Lanthanide Phosphonates and Phosphates in Molecular Magnetism.

Phosphonate and phosphate ligands have historically received less attention when compared to the widely prevalent carboxylate ligand system. Phosphonates possess multiple donating sites, often leading to the formation of larger aggregates with limited solubility. Conversely, the P-O bond within phosphates is highly susceptible to hydrolysis, resulting in the precipitation of insoluble compounds, particularly when interacting with lanthanide metal ions.

Mechanical imbalance between normal and transformed cells drives epithelial homeostasis through cell competition.

Cell competition in epithelial tissue eliminates transformed cells expressing activated oncoproteins to maintain epithelial homeostasis. Although the process is now understood to be of mechanochemical origin, direct mechanical characterization and associated biochemical underpinnings are lacking. Here, we employ tissue-scale stress and compressibility measurements and theoretical modeling to unveil a mechanical imbalance between normal and transformed cells, which drives cell competition.

A versatile and narrow linewidth infrared radiation source for ro-vibration state-selected preparation of molecules in molecular beams.

We describe the design and characterization of a versatile pulsed (5 ns, 10 Hz repetition rate) optical parametric oscillator and amplifier system capable of generating single longitudinal mode, narrow linewidth (0.01 cm-1) radiations in the wavelength range of 680-870 nm and 1380-4650 nm. Using a combination of power-normalized photoacoustic signal and a Fizeau interferometer-based wavemeter, we are able to actively stabilize the output wavenumber to within 0.

Lewis Acid Stabilized Diatomic Molecules of Group 14: A Computational Study on [(CO)Fe]E (E = C, Si, Ge, Sn, Pb).

A Lewis base and acid combination has been effectively employed to stabilize and isolate the low-valent group 14 compounds. We report DFT studies on stabilizing low-valent group 14 diatomics as adducts of Lewis acids employing transition metal carbonyl fragment iron tetracarbonyl [Fe(CO)] as Lewis acid. Computational studies on [(CO)Fe]E, E = C, Si, Ge, Sn, and Pb, predict five plausible isomers on its potential energy surface: linear (), bent (), three-membered (), dibridged (), and four-membered ().

Comment on "Disclosing Cyclic(Alkyl)(Amino)Carbenes as a One-Electron Reductant: Synthesis of Acyclic(Amino)(Aryl)Carbene-Based Kekulé Diradicaloids".

This correspondence addresses a misassignment of an EPR spectrum of 2 in a recent publication (Chem. Eur. J.

Improving In Vivo Tumor Accumulation and Efficacy of Platinum Antitumor Agents by Electronic Tuning of the Kinetic Lability.

The impact of kinetic lability or reactivity on in vitro cytotoxicity, stability in plasma, in vivo tumor and tissue accumulation, and antitumor efficacy of functional platinum(II) (Pt) anticancer agents containing a O˄O β-diketonate leaving ligand remain largely unexplored. To investigate this, we synthesized Pt complexes [(NH ) Pt(L1-H)]NO and [(DACH)Pt(L1-H)]NO (L1=4,4,4-trifluoro-1-ferrocenylbutane-1,3-dione, DACH=1R,2R-cyclohexane-1,2-diamine) containing an electron deficient [L1-H] O˄O leaving ligand and [(NH ) Pt(L2-H)]NO and [(DACH)Pt(L2-H)]NO (L2=1-ferrocenylbutane-1,3-dione) containing an electron-rich [L2-H] O˄O leaving ligand. While all four complexes have comparable lipophilicity, the presence of the electron-withdrawing CF group was found to dramatically enhance the reactivity of these complexes toward nucleophilic biomolecules.

Interplay of cell motility and self-secreted extracellular polymeric substance induced depletion effects on spatial patterning in a growing microbial colony.

Reproducing bacteria self-organize to develop patterned biofilms in various conditions. Various factors contribute to the shaping of a multicellular bacterial organization. Here we investigate how motility force and self-secreted extracellular polymeric substances (EPS) influence bacterial cell aggregation, leading to phase-separated colonies using a particle-based/individual-based model.

Advancing large-scale production of TEV protease through an innovative NT* tag-based fusion construct.

Tobacco etch virus Protease (TEVp), a cysteine protease, is renowned for its remarkable specific proteolysis, making it an invaluable tool for removing fusion tags from recombinant proteins. However, TEV protease's inherent insolubility limits its broad application. Fusion constructs like an N-terminal MBP fusion, known for its improved solubility, have been employed for TEVp production to address this issue.

Total Chemical Synthesis of the SARS-CoV-2 Spike Receptor-Binding Domain.

SARS-CoV-2 and its global spread have created an unprecedented public health crisis. The spike protein of SARS-CoV-2 has gained significant attention due to its crucial role in viral entry into host cells and its potential as both a prophylactic and a target for therapeutic interventions. Herein, we report the first successful total synthesis of the SARS-CoV-2 spike protein receptor binding domain (RBD), highlighting the key challenges and the strategies employed to overcome them.

Carrier multiplication in perovskite solar cells with internal quantum efficiency exceeding 100.

Carrier multiplication (CM) holds great promise to break the Shockley-Queisser limit of single junction photovoltaic cells. Despite compelling spectroscopic evidence of strong CM effects in halide perovskites, studies in actual perovskite solar cells (PSCs) are lacking. Herein, we reconcile this knowledge gap using the testbed CsFAMAPbSnI system exhibiting efficient CM with a low threshold of 2E (~500 nm) and high efficiency of 99.

Field induced single ion magnet behavior in Co complexes in a distorted square pyramidal geometry.

We report three Co-based complexes with the general formula [Co(L)(X)] by changing the halide/pseudo-halide ions [X = NCSe (1SeCN); Cl (2Cl) and Br (3Br)]. The obtained and values confirm a distorted square pyramidal geometry around the Co ion in all these complexes. In these three complexes, the central Co ion is situated above the basal plane of the square pyramidal geometry.

Ultrafast carrier dynamics in vanadium-doped MoS alloys.

Substitutional doping is a most promising approach to manipulate the electronic and optical properties of two-dimensional (2D) transition metal dichalcogenides (TMDCs). In addition to inducing magnetism, vanadium (V) doping can lead to semiconductor-metal transition in TMDCs. However, the dynamics of charge carriers that governs the optoelectronic properties of doped TMDCs has been rarely revealed.

Introducing an orthogonally polarized electron-rich alkene: synthesis of a zwitterionic boron-containing π-conjugated system.

The synthesis of an alkene is reported which is concurrently twisted (twist angle = 86.6(8)°), push-pull (dipole moment = 7.48 D), and electron-rich ( = -1.

On the electronic and spin-valley coupling of vanadium doped MoSSemonolayers.

Monolayers of MoSwith tunable bandgap and valley positions are highly demanding for their applications in opto-spintronics. Herein, selenium (Se) and vanadium (V) co-doped MoSmonolayers (vanadium doped MoSSe(V-MoSSe)) are developed and showed their variations in the electronic and optical properties with dopant content. Vanadium gets substitutionally (in place of Mo) doped within the MoSlattice while selenium doped in place of sulfur, as shown by a detailed microstructure and spectroscopy analyses.

Bis-Olefin Based Crystalline Schlenk Hydrocarbon Diradicals with a Triplet Ground State.

A modular approach for the synthesis of isolable crystalline Schlenk hydrocarbon diradicals from m-phenylene bridged electron-rich bis-triazaalkenes as synthons is reported. EPR spectroscopy confirms their diradical nature and triplet electronic structure by revealing a half-field signal. A computational analysis confirms the triplet state to be the ground state.

Zinc Catalyzed Hydroboration of Esters and Nitriles with Pinacolborane.

We developed a bench-stable iminopyridine-ligated zinc complex for the effective catalytic hydroboration of esters and nitriles under solvent-free conditions. Various esters and nitriles bearing different functionalities were selectively reduced to form corresponding alcohols and amines in good yields. Detailed Hammett plots are provided to explain the electronic effects on the phenyl ring.

Probing excited state Hα chemical shifts in intrinsically disordered proteins with a triple resonance-based CEST experiment: Application to a disorder-to-order switch.

Over 40% of eukaryotic proteomes and 15% of bacterial proteomes are predicted to be intrinsically disordered based on their amino acid sequence. Intrinsically disordered proteins (IDPs) exist as heterogeneous ensembles of interconverting conformations and pose a challenge to the structure-function paradigm by apparently functioning without possessing stable structural elements. IDPs play a prominent role in biological processes involving extensive intermolecular interaction networks and their inherently dynamic nature facilitates their promiscuous interaction with multiple structurally diverse partner molecules.

A roadmap to enhance gas permselectivity in metal-organic framework-based mixed-matrix membranes.

Performing gas separation at high efficiency with minimum energy input and reduced carbon footprint is a major challenge. While several separation methods exist at various technology readiness levels, porous membrane-based separation is considered as a disruptive technology. To attain sustainability and required efficiency, different approaches of membrane design have been explored.

Collective heterogeneity of mitochondrial potential in contact inhibition of proliferation.

In the epithelium, cell density and cell proliferation are closely connected to each other through contact inhibition of proliferation (CIP). Depending on cell density, CIP proceeds through three distinct stages: the free-growing stage at low density, the pre-epithelial transition stage at medium density, and the post-epithelial transition stage at high density. Previous studies have elucidated how cell morphology, motion, and mechanics vary in these stages.

Synthesis, structures and magnetic studies of hexanuclear lanthanide complexes: SMM behavior of the Dy analogue and MCE properties of the Gd analogue.

The synthesis, structure and magnetic properties of homometallic hexanuclear lanthanide complexes [Ln(HL)(tfa)(S)]·2NO· HO·MeOH (1, Ln = Gd, S = MeOH, = 0, = 0; 2, Ln = Tb, S = HO, = 2, = 2; 3, Ln = Dy, S = MeOH, = 0, = 2; 4, Ln = Er, S = MeOH, = 0, = 2). [(HL) = 6-((bis(2-hydroxyethyl)amino)-'-(2-hydroxybenzylidene)picolinohydrazide) (tfa = trifloroacetylacetone)] are reported. These hexanuclear assemblies are made up of two trinuclear triangular sub-units linked through the oxygen atoms of two phenoxide bridging groups in a corner sharing arrangement.

Tunable J-type aggregation of silicon phthalocyanines in a surface-anchored metal-organic framework thin film.

Organic chromophores and semiconductors, like anthracene, pentacene, perylene, and porphyrin, are prone to aggregation, and their packing in the solid state is often hard to predict and difficult to control. As the condensed phase structures of these chromophores and semiconductors are of crucial importance for their optoelectronic functionality, strategies to control their assembly and provide new structural motifs are important. One such approach uses metal-organic frameworks (MOFs); the organic chromophore is converted into a linker and connected by metal ions or nodes.

Metabolic regulation of CTCF expression and chromatin association dictates starvation response in mice and flies.

Coordinated temporal control of gene expression is essential for physiological homeostasis, especially during metabolic transitions. However, the interplay between chromatin architectural proteins and metabolism in regulating transcription is less understood. Here, we demonstrate a conserved bidirectional interplay between CTCF (CCCTC-binding factor) expression/function and metabolic inputs during feed-fast cycles.

Shaping mitochondria through fed-fast and circadian cycles.

Energy and metabolic homeostasis at the level of the whole body are dictated by the balance between nutrient intake/utilization, bioenergetic potential, and energy expenditure, which are tightly coupled with fed/fast cycles and circadian oscillation. Emerging literature has highlighted the importance of each of these mechanisms that are essential to maintain physiological homeostasis. Lifestyle changes predominantly associated with altered fed-fast and circadian cycles are well established to affect systemic metabolism and energetics, and hence contribute to pathophysiological states.

Highly efficient and well-controlled ROP and copolymerization of cyclic esters using a cesium complex.

A cesium imino-phosphanamidinate, [{NHIP(Ph)NDipp}Cs], enabling efficient ring-opening (co)polymerization of -LA and ε-CL is disclosed. Owing to the highly controlled polymerization, precise di-block copolymers (PLA--PCL) with different block lengths can be produced by a simple one-pot reaction. NMR, GPC, DSC and microscopic analyses confirm the production of di-block copolymers with crystalline properties.