Pridgenbarr9052

Molten salts are promising reaction media candidates for the discovery of novel materials; however, they offer little control over oxidation state compared to aqueous solutions. Here, we demonstrated that when two hydroxides are mixed, their melts become fluxes with tunable solubility, which are surprisingly powerful solvents for ternary chalcogenides and offer effective paths for crystal growth to new compounds. We report that precise control of the oxidation state of Ni is achievable in mixed molten LiOH/KOH to grow single crystals of all known ternary K-Ni-S compounds. It is also possible to access several new phases, including a new polytope of β-K2Ni3S4, as well as low-valence KNi4S2 and K4Ni9S11. KNi4S2 is a two-dimensional low-valence nickel-rich sulfide, and β-K2Ni3S4 has a hexagonal lattice. Moreover, using KNi4S2 as a template, we obtained a new layered binary Ni2S by topotactic deintercalation of K. The new binary Ni2S has a van der Waals gap and can function as a new host layer for intercalation chemistry, as demonstrated by the intercalation of LiOH between its layers. The oxidation states of low-valence KNi4S2 and Ni2S were studied using X-ray absorption spectroscopy and X-ray photoelectron spectroscopy. Density functional theory calculations showed large antibonding interactions at the Fermi level for both KNi4S2 and Ni2S, corresponding to the flat-bands with large Ni-dx2-y2 character.Elucidating the nature, strength, and siting of acid sites in zeolites is fundamental to fathom their reactivity and catalytic behavior. Despite decades of research, this endeavor remains a major challenge. Trimethylphosphine oxide (TMPO) has been proposed as a reliable probe molecule to study the acid properties of solid acid catalysts, allowing the identification of distinct Brønsted and Lewis acid sites and the assessment of Brønsted acid strengths. Recently, doubts have been raised regarding the assignment of the 31P NMR resonances of TMPO-loaded zeolites. Here, it is shown that a judicious control of TMPO loading combined with two-dimensional 1H-31P HETCOR solid-state NMR, DFT, and ab initio molecular dynamics (AIMD)-based computational modeling provides an unprecedented atomistic description of the host-guest and guest-guest interactions of TMPO molecules confined within HZSM-5 molecular-sized voids. 31P NMR resonances usually assigned to TMPO molecules interacting with Brønsted sites of different acid strength arise instead from both changes in the probe molecule confinement effects at ZSM-5 channel system and the formation of protonated TMPO dimers. Moreover, DFT/AIMD shows that the 1H and 31P NMR chemical shifts strongly depend on the siting of the framework aluminum atoms. This work overhauls the current interpretation of NMR spectra, raising important concerns about the widely accepted use of probe molecules for studying acid sites in zeolites.Inspired by the induced-fit mechanism in nature, we developed the process of water-induced self-assembly (WISA) to make water an active substrate that regulates the self-assembly and function of amphiphilic discotic molecules (ADMs). The ADM is an isotropic liquid that self-assembles only when in contact with water. Characterization results indicate that water fits into the hydrophilic core of the ADMs and induces the formation of a hexagonal columnar phase (Colh), where each column contains a hydrated artificial water channel (AWC). The hydrated AWCs are adaptive rather than static; the dynamic incorporation/removal of water results in the reversible assembly/disassembly of the adaptive AWCs (aAWCs). Furthermore, its dynamic characteristics can enable water to act as an orientation-directional guest molecule that controls the growth direction of the aAWCs. Well-aligned aAWC arrays that showed the ability of water transport were obtained via a "directional WISA" method. In WISA, water thus governs the supramolecular chemistry and function of synthetic molecules as it does with natural materials. By making water an active component in adaptive chemistry and enabling host molecules to dynamically interact with water, this adaptive aquatic material may motivate the development of synthetic molecules further toward biomaterials.Four copper(I) alkynyl complexes incorporating phosphate ligands, namely, [Cu16(tBuC≡C)12(PhOPO3)2]n (1; PhOPO3 = phenyl phosphate), [Cu16(tBuC≡C)12(1-NaphOPO3)2]n (2; 1-NaphOPO3 = 1-naphthyl phosphate), [VO4@Cu25(tBuC≡C)19(1-NaphOPO3)](PF6)0.5(F)0.5 (3), and [PO4@Cu25(tBuC≡C)19(1-NaphOPO3)](PF6)0.5(F)0.5 (4), were solvothermally synthesized and well-characterized by IR spectroscopy, powder X-ray diffraction, and single-crystal X-ray diffraction. Single-crystal X-ray analysis revealed that the Cu16 cluster-based coordination chain polymers 1 and 2 are formed by assembly during crystallization, while 3 and 4 contain high-nuclearity copper(I) composite clusters enclosing orthovanadate and phosphate template ions, respectively, that are supported by ROPO32- ligands. Complexes 1-4 exhibit crystallization-induced emission enhancement. Their crystalline state shows strong luminescence, in striking contrast to the weak emission of the amorphous state and solution phase. A detailed investigation of the crystal structure suggests that well-arranged C-H···π and π···π interactions between the ligands are the major factors for this enhanced emission. Clusters 3 and 4 also exhibit photocurrent responses upon visible-light illumination.Many Staphylococcus bacteria are pathogenic and harmful to humans. Noticeably, some Staphylococcus, including vancomycin-resistant S. aureus (VRSA), have become notoriously resistant to antibiotics and have spread rapidly, becoming threats to public health. Here, we designed a dual fluorescent probe scheme combining siderophores and antibiotics as the guiding units to selectively target VRSA and vancomycin-sensitive S. aureus (VSSA) in complex bacterial samples. Siderophore-mediated iron uptake is the key pathway by which S. aureus acquires iron in limited environments. Therefore, the siderophore-derivative probe could differentiate between S. aureus and other bacteria. Moreover, by fine-tuning the vancomycin-derivative probes, we could selectively target only VSSA, further differentiating VRSA and VSSA. Finally, by combining the siderophore-derivative probe and the vancomycin-derivative probe, we successfully targeted and differentiated between VRSA and VSSA in complicated bacterial mixtures.Novel methods to synthesize electron-deficient π-conjugated polymers utilizing transition-metal-free coupling reactions for the use of nonfunctionalized monomers are attractive due to their improved atom economy and environmental prospective. Herein we describe the use of iPrMgCl·LiCl complex to afford thiazole-based conjugated polymers in the absence of any transition metal catalyst, that enables access to well-defined polymers with good molecular weights. The mechanistically distinct polymerizations proceeded via nucleophilic aromatic substitution (SNAr) reaction supported by density functional theory (DFT) calculations. This work demonstrates the first example of fully conjugated thiazole-based aromatic homopolymers without the need of any transition metal catalyst.The detection of SO2 and its derivatives is indispensable for monitoring atmospheric, water quality, and biological fluctuation of oxidative stress and metabolism of biothiols within native cellular contexts. In this article, the brush copolymer nanoreactors containing amine-terminated PDMS were used to encapsulate the fluorescent indicator C11-BDP, forming sulfite-sensitive nanoreactors (ssNRs). Surprisingly, the ssNRs were found to be highly selective to sulfite over a range of reactive oxygen/nitrogen/sulfur species and anions, which was not observed with freely dissolved indicators. The ssNRs showed a rapid response (t95 = 65 s), an excellent detection limit (0.7 μM), and a very high sensitivity (ca. 1000-fold ratiometric intensity change) to sulfite. For cellular studies, the ssNRs exhibited negligible toxicity and could be endocytosed into endosomes and lysosomes. Finally, the ssNRs allowed us to visualize the different responses of three different types of cells (pre-adipocytes, RAW264.7, and HeLa cells) to external stimuli in the culture media with sulfites and lipopolysaccharides.

Septic cardiomyopathy is a common complication of sepsis with high morbidity and mortality, but lacks specific therapy. This study aimed to reveal the role of circTLK1 and its potential mechanisms in septic cardiomyopathy.

The in vitro and in vivo models of septic cardiomyopathy were established. Cell viability and apoptosis were detected by CCK8, TUNEL and flow cytometry, respectively. LDH, CK, SOD, MDA, ATP, 8-OHdG, NAD+/NADH ratio, ROS level, mitochondrial membrane potential and cytochrome C distribution were evaluated using commercial kits. qRT-PCR and western blotting were performed to detect RNA and protein levels. Mitochondrial DNA (mtDNA) copy number and transcription were assessed by quantitative PCR. Dual-luciferase assay, RNA immunoprecipitation and co-immunoprecipitation were performed to verify the interaction between circTLK1/PARP1 and miR-17-5p.

CircTLK1, PARP1 and HMGB1 were up-regulated in the in vitro and in vivo models of septic cardiomyopathy. CircTLK1 inhibition restrained LPS-induced up-regulation of PARP1 and HMGB1. Moreover, circTLK1 knockdown repressed sepsis-induced mtDNA oxidative damage, mitochondrial dysfunction and consequent cardiomyocyte apoptosis by inhibiting PARP1/HMGB1 axis in vitro and in vivo. In addition, circTLK1 enhanced PARP1 expression via sponging miR-17-5p. MEK inhibitor Inhibition of miR-17-5p abolished the protective effects of circTLK1 silencing on oxidative mtDNA damage and cardiomyocyte apoptosis.

CircTLK1 sponged miR-17-5p to aggravate mtDNA oxidative damage, mitochondrial dysfunction and cardiomyocyte apoptosis via activating PARP1/HMGB1 axis during sepsis, indicating that circTLK1 may be a putative therapeutic target for septic cardiomyopathy.

CircTLK1 sponged miR-17-5p to aggravate mtDNA oxidative damage, mitochondrial dysfunction and cardiomyocyte apoptosis via activating PARP1/HMGB1 axis during sepsis, indicating that circTLK1 may be a putative therapeutic target for septic cardiomyopathy.Pancreatic ductal adenocarcinoma (PDAC) is the most common cancer of the exocrine part of the pancreas with poor prognosis. Up to 85% of PDAC patients are diagnosed with diabetes or hyperglycaemia at the time of diagnosis indicating that impaired glucose homeostasis is a common event in this cancer. A mechanism of association between PDAC and diabetes is very complex and still not fully understood. Currently, the various classes of anti-diabetic drugs are used in diabetes treatment. It is possible that specific types of anti-diabetic drugs for diabetes may have different impacts on pancreatic cancer development. Moreover, the intriguing question of whether diabetes can facilitate PDAC development remains unanswered. This paper presents the results of recent studies on the effect of the anti-diabetic treatment used on pancreatic cancer risk in diabetic patients.Single-plate fixation bridging bone defects provokes nonunion and risks plate-fatigue failure due to under- dimensioned implants. Adding a helical plate to bridge the fracture increases stiffness and balances load sharing. This study compares the stiffness and plate surface strain of different constructs in a transverse contact and gap femoral shaft fracture model. Eight groups of six synthetic femora each were formed intact femora; intact femora with lateral locking plate; contact and gap transverse shaft osteotomies each with lateral locking plate, lateral locking plate and helical locking plate, and long proximal femoral nail. Constructs underwent non-destructive quasi-static axial and torsional loading. Plate surface strain evaluation was performed under 200 N axial loading. Constructs with both lateral and helical plates demonstrated similar axial and torsional stiffness- independent of the contact or gap situations - being significantly higher compared to lateral plating (p less then 0.01). Torsional stiffness of the constructs, with both lateral and helical plates in the gap situation, was significantly higher compared to this situation stabilised by a nail (p less then 0.