Supramolecular Preorganization of Amine-functionalized Diacetylene Monomers in their Crystals Allows their Topochemical Polymerization to Polydiacetylenenes Capable of CO2 Capture.

We designed and synthesized three diacetylene monomers M1-M3 having two NH2 groups. As anticipated, the NH2 groups aided the preorganization of these monomers by N-H…N hydrogen bonding. In the crystals of monomer M1 and M2, the intermolecular N-H…N hydrogen bonding preorganized the diyne units in an orientation suitable for their topochemical polymerization, but in the case of monomer M3, the distance was slightly larger than that recommended for the topochemical reaction.

Spin-Frustrated Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) are a fascinating class of structured materials with diverse functionality originating from the distinctive physicochemical properties. This review focuses on the specific chemical design of geometrically frustrated MOFs along with the origin of the intriguing magnetic properties. We have discussed the arrangement of spin centres (metal and ligand) which are responsible for the unusual magnetic phenomena in MOFs.

A Non-Benzenoid Route to Thio-Oxybenzone Analogs: Superior UV Protection with Reduced Cytotoxicity.

A one-pot methodology for the tandem acylation and oxidative aromatization of vinylogous thioesters to 2-acyl-5-(alkyl/arylthio)phenols is presented. Initially, cyclohexane-1,3-diones were converted to vinylogous thioesters through FeCl3-mediated thioenolization. This was followed by LiTMP-mediated acylation and DDQ-mediated aromatization, which resulted in the synthesis of sulphur derived oxybenzone analogs.

Ce[N(SiMe3)2]3(THF)3-Catalyzed Hydroboration of CO2, Esters and Epoxides with Pinacolborane: Selective Synthesis of Methanol in Multigram Scale.

In this work, we have reduced CO2 with HBpin to afford borylated methanol product selectively in ~99% yield using Ce[N(SiMe3)2]3(THF)3 as a catalyst. This led to multigram scale isolation of methanol obtained from CO2 reduction via the hydrolysis of borylated methanol, this establishes the potential of Ce[N(SiMe3)2]3(THF)3 as an efficient homogeneous catalyst for the bulk scale methanol synthesis. A practical application of this catalytic system was also shown by reducing CO2-containing motorbike exhaust efficiently and selectively.

A face-off between Smaug and Caspar modulates primordial germ cell count and identity in embryos.

Proper formation and specification of Primordial Germ Cells (PGCs) is of special significance as they gradually transform into Germline Stem Cells (GSCs) that are ultimately responsible for generating the gametes. Intriguingly, not only the PGCs constitute the only immortal cell type but several specific determinants also underlying PGC specification such as Vasa, Nanos and Germ-cell-less are conserved through evolution. In , PGC formation and specification depends on two independent factors, the maternally deposited specialized cytoplasm (or germ plasm) enriched in germline determinants, and the mechanisms that execute the even partitioning of these determinants between the daughter cells.

EARTH-ABUNDANT 3d-TRANSITION METAL METASILICATES AS EFFECTIVE ELECTROCATALYSTS FOR ALKALINE HER: CuZnSiO3 OUTPERFORMS CuSiO3 AND ZnSiO3.

Hydrogen evolution reaction (HER) is a key reaction in electrochemical water splitting for hydrogen production leading to the development of potentially sustainable energy technology. Importantly, the catalysts required for HER must be earth-abundant for their large-scale deployment; silicates representing one such class. Herein, we have synthesized a series of transition mono- and bi- metal metasilicates (with SO32- group) using facile wet-chemical method followed by calcination at a higher temperature.

Ellagic Acid Induces DNA Damage and Apoptosis in Cancer Stem-like Cells and Overcomes Cisplatin Resistance.

Cancer stem cells (CSCs) are responsible for chemoresistance and tumor relapse in many solid malignancies, including lung and ovarian cancer. Ellagic acid (EA), a natural polyphenol, exhibits anticancer effects on various human malignancies. However, its impact and mechanism of action on cancer stem-like cells (CSLCs) are only partially understood.

Caspar specifies primordial germ cell count and identity in .

Repurposing of pleiotropic factors during execution of diverse cellular processes has emerged as a regulatory paradigm. Embryonic development in metazoans is controlled by maternal factors deposited in the egg during oogenesis. Here, we explore maternal role(s) of Caspar (Casp), the orthologue of human Fas-associated factor-1 (FAF1) originally implicated in host-defense as a negative regulator of NF-κB signaling.

Design, Synthesis, Magnetic Properties, and Hydrogen Evolution Reaction of a Butterfly-like Heterometallic Trinuclear [CuMn] Cluster.

A novel heterometallic trinuclear cluster [CuMn(cpdp)(NO)(Cl)] () has been designed and synthesized by employing a molecular library approach that uses CuCl·2HO and Mn(NO)·4HO as inorganic metal salts and Hcpdp as a multifunctional organic scaffold (Hcpdp = ,'-bis[2-carboxybenzomethyl]-,'-bis[2-pyridylmethyl]-1,3-diaminopropan-2-ol). This heterometallic cluster has emerged as an unusual ferromagnetic material and promising electrocatalyst for hydrogen evolution reaction (HER) in the domain of inorganic and materials chemistry. Crystal structure analysis establishes the structural arrangement of , revealing a butterfly-like topology with an unusual seven-coordinated Mn(II) center.

Site-Selective Direct γ-Difunctionalization of Diazoenals: Application to the Synthesis of Enal-Functionalized Allenes and Furans.

A new approach for the synthetically important γ-functionalized enals has been developed. The strategy involves rhodium-catalyzed direct C-C & C-S bond forming site-selective γ-difunctionalization of diazoenals with aryl propargyl sulfides via sulfur ylide [2,3] sigmatropic rearrangement, resulting in the highly functionalized γ-allenyl(sulfanyl)enals in excellent yield at ambient temperature. This highly versatile approach constitutes a viable alternative to the remote carbonyl-directed γ-functionalization of unmodified enals which suffer from competitive side reactions.

Synergistic Rh(II)- and Zn(II)-Catalyzed [3 + 3] Annulation of Diazoenals and α-Hydroxy Ketones for the Direct Synthesis of 2-Pyrans, A Gateway Toward γ-Pyrones.

A new synergistic Rh(II)/Zn(II)-catalyzed [3 + 3] annulation has been developed between diazoenals and α-hydroxy ketones enabling the direct synthesis of 4-formyl-2-pyrans. The reaction involves the formation of protic oxonium ylides from highly electrophilic Rh-enalcarbenoids followed by Zn-templated regioselective intramolecular aldol condensation. Subsequent investigations demonstrated that 4-formyl-2-pyrans are unique precursors of γ-pyrones.

Anomalous lattice contraction and emerging topological phases in Bi-substituted SmIrO.

We demonstrate that substituting Bi for Sm in the pyrochlore Sm$_2$Ir$_2$O$_7$ induces an anomalous lattice contraction, with $\Delta a \sim -0.012$~\AA~observed at 10\% Bi substitution, where 'a' denotes the lattice constant. Beyond 10\% Bi substitution, the lattice expands according to Vegard's law.

Coexistence of multiple magnetic interactions in oxygen-deficient V2O5 nanoparticles.

This paper reports on the spin glass-like coexistence of competing magnetic orders in oxygen-deficient V2O5 nanoparticles with a broad size distribution. X-ray photoelectron spectroscopy yields the surface chemical stoichiometry of nearly V2O4.65 due to significant defect density.

Triple Nucleophilic Head-to-Tail Cascade Polycyclization of Diazodienals via Combination Catalysis: Direct Access to Cyclopentane Fused Aza-Polycycles with Six-Contiguous Stereocenters.

Reported herein are the bench stable (24)-diazohexa-2,4-dienals (diazodienals) and their unprecedented polycyclization with aldimine and arylamines enabled by Rh(II)/Brønsted acid relay catalysis. This scalable and atom-economical reaction provides direct access to the biologically important azatricyclo[6.2.

Fruit ripening retardant Daminozide induces cognitive impairment, cell specific neurotoxicity, and genotoxicity in Drosophila melanogaster.

Background: We explored neurotoxic and genotoxic effects of Daminozide, a fruit ripening retardant, on the brain of Drosophila melanogaster, based on our previous finding of DNA fragmentation in larval brain cell in the flies experimentally exposed to this chemicals.

Methods: Adult flies were subjected to two distinct concentrations of daminozide (200 mg/L and 400 mg/L) mixed in culture medium, followed by an examination of specific behaviors such as courtship conditioning and aversive phototaxis, which serve as indicators of cognitive functions. We investigated brain histology and histochemistry to assess the overall toxicity of daminozide, focusing on neuron type-specific effects.

A combined theoretical and experimental approach to determine the right choice of co-ligand to impart spin crossover in Fe(II) complexes based on 1,3,4-oxadiazole ligands.

We present the synthesis of two new novel tetradentate ligands based on 1,3,4-oxadiazole, 2-(2-pyridyl)-5-[,-bis(2-pyridylmethyl)aminomethyl]-1,3,4-oxadiazole (LTetraPy-ODA) and 2-(2-phenyl)-5-[,-bis(2-pyridylmethyl)aminomethyl]-1,3,4-oxadiazole (LTetraPh-ODA). The ligands were used to prepare six mononuclear complexes [Fe(LTetraPy-ODA)(NCE)] (C1-C3) and [Fe(LTetraPh-ODA)(NCE)] (C4-C6) where E = S, Se or BH. In addition, the ligand LTetraPy-ODA was employed in the synthesis of a new di-nuclear complex [FeII2(LTetraPh)](ClO)·1 CHNO·1.

Extracellular signals induce dynamic ER remodeling through αTAT1-dependent microtubule acetylation.

Dynamic changes in the endoplasmic reticulum (ER) morphology are central to maintaining cellular homeostasis. Microtubules (MT) facilitate the continuous remodeling of the ER network into sheets and tubules by coordinating with many ER-shaping protein complexes, although how this process is controlled by extracellular signals remains unknown. Here we report that TAK1, a kinase responsive to various growth factors and cytokines including TGF-β and TNF-α, triggers ER tubulation by activating αTAT1, an MT-acetylating enzyme that enhances ER-sliding.

Age-dependent dynamics of neuronal VAPB inclusions in the adult brain.

Amyotrophic Lateral Sclerosis (ALS) is a relentlessly progressive and fatal disease, caused by the degeneration of upper and lower motor neurons within the brain and spinal cord in the ageing human. The dying neurons contain cytoplasmic inclusions linked to the onset and progression of the disease. Here, we use a Drosophila model of ALS8 (VAP) to understand the modulation of these inclusions in the ageing adult brain.

[3+3] Annulation of Diazoenals and α-Mercapto Ketones via Protic Sulfonium Ylides: Direct Synthesis of 2-Thiopyrans, Innovative Progenitors for Unstudied 2-Thiopyran-2-ones and 4-Thiopyran-4-ones.

Herein, we report a new Rh(II)/Sc(III)-catalyzed [3+3] annulation between diazoenals and α-mercapto ketones for the direct synthesis of 4-formyl-2-thiopyrans. The reaction proceeds via protic sulfonium ylides derived from highly electrophilic Rh-enalcarbenoids, followed by regioselective intramolecular aldol condensation. Further studies revealed that 4-formyl-2-thiopyrans are novel precursors for unstudied 2-thiopyran-2-ones and 4-thiopyran-4-ones.

Role of Macrophage PIST Protein in Regulating Infection.

PDZ protein interacting specifically with Tc10 or PIST is a mammalian trans-Golgi resident protein that regulates subcellular sorting of plasma membrane receptors. PIST has recently emerged as a key player in regulating viral pathogenesis. Nevertheless, the involvement of PIST in parasitic infections remains unexplored.

Taxonomic notes on the genus Afghanicenus Heyrovsk, 1941 (Coleoptera: Cerambycidae), with the first record of Afghanicenus nuristanicus (Heyrovsk, 1936) from Pakistan.

Afghanicenus nuristanicus (Heyrovsk, 1936) is hereby newly recorded from Pakistan based on a specimen collected at the beginning of the 20th century and preserved in the collection of the Natural History Museum, London. High quality colour images of the type material (a male syntype of Purpuricenus nuristanicus and a female syntype of P. nuristanicus f.

Using Chaos-Game-Representation for Analysing the SARS-CoV-2 Lineages, Newly Emerging Strains and Recombinants.

Background: Viruses have high mutation rates, facilitating rapid evolution and the emergence of new species, subspecies, strains and recombinant forms. Accurate classification of these forms is crucial for understanding viral evolution and developing therapeutic applications. Phylogenetic classification is typically performed by analyzing molecular differences at the genomic and sub-genomic levels.

Rh-Catalyzed Chemodivergent [3+3] Annulations of Diazoenals and α-Aminoketones: Direct Synthesis of Functionalized 1,2-Dihydropyridines and Fused 1,4-Oxazines.

Novel rhodium-catalyzed [3+3] annulations of diazoenals and α-amino ketones has been disclosed here. The reactivity of diazoenals has been switched from carbenoid to vinylogous NH-insertion by altering acyclic to cyclic α-amino ketones. In this direction, we report an efficient strategy to synthesize 1,2-dihydropyridines (DHPs) and fused 1,4-oxazines.

Physical vapor deposition-free scalable high-efficiency electrical contacts to MoS.

Fermi-level pinning caused by the kinetic damage during metallization has been recognized as one of the major reasons for the non-ideal behavior of electrical contacts, forbidding reaching the Schottky-Mott limit. In this manuscript, we present a scalable technique wherein Indium, a low-work-function metal, is diffused to contact a few-layered MoSflake. The technique exploits a smooth outflow of Indium over gold electrodes to make edge contacts to pre-transferred MoSflakes.