Synthetically Reversible, Proton-Mediated Nitrite N-O Bond Cleavage at a Dicopper Site.

A monocationic dicopper(I,I) nitrite complex [Cu(μ-κ:κ-ON)DPFN][NTf] () (DPFN = 2,7-bis(fluoro-di(2-pyridyl)methyl)-1,8-naphthyridine, NTf = N(SOCF)), was synthesized by treatment of a dicopper acetonitrile complex, [Cu(μ-MeCN)DPFN][NTf] (), with tetrabutylammonium nitrite ([BuN][NO]). DFT calculations indicate that is one of three linkage isomers that are close in energy and presumably accessible in solution. Reaction of the μ-κ:κ-ON complex with -TolSH produces nitrous acid (HONO) and the corresponding dicopper thiolate species via an acid-base exchange reaction.

Isosteric 3D Bicyclo[1.1.1]Pentane (BCP) Core-Based Lipids for mRNA Delivery and CRISPR/Cas Gene Editing.

Lipid nanoparticles (LNPs) are an essential component of messenger RNA (mRNA) vaccines and genome editing therapeutics. Ionizable amino lipids, which play the most crucial role in enabling mRNA to overcome delivery barriers, have, to date, been restricted to two-dimensional (2D) architectures. Inspired by improved physicochemical properties resulting from the incorporation of three-dimensionality (3D) into small-molecule drugs, we report the creation of 3D ionizable lipid designs through the introduction of bicyclo[1.

Integration of Immunosyringe Sensors with Bar-Chart Chips for Prick-and-Read Testing of Prostate Specific Antigen.

Pressure-based signal transduction is of promise in developing microfluidic immunoassays such as volumetric bar-chart chips (V-chips), but new working principles are required to further simplify the methods in point-of-care testing (POCT). Herein, we developed immunosyringe sensors and integrated them with bar-chart chips for simple prick-and-read testing of prostate specific antigen (PSA) as a model target. Disposable syringes served as the host for the construction of the sandwich-type immuno-recognition system.

Ultrahigh-Resolution Mass Spectrometry Advances for Biogeochemical Analysis: From Seafloor Sediments to Petroleum and Marine Oil Spills.

This Perspective explores the transformative impact of ultrahigh-resolution mass spectrometry (UHR-MS), particularly Fourier transform ion cyclotron resonance (FT-ICR-MS), in the characterization of complex environmental and petroleum samples. UHR-MS has significantly advanced our ability to identify molecular formulas in complex mixtures, revolutionizing the study of biogeochemical processes and organic matter evolution on wide time scales. We start by briefly reviewing the main technological advances of UHR-MS in the context of petroleum and environmental applications, highlighting some of the challenges of the technology such as quantitation and structural identification.

Iridium Complexes of a Bis(-pyrrolyl)boryl/Bis(phosphine) PBP Pincer Ligand.

This work reports the synthesis of a bis(pyrrolylphosphino)phenyl borane (PBP)Ph () and its incorporation of Ir by metal insertion into B-Ph to afford the dipyrrolylboryl/bis(phosphine) pincer complex (PBP)Ir(Ph)Cl (). Hydrogenolysis of afforded (PBP)Ir(H)Cl (). Compound was converted into (PBP)IrCl () via reaction with -chlorosuccinimide, and exposure of to CO produced (PBP)IrCl(CO) ().

Parahydrogen Polarization in Reverse Micelles and Application to Sensing of Protein-Ligand Binding.

A medium containing reverse micelles supports non-hydrogenative parahydrogen induced polarization (nhPHIP) in the organic phase while solubilizing a protein in the aqueous phase. Strongly enhanced NMR signals from iridium hydride complexes report on a ligand, 4-amino-2-benzylaminopyrimidine, which crosses the phase boundary and interacts with the thiaminase protein TenA. The calculation of binding equilibria reveals a of 39.

Chromatin folding through nonuniform motorization by responsive motor proteins.

Chromatin is partially structured through the effects of biological motors. "Swimming motors" such as RNA polymerases and chromatin remodelers are thought to act differentially on the active parts of the genome and the stored inactive part. By systematically expanding the many-body master equation for chromosomes driven by swimming motors, we show that this nonuniform aspect of motorization leads to heterogeneously folded conformations, thereby contributing to chromosome compartmentalization.

Correction: Ion pair extractant selective for LiCl and LiBr.

[This corrects the article DOI: 10.1039/D4SC03760J.].

Tetrapodal iron complexes invoke observable intermediates in nitrate and nitrite reduction.

This study investigates the mechanistic pathways of nitrate and nitrite reduction by the tetrapodal iron complex [PyPy(afa)Fe]OTf, revealing key intermediates to elucidate the reaction process. Using UV-Vis, IR, mass and NMR spectroscopies, stable binding of oxyanions to the iron centre was observed, supporting the formation of the iron(iii)-hydroxide intermediate [PyPy(afa)Fe(OH)]OTf. This intermediate is less stable than in previous systems, providing insights into the behaviour of metalloenzymes.

Palladium-Catalyzed -Selective Arylation of 1-Naphthamide.

Remote C4-H functionalization of -naphthoic acids is highly challenging due to the presence of proximally more accessible C-H bonds at the C2 and C8 positions. Herein, we report the first palladium-catalyzed direct C4 arylation of 1-naphthamides with high regioselectivity and excellent functional group compatibility. Diverse aryl couples were found to be compatible with C4 arylation.

Mn and Zn-Doped Multivariate Metal-Organic Framework as a Metalloimmunological Adjuvant to Promote Protection Against Tuberculosis Infection.

A first-in-class vaccine adjuvant delivery system, Mn-ZIF, is developed by incorporating manganese (Mn) into the zinc-containing zeolitic-imidazolate framework-8 (ZIF-8). The mixed metal approach, which allowed for tunable Mn doping, is made possible by including a mild reducing agent in the reaction mixture. This approach allows up to 50% Mn, with the remaining 50% Zn within the ZIF.

A Review on Hepatoprotective Effect of Chrysin: Preclinical Implications and Molecular Cascades Came into Focus.

Chrysin, a flavone nutraceutical, possesses several beneficial pharmacological properties, which has gained much emphasis in recent years. The biological effects of chrysin are exerted due to impeding or activating multifarious cellular and molecular pathways. Our findings indicated that chrysin inhibited tumor progression in various cancer cell lines by repressing the formation of a sphere and upregulated protein expression of Src homology region 2 domain-containing phosphatase-1 (SHP-1), alleviating phosphorylated-signal transducer and activator of transcription 3 (p-STAT3) and transaction workflow innovation standards team1 (Twist1), sustaining phosphorylation of extracellular signal-regulated kinase 1/2 (ERK1/2) and endorsing mitogen-activated protein kinase kinase1 (MEK1) overexpression, increasing the cytochrome c release, mitochondrial reactive oxygen species (ROS) formation, matrix metalloproteinases (MMP) collapse, and caspase-3 activity, modulating p53/ B-cell lymphoma-2 (Bcl-2)/caspase-9 cascade, cyclooxygenase- 2 (COX-2), nuclear factor kappa B proposition 65 (NF-kB p65) expression and also decreasing the expression of nuclear factor erythroid 2-related factor 2 (Nrf2).

Kilogram Flash Joule Heating Synthesis with an Arc Welder.

Flash Joule heating has been used as a versatile solid-state synthesis method in the production of a wide range of products, including organic, inorganic, and ceramic products. Conventional flash Joule heating systems are large and customized, presenting significant barriers in the cost of assembly, the expertise needed to operate, and uniformity of results between different systems. Even laboratory-scale flash Joule heating systems struggle to operate above 10 g capacity, and they suffer from poor temperature controllability.

Nuclear GTPSCS functions as a lactyl-CoA synthetase to promote histone lactylation and gliomagenesis.

Histone lysine lactylation is a physiologically and pathologically relevant epigenetic pathway that can be stimulated by the Warburg effect-associated L-lactate. Nevertheless, the mechanism by which cells use L-lactate to generate lactyl-coenzyme A (CoA) and how this process is regulated remains unknown. Here, we report the identification of guanosine triphosphate (GTP)-specific SCS (GTPSCS) as a lactyl-CoA synthetase in the nucleus.

Ultrathin rubbery bio-optoelectronic stimulators for untethered cardiac stimulation.

Untethered electrical stimulation or pacing of the heart is of critical importance in addressing the pressing needs of cardiovascular diseases in both clinical therapies and fundamental studies. Among various stimulation methods, light illumination-induced electrical stimulation via photoelectric effect without any genetic modifications to beating cells/tissues or whole heart has profound benefits. However, a critical bottleneck lies in the lack of a suitable material with tissue-like mechanical softness and deformability and sufficient optoelectronic performances toward effective stimulation.

Sequence complexity and monomer rigidity control the morphologies and aging dynamics of protein aggregates.

Understanding the biophysical basis of protein aggregation is important in biology because of the potential link to several misfolding diseases. Although experiments have shown that protein aggregates adopt a variety of morphologies, the dynamics of their formation are less well characterized. Here, we introduce a minimal model to explore the dependence of the aggregation dynamics on the structural and sequence features of the monomers.

In vivo scanning laser fundus and high-resolution OCT imaging of retinal ganglion cell injury in a non-human primate model with an activatable fluorescent-labeled TAT peptide probe.

The optical imaging agent TcapQ488 has enabled imaging of retinal ganglion cell (RGC) injury in vivo in rodents and has potential as an effective diagnostic probe for early detection and intervention monitoring in glaucoma patients. In the present study, we investigated TcapQ488 in non-human primates (NHPs) to identify labeling efficacy and early signals of injured RGC, to determine species-dependent changes in RGC probe uptake and clearance, and to determine dose-limiting toxicities. Doses of 3, 6, and 12 nmol of TcapQ488 were delivered intravitreally to normal healthy NHP eyes and eyes that had undergone hemiretinal endodiathermy axotomy (HEA) in the inferior retina.

Fully atomistic molecular dynamics modeling of photoswitchable azo-PC lipid bilayers: structure, mechanical properties, and drug permeation.

Phospholipid based vesicles called liposomes are commonly used as packaging in advanced drug delivery applications. Stimuli-responsive liposomes have been designed to release their contents under certain conditions, for example through heating or illumination. However, in the case of photosensitive liposomes based on azo-PC, namely phosphatidylcholine lipids with azobenzene incorporated into one of the two lipid tails, the release mechanism is not known.