced from heterogeneous, phosphorus-rich biowastes are becoming increasingly relevant. Treatment and processing (combustion, pyrolysis, anaerobic digestion, etc.) increase the diversity of their physico-chemical composition even further. We investigated several approaches to characterize P availability from a set of 13 contrasting fertilizers. We tested them directly using standard fertilizer extractions, as well as a continuous, sink-based P extraction (iron bag) method. We also performed Olsen, CAL and diffusive gradients in thin films (DGT) tests on fertilized soil. Standard extractions correlated only weakly, whereas the iron bag method correlated highly (0.73

The Role of Metal Transport and Tolerance in Nickel Hyperaccumulation by Thlaspi goesingense Halacsy.

Metal hyperaccumulators are plants that are capable of extracting metals from the soil and accumulating them to extraordinary concentrations in aboveground tissues (greater than 0.1% dry biomass Ni or Co or greater than 1% dry biomass Zn or Mn). Approximately 400 hyperaccumulator species have been identified, according to the analysis of field-collected specimens. Metal hyperaccumulators are interesting model organisms to study for the development of a phytoremediation technology, the use of plants to remove pollutant metals from soils. However, little is known about the molecular, biochemical, and physiological processes that result in the hyperaccumulator phenotype. We investigated the role of Ni tolerance and transport in Ni hyperaccumulation by Thlaspi goesingense, using plant biomass production, evapotranspiration, and protoplast viability assays, and by following short- and long-term uptake of Ni into roots and shoots. As long as both species (T. goesingense and Thlaspi arvense) were unaffected by Ni toxicity, the rates of Ni translocation from roots to shoots were the same in both the hyper- and nonaccumulator species. Our data suggest that Ni tolerance is sufficient to explain the Ni hyperaccumulator phenotype observed in hydroponically cultured T. goesingense when compared with the Ni-sensitive nonhyperaccumulator T. arvense.

Neural evidence that suspense narrows attentional focus.

The scope of visual attention changes dynamically over time. Although previous research has reported conditions that suppress peripheral visual processing, no prior work has investigated how attention changes in response to the variable emotional content of audiovisual narratives. We used fMRI to test for the suppression of spatially peripheral stimuli and enhancement of narrative-relevant central stimuli at moments when suspense increased in narrative film excerpts. Participants viewed films presented at fixation, while flashing checkerboards appeared in the periphery. Analyses revealed that increasing narrative suspense caused reduced activity in peripheral visual processing regions in the anterior calcarine sulcus and in default mode network nodes. Concurrently, activity increased in central visual processing regions and in frontal and parietal regions recruited for attention and dynamic visual processing. These results provide evidence, using naturalistic stimuli, of dynamic spatial tuning of attention in early visual processing areas due to narrative context.

All-atom folding of the three-helix HIV accessory protein with an adaptive parallel tempering method.

All-atom protein structure prediction from the amino acid sequence alone remains an important goal of biophysical chemistry. Recent progress in force field development and validation suggests that the PFF01 free-energy force field correctly predicts the native conformation of various helical proteins as the global optimum of its free-energy surface. Reproducible protein structure prediction requires the availability of efficient optimization methods to locate the global minima of such complex potentials. Here we investigate an adapted version of the parallel tempering method as an efficient parallel stochastic optimization method for protein structure prediction. Using this approach we report the reproducible all-atom folding of the three-helix 40 amino acid HIV accessory protein from random conformations to within 2.4 A backbone RMS deviation from the experimental structure with modest computational resources.

Visually evoked potentials in Friedreich's ataxia.

Visual evoked potentials to pattern-reversal stimulation have been recorded in 45 patients with Friedreich's ataxia. In six patients, no response could be obtained because of optic atrophy; altogether, pathological results were found in 25 patients (55%). Normal latencies were recorded in 20 patients (45%). No statistically significant connection could be drawn between the result of the VEP testing and visual acuity, age, or onset and duration of sickness, but there was a strikingly familiar accumulation of results. There is a good conformity between our results and the incidence of optic atrophy in later stages of the disease as shown by pathological-anatomical and epidemiological studies. We have demonstrated that optic nerve lesions in Friedreich's ataxia are not as rare as is frequently assumed and that the VEP is a valuable tool for detecting them. On the other hand, unfortunately, the VEP is of no help in the differential diagnosis of Friedreich's ataxia versus multiple sclerosis.

Rhizosphere characteristics of indigenously growing nickel hyperaccumulator and excluder plants on serpentine soil.

The role of rhizosphere processes in metal hyperaccumulation is largely unexplored and a matter of debate, related field data are virtually not available. We conducted a field survey of rhizosphere characteristics beneath the Ni hyperaccumulator Thlaspi goesingense Hálácsy and the metal-excluder species Silene vulgaris L. and Rumex acetosella L. growing natively on the same serpentine site. Relative to bulk soil and to the rhizosphere of the excluder species, we found significantly increased DOC and Ni concentrations in water extracts of T. goesingense rhizosphere, whereas exchangeable Ni was depleted due to excessive uptake of Ni. Chemical speciation analysis using the MINTEQA2 software package revealed that enhanced Ni solubility in Thlaspi rhizosphere is driven by the formation of Ni-organic complexes. Moreover, ligand-induced dissolution of Ni-bearing minerals is likely to contribute to enhanced Ni solubility. Increased Mg and Ca concentrations and pH in Thlaspi rhizosphere are consistent with ligand-induced dissolution of orthosilicates such as forsterite (Mg(2)SiO(4). Our field data reinforce the hypothesis that exudation of organic ligands may contribute to enhanced solubility and replenishment of metals in the rhizosphere of hyperaccumulating species.

HUMTRN and EFFECTS: age and sex specific dosimetric and physiological human population dynamics models for dose assessment.

A human simulation model called HUMTRN and a population risk assessment model called EFFECTS were developed at Los Alamos National Laboratory as a major component of the BIOTRAN environmental risk assessment model. HUMTRN simulates growth using dietary and physiological characteristics and kinetics of radionuclides to predict radiation doses to selected organs of both sexes in different age groups. The model called EFFECTS was interfaced with output from HUMTRN to predict cancer risks in a dynamic human population. EFFECTS is based on the National Research Council Committee on the Biological Effects of Ionizing Radiation (BEIR)-III radiation cancer mortality estimates from the U.S. population mortality and natality estimates for both sexes between the ages of 1 and 70. These models track radiation intake from air, water, and food, calculate uptake in major growing organs, and estimate cancer mortality risks. This report documents the use of an IBM Personal Computer AT to run HUMTRN and EFFECTS. Air, water, and food contaminant concentrations are provided as input to HUMTRN, which then provides input for EFFECTS. The limitations of this approach are also discussed.

Involving general practitioners in public health initiatives--an increasing role.

Two community studies of campaigns conducted in the Illawarra Area of New South Wales demonstrate how GPs can successfully participate in structured public health initiatives. This approach is felt to bring benefits to the patient, the participating GP, and the wider community, and serves as a model for increased involvement in such programmes.

In silico discovery of a compound with nanomolar affinity to antithrombin causing partial activation and increased heparin affinity.

The medical and socioeconomic relevance of thromboembolic disorders promotes an ongoing effort to develop new anticoagulants. Heparin is widely used as activator of antithrombin but incurs side effects. We screened a large database in silico to find alternative molecules and predicted d-myo-inositol 3,4,5,6-tetrakisphosphate (TMI) to strongly interact with antithrombin. Isothermal titration calorimetry confirmed a TMI affinity of 45 nM, higher than the heparin affinity (273 nM). Functional studies, fluorescence analysis, and citrullination experiments revealed that TMI induced a partial activation of antithrombin that facilitated the interaction with heparin and low affinity heparins. TMI improved antithrombin inhibitory function of plasma from homozygous patients with antithrombin deficiency with a heparin binding defect and also in a model with endothelial cells. Our in silico screen identified a new, non-polysaccharide scaffold able to interact with the heparin binding domain of antithrombin. The functional consequences of this interaction were experimentally characterized and suggest potential anticoagulant therapeutic applications.