Single crystals of mixed Br/Cl and Sn-doped formamidinium lead halide perovskites inverse temperature crystallization.

Hybrid organic-inorganic perovskite mixed halides of FAPbBr Cl and doped FAPb Sn Br were synthesized using a generalized inverse temperature crystallization (ITC) method. With an appropriate choice of solvents and crystallization temperatures we show that large millimeter sized single crystals of these hybrid perovskites can be grown in a matter of hours to days using ITC. The structural and optical properties of these single crystals were characterized systematically.

Kinase-Inhibitory Nucleoside Derivatives from the Pacific Bryozoan .

Marine organisms are a valuable source of bioactive natural products, yet bryozoan invertebrates have been relatively understudied. Herein, we report nelliellosides A and B, new secondary metabolites of the Pacific bryozoan , found using NMR-guided isolation. Their structures, including absolute configurations, were elucidated using spectroscopic and chromatographic techniques.

Ground and Excited States of Bis-4-Methoxybenzyl-Substituted Diketopyrrolopyrroles: Spectroscopic and Electrochemical Studies.

A series of symmetrically bis-4-methoxybenzyl (4MB) N-substituted 1,4-diketopyrrolo[3,4-c]pyrrole (DPP) derivatives have been synthesized. The 4MB unit makes the DPP core soluble, and shows subtle modification of up to 0.2 eV in ground and excited states of the core when compared with related alkyl derivatives.

A Projective Method for the Calculation of Excited-State Electronic Coupling: Isolating Charge Transfer/Recombination Processes in Organic Photovoltaics.

Electronic coupling between excited states is a vital parameter required to describe ultrafast energy and charge transfer processes that occur in photoresponsive organic materials. In such systems, short-range Coulombic, exchange, overlap, and configuration interaction effects must all be accounted for. Although a number of methods are available, the evaluation of coupling between arbitrary excited states remains challenging.

ortho-Substituted lipidated Brartemicin derivative shows promising Mincle-mediated adjuvant activity.

The macrophage inducible C-type lectin (Mincle) is a pathogen recognition receptor (PRR) that is a promising target for the development of Th1-polarising vaccine adjuvants. We recently reported on the synthesis and evaluation of lipidated Brartemicin analogues that showed Mincle agonist activity, with our lead agonist exhibiting potent Th1 adjuvant activity that was greater than that of trehalose dibehenate (TDB). Herein, we report on the efficient synthesis and subsequent biological evaluation of additional lipidated Brartemicin analogues that were designed to determine the structural requirements for optimal Mincle signalling.

The "Metallo"-Diels-Alder Reactions: Examining the Metalloid Behavior of Germanimines.

Addition of MesN (Mes=2,4,6-Me C H ) to germylene [(NON )Ge] (NON =O(SiMe NtBu) ) (1) gives germanimine, [(NON )Ge=NMes] (2). Compound 2 behaves as a metalloid, showing reactivity reminiscent of both transition metal-imido complexes, undergoing [2+2] addition with heterocumulenes and protic sources, as well as an activated diene, undergoing a [4+2] cycloaddition, or "metallo"-Diels-Alder, reaction. In the latter case, the diene includes the Ge=N bond and π-system of the Mes substituent, which is reactive towards dienophiles including benzaldehyde, benzophenone, styrene, and phenylacetylene.

A Stable Calcium Alumanyl.

A seven-membered N,N'-heterocyclic potassium alumanyl nucleophile is introduced and utilised in the metathetical synthesis of Mg-Al and Ca-Al bonded derivatives. Both species have been characterised by experimental and theoretical means, allowing a rationalisation of the greater reactivity of the heavier group 2 species implied by an initial assay of their reactivity.

Ultra stable superatomic structure of doubly magic Ga and GaLi electrolyte.

We report the extreme thermal stability of the superatomic electronic structure for 13-atom gallium clusters and the GaLi electrolyte. Using previously-validated first-principles simulations, [K. G.

A methodology for characterising nanoparticle size and shape using nanopores.

The discovery and characterisation of nanomaterials represents a multidisciplinary problem. Their properties and applications within biological, physical and medicinal sciences depend on their size, shape, concentration and surface charge. No single technology can currently measure all characteristics.

Calcification Microstructure Reflects Breast Tissue Microenvironment.

Microcalcifications are important diagnostic indicators of disease in breast tissue. Tissue microenvironments differ in many aspects between normal and cancerous cells, notably extracellular pH and glycolytic respiration. Hydroxyapatite microcalcification microstructure is also found to differ between tissue pathologies, including differential ion substitutions and the presence of additional crystallographic phases.

Stereochemistry, lipid length and branching influences Mincle agonist activity of monoacylglycerides.

Herein, we report on the synthesis of a series of enantiomerically pure linear, iso-branched, and α-branched monoacyl glycerides (MAGs) in 63-72% overall yield. The ability of the MAGs to signal through human macrophage inducible C-type lectin (hMincle) using NFAT-GFP reporter cells was explored, as was the ability of the compounds to activate human monocytes. From these studies, MAGs with an acyl chain length ≥C22 were required for Mincle activation and the production of interleukin-8 (IL-8) by human monocytes.

Reisolation and NMR characterization of the satratoxins G and H.

The exquisitely cytotoxic macrolides, satratoxins G and H, have been reisolated from a solvent extract of a rice culture inoculated with Stachybotrys chartarum to be used as high-purity reference compounds for analytical analyses. Extensive chromatographic separation realized the compounds that were fully recharacterized in two solvents by 1D- and 2D-NMR spectroscopy, revealing some discrepancies in the nuclear magnetic resonance (NMR) data as compared with the previously reported values found in the literature. Detailed spectra are provided in order to aid future identification and dereplication.

An efficient synthesis of a 6″-BODIPY-α-Galactosylceramide probe for monitoring α-Galactosylceramide uptake by cells.

Herein, an efficient synthesis of BODIPY-α-Galactosylceramide 3, which can be used to study the cellular uptake of the potent immunostimulatory parent compound α-Galactosylceramide, is reported. Key in our synthetic strategy is the six-step synthesis of the core BODIPY scaffold (64% yield overall) and its quantitative conversion to an N-hydroxysuccinimidyl ester to facilitate conjugation and purification of the target glycolipid. For the preparation of the core of the glycolipid, the solubility of the lipid acceptor proved to be critical.

Reactions of In-Zn bonds with organic azides: products that result from hetero- and homo-bimetallic behaviour.

The indyl anion, K[In(NON)] (NON = [O(SiMeNDipp)], Dipp = 2,6-iPrCH) reacts with group 12 compounds M(BDI)Cl (M = Zn, Cd; BDI = [HC{C(Me)NR}], R = 2,4,6-MeCH (Mes), Dipp) to afford the heterobimetallic compounds (NON)In-M(BDI) that contain the first In-Zn and In-Cd bonds. The reactivity of the In-Zn bonds towards organic azides, R'N (R' = Mes, Dipp, Ph) was investigated. (NON)In-Zn(BDI) reduces MesNvia an isolable triazenide intermediate to generate the bridging imido compound, (NON)In-(μ-NMes)-Zn(BDI).

Combined Extinction and Absorption UV-Visible Spectroscopy as a Method for Revealing Shape Imperfections of Metallic Nanoparticles.

Metallic nanoparticle solutions are routinely characterized by measuring their extinction spectrum (with UV-vis spectroscopy). Theoretical predictions such as Mie theory for spheres can then be used to infer important properties, such as particle size and concentration. Here we highlight the benefits of measuring not only the extinction (the sum of absorption and scattering) but also the absorption spectrum (which excludes scattering) for routine characterization of metallic nanoparticles.

Exploring a glycosylation methodology for the synthesis of hydroxamate-modified alginate building blocks.

Alginate, an anionic polysaccharide, is an important industrial biomaterial naturally harvested from seaweed. Many of its important physicochemical properties derive from the presence of charged carboxylate groups presented as uronic acids within the polysaccharide backbone. An ability to modify these carboxylates with alternate functional groups would enable the design and implementation of new alginate systems possessing different physicochemical properties.

Improved uniaxial dielectric properties in aligned diisopropylammonium bromide (DIPAB) doped poly(vinylidene difluoride) (PVDF) nanofibers.

Diisopropylammonium bromide (DIPAB) doped poly(vinylidene difluoride) (PVDF) nanofibers (5, 10 and 24 wt% DIPAB doping) with improved and tunable dielectric properties were synthesised electrospinning. DIPAB nanoparticles were grown during the nanofiber formation. X-Ray diffraction (XRD) patterns and Fourier transform infrared spectroscopy (FTIR) proved that electrospinning of DIPAB doped PVDF solutions led to the formation of a highly electro-active β-phase in the nanofibers.

Aluminium-Mediated Carbon Dioxide Reduction by an Isolated Monoalumoxane Anion.

The deoxygenative conversion of carbon dioxide to carbon monoxide is promoted by the aluminyl anion [Al(NON )] (NON =[O(SiMe NAr) ] , Ar=2,6-iPr C H ). The reaction proceeds via the isolable monoalumoxane anion [Al(NON )(O)] , containing a terminal aluminum-oxygen bond. This species reacts with a second equivalent of carbon dioxide to afford the carbonate [Al(NON )(CO )] , and with nitrous oxide to generate the hyponitrite anion, [Al(NON )(κ O,O'-N O )] .

Correction: Synthesis of nanostructured catalysts by surfactant-templating of large-pore zeolites.

[This corrects the article DOI: 10.1039/C9NA00004F.].

The effect of MR1 ligand glyco-analogues on mucosal-associated invariant T (MAIT) cell activation.

Mucosal-associated invariant T (MAIT) cells are a subset of recently identified innate-like T lymphocytes that appear to play an important role in many pathologies ranging from viral and bacterial infection, to autoimmune disorders and cancer. MAIT cells are activated via the presentation of ligands by MR1 on antigen presenting cells to the MAIT T cell receptor (TCR), however few studies have explored the effects of systematic changes to the ligand structure on MR1 binding and MAIT cell activation. Herein, we report on the first study into the effects of changes to the sugar motif in the known MAIT cell agonists 7-hydroxy-6-methyl-8-d-ribityllumazine (RL-6-Me-7-OH) and 5-(2-oxopropylideneamino)-6-d-ribitylaminouracil (5-OP-RU).

Experimental and theoretical studies into the release of blood droplets from weapon tips.

The formation and release under gravity of blood droplets from simulated weapon tips has been investigated experimentally and the results analysed and interpreted using established theoretical models for detached pendent drops. Droplets were produced from a series of conical nozzles, manufactured with a range of cone angles and including a set of un-bored conical tips, under conditions where the tip was either non-wetted or pre-wetted with blood. For the former, radius-limited case, detached droplet volumes were found to agree well with the predictions of both the pendent drop weight and drop shape models.

Present and Future of Surface-Enhanced Raman Scattering.

The discovery of the enhancement of Raman scattering by molecules adsorbed on nanostructured metal surfaces is a landmark in the history of spectroscopic and analytical techniques. Significant experimental and theoretical effort has been directed toward understanding the surface-enhanced Raman scattering (SERS) effect and demonstrating its potential in various types of ultrasensitive sensing applications in a wide variety of fields. In the 45 years since its discovery, SERS has blossomed into a rich area of research and technology, but additional efforts are still needed before it can be routinely used analytically and in commercial products.

Phenotypic Plasticity of Nest-Mate Recognition Cues in Formica exsecta Ants.

It is well established that many ant species have evolved qualitatively distinct species-specific chemical profile that are stable over large geographical distances. Within these species profiles quantitative variations in the chemical profile allows distinct colony-specific odours to arise (chemotypes) that are shared by all colony members. This help maintains social cohesion, including defence of their colonies against all intruders, including con-specifics.