Photoinduced Cobaloxime-Catalyzed Regio- and Diastereoselective Hydrogen-Evolution C(sp)-H Phosphorylation of Bicyclo[1.1.0]butanes.

Radical-initiated functionalization of bicyclo[1.1.0]butanes (BCBs) is a straightforward approach to accessing diverse cyclobutane derivatives.

Chemodivergent and Enantioselective Synthesis of Spirobi[dihydrophenalene] Structures.

The development and enantioselective synthesis of two types of -symmetric spirobi[dihydrophenalene] structures is reported. The reaction proceeds via rhodium-catalyzed 2-fold asymmetric conjugate arylation of dienones followed by BF·OEt-promoted spirocyclization to give the enantiopure spiro products. Additive-dependent chemodivergent synthesis of 3,3'-diarylated 2,2',3,3'-tetrahydro-1,1'-spirobi[phenalene]-9,9'-diols (3,3'-Ar-SPHENOLs) and the corresponding spiro diary ethers from the same intermediate is achieved.

Bone-seeking tumor cells alter bone material quality parameters on the nanoscale in mice.

Bone metastases related to breast and prostate cancer present with multiple challenges and skeletal related events like fragility fractures impair the quality of life of the patients significantly. To determine local alterations in bone material quality with bone metastasis, we subjected murine tibial specimens, generated after intratibial injections of either RM1 prostate cancer cells or EO771 breast cancer cells into male and female mice respectively, to high-resolution imaging modalities. Small and wide-angle X-ray scattering showed unaltered mineral characteristics in the more osteosclerotic prostate cancer model, while the quantification of calcium weight percentage via backscattered electron microscopy determined minor differences along the perilacunar bone matrix.

Switchable Divergent Electrochemical Hydrodehalogenation of -Dihalocyclopropanes.

A comprehensive and effective electrochemical methodology is introduced for the diverse hydrodechlorination of -dichlorocyclopropanes and the ring cleavage hydrodefluorination of -difluorocyclopropanes under uniform electrochemical conditions. Moreover, the water content allows for the adjustable monohydrodechlorination or dihydrodechlorination of -dichlorocyclopropanes with exceptional chemoselectivity. Additionally, the mildness and practicality of this protocol facilitate its application to the late-stage functionalization of bioactive molecules.

Biologically Synthesized Gold Nanoparticles with Enhanced Antioxidant and Catalytic Properties.

Increasing levels of reactive oxygen species generate oxidative stress in the human body that can lead to various medical conditions. The use of nanomaterials exhibiting antioxidant properties may prevent these effects. The biological synthesis of metallic nanoparticles using plant extracts with antioxidant properties can offer benefits due to their active compounds.

Electrooxidative 1,3-Oxo/Carboamination of Arylcyclopropanes.

Herein, the work demonstrates an electrochemically paired electrolysis approach facilitating the efficient achievement of the electrooxidative 1,3-oxo/carboamination of arylcyclopropanes under mild conditions. The formation of 1,3-arylamination of arylcyclopropanes involves commercially available amine redox mediators through a radical-radical process. In addition, the successful execution of β-amino ketones also occurs under atmospheric conditions.

Dipolar Order Controls Dielectric Response of Glass-Forming Liquids.

The dielectric response of liquids reflects both reorientation of single molecular dipoles and collective modes, i.e., dipolar cross-correlations.

UV-Vis-NIR Broadband Self-Powered CuInS/SnO Photodetectors and the Application in Encrypted Optical Communication.

Photodetectors (PDs) with broadband photoresponse can meet the demand for multiband detection in complex environments, overcoming the technological complexity issue of integrated narrow-band PDs. Self-powered heterojunction PDs having ultraviolet-visible-near-infrared broadband photoresponse were constructed by using SnO nanopillars and CuInS nanoflakes. The dimension, crystalline quality, and energy level structure of the SnO nanopillars were regulated by changing the concentration of Sn ions in the precursor solution.

Ex-vivo validation of spatial gain sonography for the quantification of echo intensity in fascicle-aligned ultrasound images in ten anatomical muscles in Bos taurus.

This study aimed to validate the concept of spatial gain sonography for quantifying texture-related echo intensity in B-mode ultrasound of skeletal muscle. Fifty-one bovine muscles were scanned postmortem using B-mode ultrasonography at varying fascicle probe angles (FPA). The relationship between mean gray values (MGV) and FPA was fitted with a sinusoidal and a linear function, the slope of which was defined as tilt echo gain (TEG).

Enrichment of linoleic acid from yellow horn seed oil through low temperature crystallization followed by urea complexation method and hypoglycemic activities.

Unlabelled: Yellow horn ( Bunge) contained abundant linoleic acid (LA), accounting for about 44% of its lipid. Here, LA was enriched by low temperature crystallization followed by urea complexation, and the optimal enrichment conditions were optimized with response surface methods (3:1 ratio of EtOH/FFA, crystallization at - 25 °C for 24.5 h; 2:1 ratio of urea/FFA, 6.

Local Structural Modifications in Metallic Micropillars Induced by Plasma Focused Ion Beam Processing.

A focused ion beam scanning electron microscope (FIB-SEM) is a powerful tool that is routinely used for scale imaging from the micro- to nanometer scales, micromachining, prototyping, and metrology. In spite of the significant capabilities of a FIB-SEM, there are inherent artefacts (e.g.

A Synthetic Approach for Oxadiazole-Decorated Azobenzene Photoswitches.

This work reports the design and synthesis of novel oxadiazole-decorated azobenzenes, structural analysis of the resulting compounds and behavior under light irradiation. The synthetic strategy involved constructing amino functionalized heterocyclic key intermediates which were used either to yield electrophilic diazonium salts able to react with phenol moieties or as nucleophilic partners in Bayer-Mills reaction with nitroso-substituted derivatives. The amino-derived oxadiazole intermediates were investigated by absorption and emission spectroscopy providing blue and green emitted light.

Defluorinative Thiolation of -Difluoroalkenes by Convergent Paired Electrolysis.

Herein, we have successfully developed a convergent paired electrolysis strategy for the defluorinative thiolation process utilizing thiols and -difluoroalkenes as precursors. This protocol exhibits remarkable tolerance toward a wide range of functional groups, as exemplified by the successful late-stage defluorothiolation of complex molecules. Additionally, this strategy is amenable to gram-scale synthesis, making use of both anodic oxidation and cathodic reduction processes in an efficient manner.

2-Isopropylthioxanthone-Catalyzed Divergent Functionalization of Bicyclo[1.1.0]butanes under Visible-Light Irradiation.

1,3-Functionalized cyclobutane structural motifs are ubiquitous in natural products and pharmaceuticals. Photoinduced alkylation of bicyclo[1.1.

Photoelectron Spectroscopy of Oppositely Charged Molecular Switches in the Aqueous Phase: Theory and Experiment.

XUV photoelectron spectroscopy (XPS) is a powerful method for investigating the electronic structures of molecules. However, the correct interpretation of results in the condensed phase requires theoretical models that account for solvation. Here we present experimental aqueous-phase XPS of two organic biomimetic molecular switches, NAIP and -HDIOP.

Thiol functionalised gold nanoparticles loaded with methotrexate for cancer treatment: From synthesis to in vitro studies on neuroblastoma cell lines.

Hypothesis: Colloidal gold nanoparticles (AuNPs) functionalised with hydrophilic thiols can be used as drug delivery probes, thanks to their small size and hydrophilic character. AuNPs possess unique properties for their use in nanomedicine, especially in cancer treatment, as diagnostics and therapeutic tools.

Experiments: Thiol functionalised AuNPs were synthesised and loaded with methotrexate (MTX).

Surface Reconstruction of Lead-Free Perovskite CsAgNaInCl:Bi by Hydroxylation with Blue-Light-Excited Performance.

Molecular surface reconfiguration strategies have been instrumental to performance improvements of halide perovskite photovoltaic applications in recent years. However, research into the optical properties of the lead-free double perovskite CsAgInCl on the complex reconstructed surface is still lacking. Here, blue-light excitation in double perovskite CsNaAgInCl with Bi doping has been successfully achieved by excess KBr coating and ethanol-driven structural reconstruction.

Alkali-Amide-Catalyzed One-Pot Aminoallylation of Aldehydes with Allylbenzenes.

The deprotonation of allylbenzene was successfully demonstrated with a catalytic alkali amide base (NaN(SiMe)). The deprotonated allyl anion could be trapped by in situ generated -(trimethylsilyl) aldimines to provide value-added homoallylic amines (39 examples, 68-98% yields) in a one-pot manner with excellent liner selectivity. Compared with the previously reported method for the synthesis of homoallylic amines, this method does not need to use the preinstalled protection groups on the imines, which need to be removed after the reaction to obtain the N-H free homoallylic amine derivatives.

Analysis of the dislocation activity of Mg-Zn-Y alloy using synchrotron radiation under tensile loading.

An understanding of deformation behavior and texture development is crucial for the formability improvement of Mg alloys. X-ray line profile analysis using the convolutional multiple whole profile (CMWP) fitting method allows the experimental determination of dislocation densities separately for different Burgers vectors up to a high deformation degree. A wider use of this technique still requires exploration and testing of various materials.

Rhodium-Catalyzed Asymmetric Annulation of Unactivated Alkynes with 3-(-Boronated Aryl) Conjugated Enones: Enantioselective Synthesis of 2,3-Disubstituted Indenes.

A rhodium-catalyzed tandem arylation/cyclization reaction of 3-(ortho-boronated aryl) conjugated enones with unactivated alkynes is reported. By using a rhodium(I)/chiral-diene complex as the catalyst, the protocol was processed smoothly to provide various 2,3-disubstituted indene compounds in high yields with excellent regioselectivities and enantioselectivities. The approach outlined herein is appealing, as simple diarylalkynes, diakylalkynes, and alkyl(aryl)alkynes are the starting materials.

Electrochemical detection of fluoride ions in water with nanoporous gold modified by a boronic acid terminated self-assembled monolayer.

Nanoporous gold (npAu) is a perfectly suited platform for the electrochemical detection of minor amounts of chemical species in solution due to its high surface-to-volume ratio. By surface-modification of the self-standing structure with a self-assembled monolayer (SAM) of 4-mercaptophenylboronic acid (MPBA) it was possible to create an electrode very sensitive towards fluoride ions in water, also suitable for mobile use in future sensing applications. The proposed detection strategy is based on the change in the charge state of the boronic acid functional groups of the monolayer, induced by fluoride binding.

Advancements in Liquid Jet Technology and X-ray Spectroscopy for Understanding Energy Conversion Materials during Operation.

ConspectusWater splitting is intensively studied for sustainable and effective energy storage in green/alternative energy harvesting-storage-release cycles. In this work, we present our recent developments for combining liquid jet microtechnology with different types of soft X-ray spectroscopy at high-flux X-ray sources, in particular developed for studying the oxygen evolution reaction (OER). We are particularly interested in the development of photon-in/photon-out techniques, such as in situ resonant inelastic X-ray scattering (RIXS) techniques at high-repetition-frequency X-ray sources, pointing toward capabilities.