Exciton diffusion in amorphous organic semiconductors: Reducing simulation overheads with machine learning.

Simulations of exciton and charge hopping in amorphous organic materials involve numerous physical parameters. Each of these parameters must be computed from costly ab initio calculations before the simulation can commence, resulting in a significant computational overhead for studying exciton diffusion, especially in large and complex material datasets. While the idea of using machine learning to quickly predict these parameters has been explored previously, typical machine learning models require long training times, which ultimately contribute to simulation overheads.

Aryl-functionalised α,α'-Trehalose 6,6'-Glycolipid Induces Mincle-independent Pyroptotic Cell Death.

α,α'-Trehalose 6,6'-glycolipids have long been known for their immunostimulatory properties. The adjuvanticity of α,α'-trehalose 6,6'-glycolipids is mediated by signalling through the macrophage inducible C-type lectin (Mincle) and the induction of an inflammatory response. Herein, we present an aryl-functionalised trehalose glycolipid, AF-2, that leads to the release of cytokines and chemokines, including IL-6, MIP-2 and TNF-α, in a Mincle-dependent manner.

Anomaly Detection for Sensor Signals Utilizing Deep Learning Autoencoder-Based Neural Networks.

Anomaly detection is a significant task in sensors' signal processing since interpreting an abnormal signal can lead to making a high-risk decision in terms of sensors' applications. Deep learning algorithms are effective tools for anomaly detection due to their capability to address imbalanced datasets. In this study, we took a semi-supervised learning approach, utilizing normal data for training the deep learning neural networks, in order to address the diverse and unknown features of anomalies.

Heterostructured Nanotetrapod Luminophores for Reabsorption Elimination within Luminescent Solar Concentrators.

Luminescent solar concentrators (LSCs) concentrate light via luminescence within a planar-waveguide and have potential use for building-integrated photovoltaics. However, their commercialization and potential applications are currently hindered greatly by photon reabsorption, where emitted waveguided light is parasitically reabsorbed by a luminophore. Nanotetrapod semiconductor materials have been theorized to be excellent luminophores for LSCs owing to their inherently large Stokes shifts.

Fine-tuning of the size of supramolecular nanotoroids suppresses the subsequent catenation of nano-[2]catenane.

A judicious combination of ring-closing supramolecular polymerization and secondary nucleation can hierarchically organize a diphenylnaphthalene barbiturate monomer bearing a 3,4,5-tri(dodecyloxy)benzyloxy unit into self-assembled nano-polycatenanes composed of nanotoroids. In our previous study, nano-polycatenanes of variable length have been formed uncontrollably from the monomer that provides nanotoroids with sufficiently wide inner void space wherein secondary nucleation is driven by non-specific solvophobic interaction. In this study, we found that the elongation of the alkyl chain length of the barbiturate monomer decreases the inner void space of nanotoroids while increasing the frequency of secondary nucleation.

Exploration of utility of combined optical photothermal infrared and Raman imaging for investigating the chemical composition of microcalcifications in breast cancer.

Microcalcifications play an important role in cancer detection. They are evaluated by their radiological and histological characteristics but it is challenging to find a link between their morphology, their composition and the nature of a specific type of breast lesion. Whilst there are some mammographic features that are either typically benign or typically malignant often the appearances are indeterminate.

The Rise and Future of Discrete Organic-Inorganic Hybrid Nanomaterials.

Hybrid nanomaterials (HNs), the combination of organic semiconductor ligands attached to nanocrystal semiconductor quantum dots, have applications that span a range of practical fields, including biology, chemistry, medical imaging, and optoelectronics. Specifically, HNs operate as discrete, tunable systems that can perform prompt fluorescence, energy transfer, singlet fission, upconversion, and/or thermally activated delayed fluorescence. Interest in HNs has naturally grown over the years due to their tunability and broad spectrum of applications.

Dynamic Activation of Ga Sites by Pt Dopant in Low-Temperature Liquid-Metal Catalysts.

Liquid GaPt catalysts with Pt concentrations as low as 1×10  atomic % have recently been identified as highly active for the oxidation of methanol and pyrogallol under mild reaction conditions. However, almost nothing is known about how liquid state catalysts support these significant improvements in activity. Here, ab initio molecular dynamics simulations are employed to examine GaPt catalysts in isolation and interacting with adsorbates.

Stictamycin, an Aromatic Polyketide Antibiotic Isolated from a New Zealand Lichen-Sourced Species.

Here we describe the isolation and characterization of stictamycin, a new aromatic polyketide with activity against . Stictamycin was identified following metabolic profiling and bioactivity guided fractionation of organic extracts from sp. 438-3, an isolate from the New Zealand lichen .

Marine natural products.

Covering: January to December 2021This review covers the literature published in 2021 for marine natural products (MNPs), with 736 citations (724 for the period January to December 2021) referring to compounds isolated from marine microorganisms and phytoplankton, green, brown and red algae, sponges, cnidarians, bryozoans, molluscs, tunicates, echinoderms, mangroves and other intertidal plants and microorganisms. The emphasis is on new compounds (1425 in 416 papers for 2021), together with the relevant biological activities, source organisms and country of origin. Pertinent reviews, biosynthetic studies, first syntheses, and syntheses that led to the revision of structures or stereochemistries, have been included.

Anion and ether group influence in protic guanidinium ionic liquids.

Ionic liquids are attractive liquid materials for many advanced applications. For targeted design, in-depth knowledge about their structure-property-relations is urgently needed. We prepared a set of novel protic ionic liquids (PILs) with a guanidinium cation with either an ether or alkyl side chain and different anions.

6-C-Linked trehalose glycolipids signal through Mincle and exhibit potent adjuvant activity.

Many studies have investigated the Mincle-mediated agonist activity of α,α'-trehalose-6,6́-glycolipids, however, none have considered how the position, or absence, of the ester moiety influences Mincle-mediated agonist activity. We prepared a variety of 6-C-linked α,α'-trehalose glycolipids containing inverted esters, ketone, carboxy or no carbonyl moieties. Modelling studies indicated that these derivatives bind to the CRD of Mincle in a manner similar to that of the prototypical Mincle agonist, trehalose dibehenate (TDB), with NFAT-GFP reporter cell assays confirming that all compounds, apart from derivatives with short alkyl chains, led to robust Mincle signalling.

Synthesis of 4-thio-d-glucopyranose and interconversion to 4-thio-d-glucofuranose.

Sulfur containing glycosides offer an exciting prospect for inclusion within noncanonical glycan sequences, particularly as enabling probes for chemical glycobiology and for carbohydrate-based therapeutic development. In this context, we required access to 4-thio-d-glucopyranose and sought its chemical synthesis. Unable to isolate this material in homogenous form, we observed instead a thermodynamic preference for interconversion of the pyranose to 4-thio-d-glucofuranose.

Reduction chemistry yields stable and soluble divalent lanthanide tris(pyrazolyl)borate complexes.

Reduction of the heteroleptic Ln(III) precursors [Ln(Tp)(OTf)] (Tp = hydrotris(1-pyrazolyl)borate; OTf = triflate) with either an aluminyl(I) anion or KC yielded the adduct-free homoleptic Ln(II) complexes dimeric 1-Eu [{Eu(Tp)(:-Tp)}] and monomeric 1-Yb [Yb(Tp)]. Complexes 1-Ln have good solubility and stability in both non-coordinating and coordinating solvents. Reaction of 1-Ln with 2 PhPO yielded 1-Ln(OPPh3)2.

Interface-Dependent Selectivity in Plasmon-Driven Chemical Reactions.

Plasmonic nanoparticles can drive chemical reactions powered by sunlight. These processes involve the excitation of surface plasmon resonances (SPR) and the subsequent charge transfer to adsorbed molecular orbitals. Nonetheless, controlling the flow of energy and charge from SPR to adsorbed molecules is still difficult to predict or tune.

Biocatalytic Approaches to Building Blocks for Enzymatic and Chemical Glycan Synthesis.

While the field of biocatalysis has bloomed over the past 20-30 years, advances in the understanding and improvement of carbohydrate-active enzymes, in particular, the sugar nucleotides involved in glycan building block biosynthesis, have progressed relatively more slowly. This perspective highlights the need for further insight into substrate promiscuity and the use of biocatalysis fundamentals (rational design, directed evolution, immobilization) to expand substrate scopes toward such carbohydrate building block syntheses and/or to improve enzyme stability, kinetics, or turnover. Further, it explores the growing premise of using biocatalysis to provide simple, cost-effective access to stereochemically defined carbohydrate materials, which can undergo late-stage chemical functionalization or automated glycan synthesis/polymerization.

Isolation of pseudocapacitive surface processes at monolayer MXene flakes reveals delocalized charging mechanism.

Pseudocapacitive charge storage in TiCT MXenes in acid electrolytes is typically described as involving proton intercalation/deintercalation accompanied by redox switching of the Ti centres and protonation/deprotonation of oxygen functional groups. Here we conduct nanoscale electrochemical measurements in a unique experimental configuration, restricting the electrochemical contact area to a small subregion (0.3 µm) of a monolayer TiCT flake.

The trehalose glycolipid C18Brar promotes antibody and T-cell immune responses to Mannheimia haemolytica and Mycoplasma ovipneumoniae whole cell antigens in sheep.

Bronchopneumonia is a common respiratory disease in livestock. Mannheimia haemolytica is considered the main causative pathogen leading to lung damage in sheep, with Mycoplasma ovipneumoniae and ParaInfluenza virus type 3, combined with adverse physical and physiological stress, being predisposing factors. A balance of humoral and cellular immunity is thought to be important for protection against developing respiratory disease.

Highly electron deficient diketopyrrolopyrroles.

The synthesis, spectroelectrochemical and structural characteristics of highly electron-accepting diketopyrrrolopyrrole (DPP) molecules with adjoining pyridinium rings is reported, along with an assessment of their toxicity, which is apparently low. The compounds show reversible electrochemistry and in one subfamily a massive increase in molar extinction coefficient upon electrochemical reduction.

Partially oxidised boron nitride as a 2D nanomaterial for nanofiltration applications.

Boron nitride (BN) based 2D nanomaterials are an emerging class of materials for the development of new membranes for nanofiltration applications. Here, we report the preparation, characterisation and testing of highly promising nanofiltration membranes produced from partially oxidised BN (BNOx) 2D nanosheets. In our work, the partial oxidation of BN was successfully achieved by heating the bulk h-BN powder in air at 1000 °C, resulting in BNOx product.

Triplets with a Twist: Ultrafast Intersystem Crossing in a Series of Electron Acceptor Materials Driven by Conformational Disorder.

Control over the populations of singlet and triplet excitons is key to organic semiconductor technologies. In different contexts, triplets can represent an energy loss pathway that must be managed (i.e.

Structural and electronic changes in Ga-In and Ga-Sn alloys on melting.

The melting behaviour of surface slabs of Ga-In and Ga-Sn is studied using periodic density functional theory and molecular dynamics. Analysis of the structure and electronics of the solid and liquid phases gives insight into the properties of these alloys, and why they may act as promising CO reduction catalysts. We report melting points for slabs of hexa-layer Ga-In (386 K) and Ga-Sn (349 K) that are substantially lower than the pure hexa-layer Ga system (433 K), and attribute the difference to the degree to which the dopant (In or Sn) disrupts the layered Ga network.

Characterization of marine-derived halogenated indoles as ligands of the aryl hydrocarbon receptor.

The aryl hydrocarbon receptor (AhR), a ligand-activated transcription factor thought to mediate a number of physiological roles in the body, is becoming a target of interest for the development of new therapeutics. However, previous research has demonstrated that the downstream effects of AhR ligands cannot be predicted based simply on whether a ligand acts as an agonist or antagonist and the persistence of AhR signaling is thought to be a key determining feature. The current study investigated the AhR activity of four halogenated indoles isolated from the New Zealand red alga, : 4,7-dibromo-2,3-dichloroindole (4DBDCI), 7-bromo-2,3-dichloro-6-iodoindole (BDCII), 6,7-dibromo-2,3-dichloroindole (6DBDCI) and 2,6,7-tribromo-3-chloroindole (TBCI).

Conformational interdomain flexibility in a bacterial α-isopropylmalate synthase is necessary for leucine biosynthesis.

α-Isopropylmalate synthase (IPMS) catalyzes the first step in leucine (Leu) biosynthesis and is allosterically regulated by the pathway end product, Leu. IPMS is a dimeric enzyme with each chain consisting of catalytic, accessory, and regulatory domains, with the accessory and regulatory domains of each chain sitting adjacent to the catalytic domain of the other chain. The IPMS crystal structure shows significant asymmetry because of different relative domain conformations in each chain.