Theoretical investigations of 2-vinylpyridine stereoselective polymerization catalyzed by cationic yttrium complexes with different ancillary ligands.

The polymerization mechanism of 2-vinylpyridine catalyzed by cationic yttrium complexes with diverse ancillary ligands, specifically [L1Y(CH2SiMe3)(THF)]+ [L1 = (2,6-Et2C6H3)NC(Me)CHC(Me)N(2,6-Et2C6H3)] (Y-1), [L2Y(CH2SiMe3)(THF)]+ [L2 = (2,6-Cl2C6H3)NC(Me)CHC(Me)N(2,6-Cl2C6H3)] (Y-2), and [L3Y(CH2SiMe3)(THF)]+ [L3 = (2,6-C6H5)NC(Me)CHC(Me)N(2,6-iPr2C6H3)] (Y-3), was studied using density functional theory (DFT) calculations. Having achieved an agreement between theory and experiment, it is found that isotactic selectivity induced by Y-1 or Y-2 results from a combination of smaller deformation of the catalyst and stronger electronic effects. Conversely, the Y-3 complex exhibits comparable energy barriers for proceeding via either isotactic or syndiotactic pathways, aligning with the production of atactic polymers as seen experimentally. To examine the steric effects on the kinetic and thermodynamic properties, a computational model of an analogue complex [L4Y(CH2SiMe3)(THF)]+ [L4 = (2,6-Cl2C6H3)NC(Me)CHC(Me)N(iPr2C6H3)] (Y-4), featuring increased steric hindrance, was analyzed. Distortion-interaction and topographic steric map analyses further affirmed that steric hindrance significantly influences stereoselectivity. A direct relationship was identified between the energy barriers of isotactic insertion transition states and the bulkiness of ancillary ligands; greater distortion energy of the catalyst correlates with higher barriers for isotactic polymerization. These findings enhance the mechanistic comprehension of 2-vinylpyridine polymerization and are expected to contribute valuable insights for the improvement of catalytic polymerization systems of 2-vinylpyridine.

RBM25 binds to and regulates alternative splicing levels of Slc38a9, Csf1, and Coro6 to affect immune and inflammatory processes in H9c2 cells.

Background: Alternative splicing (AS) is a biological process that allows genes to be translated into diverse proteins. However, aberrant AS can predispose cells to aberrations in biological mechanisms. RNA binding proteins (RBPs), closely affiliated with AS, have gained increased attention in recent years. Among these RBPs, RBM25 has been reported to participate in the cardiac pathological mechanism through regulating AS; however, the involvement of RBM25 as a splicing factor in heart failure remains unclarified. Methods: RBM25 was overexpressed in H9c2 cells to explore the target genes bound and regulated by RBM25 during heart failure. RNA sequencing (RNA-seq) was used to scrutinize the comprehensive transcriptional level before identifying AS events influenced by RBM25. Further, improved RNA immunoprecipitation sequencing (iRIP-seq) was employed to pinpoint RBM25-binding sites, and RT-qPCR was used to validate specific genes modulated by RBM25. Results: RBM25 was found to upregulate the expression of genes pertinent to the inflammatory response and viral processes, as well as to mediate the AS of genes associated with cellular apoptosis and inflammation. Overlap analysis between RNA-seq and iRIP-seq suggested that RBM25 bound to and manipulated the AS of genes associated with inflammation in H9c2 cells. Moreover, qRT-PCR confirmed Slc38a9, Csf1, and Coro6 as the binding and AS regulatory targets of RBM25. Conclusion: Our research implies that RBM25 plays a contributory role in cardiac inflammatory responses via its ability to bind to and regulate the AS of related genes. This study offers preliminary evidence of the influence of RBM25 on inflammation in H9c2 cells.

Mechanism and Origin of Site Selectivity and Regioselectivity of Scandium-Catalyzed Benzylic C-H Alkylation of Tertiary Anilines with Alkenes.

Benzylic C(sp3)-H alkylation of tertiary anilines with alkenes by an anilido-oxazoline-ligated scandium alkyl catalyst was recently reported with C-H site selectivity and alkene-dependent regioselectivity. Revealing the mechanism and origin of selectivity is undoubtedly of great importance for understanding experimental observations and developing new reactions. Herein, density functional theory (DFT) calculations have been carried out on the model reaction of Sc-catalyzed benzylic C(sp3)-H alkylation of N,N-dimethyl-o-toluidine with allylbenzene. The reaction generally undergoes the generation of active species, alkene insertion, and protonation steps. The difference of the distortion energy of the aniline moiety in transition states, which is related to the ring size of the forming metallacycles, accounts for the site selectivity of C-H activation. Benzylic C(sp3)-H activation possessing less strained five-membered metallacycle compared to the ortho-C(sp2)-H and α-methyl C(sp3)-H activation results in benzylic C(sp3)-H alkylation observed experimentally. Both steric and electronic factors are responsible for the 1,2-insertion regioselectivity for alkyl-substituted alkenes, while electronic factors control the 2,1-insertion manner for vinylsilanes. The analysis of original alkene substrates further strengthens the understanding of the alkene-dependent regioselectivity. These results help us to obtain the mechanistic understanding and are expected to be conducive to the development of new C-H functionalization reactions.

The charge-transfer states and excitation energy transfers of halogen-free organic molecules from first-principles many-body Green's function theory.

The organic solar cells based on halogen-free components, have been the new favorites to develop green and renewable energy. PBDB-T and its derivatives are considered the superior electron donors to construct the solar cells. Although there are plenty of researches about them, the charge-transfer mechanisms and excitation energy transfers of relative organic solar cells are still unclear, the developments of photovoltaic devices are restricted consequently. In this work, we calculate the electronic structures and excited-state properties of PBDB-T, PBT1-C, PBT1-O and PBT1-S donors in the gas phase from the many-body Green's function theory. With BTP-IC and BTP-IS as the acceptors, we consider the Förster, Dexter, and overlap electronic couplings to compute the excitation energy transfers of the dimers. The ionization energies and excited-state energies of the four donors calculated by GW + BSE are in good agreement with experiments, and they are sensitive to the functionals in the computation. We find two charge transfer schemes. The thienyl of PBDB-T molecule makes its charge-transfer state at the lowest energy, and the total electronic coupling of PBDB-T based dimer is the strongest. The Dexter, and overlap types electronic couplings are significant to study the excitation energy transfer of organic heterojunctions. We provide a theoretical guide in the design and synthesis of higher-performance halogen-free donors.

Thermodynamic and Dynamic Modeling of the Boron Species in Aqueous Potassium Borate Solution.

The concentration of B(OH)3, B(OH)4 -, B3O3(OH)4 -, and B4O5(OH)4 2- in the solution and the solubilities in the system KCl-K2SO4-K2B4O7-H2O and its subsystems were calculated on the basis of the Pitzer model. The mole fraction of the four boron species is mainly affected by m(B) in the solution but less by m(Cl-) and m(SO4 2-). m(Cl-) and m(SO4 2-) mainly affect the solubility of K2B4O5(OH)4·2H2O. The calculated solubilities in the system KCl-K2B4O7-H2O agree well with the experimental data. The results show that the standard chemical potentials of K2B4O5(OH)4·2H2O at 298.15 K obtained in this work is reliable. The transformation between the boron species at 298.15 K was also conducted with the density functional theory (DFT) method. The results affirm that the boron species can transform other boron species as the boron concentration in the solution changes.

Visible Light-Induced Aerobic Epoxidation of α,ß-Unsaturated Ketones Mediated by Amidines.

An aerobic photoepoxidation of α,ß-unsaturated ketones driven by visible light in the presence of tetramethylguanidine (3b), tetraphenylporphine (H2TPP), and molecular oxygen under mild conditions was revealed. The corresponding α,ß-epoxy ketones were obtained in yields of up to 94% in 96 h. The reaction time was shortened to 4.6 h by flow synthesis. The mechanism related to singlet oxygen was supported by experiments and density functional theory (DFT) calculations.

Impact of Dexmedetomidine on Intraoperative Wake-Up Tests in Patients Undergoing Spinal Surgery.

PURPOSE: To evaluate the impact of dexmedetomidine (DEX) on intraoperative wake-up tests. DESIGN: American Society of Anesthesiologists category I or II patients were divided into two groups: a propofol-remifentanil group (group R, n = 20) and a DEX-propofol-remifentanil group (group D, n = 20). METHODS: The patients in group D received DEX, whereas the patients in group R received the same volume of saline. The other anesthetic methods and drugs (propofol and remifentanil) were the same in both groups. During the wake-up test, patients were repeatedly asked to move their fingers. FINDINGS: All the wake-up tests were successfully performed. There was no significant difference in the mean wake-up time between the two groups. Eighteen patients exhibited better wake-up quality in group D as did eight patients in group R. The patients in group D had a significantly better overall wake-up quality than those in group R (P <.05). CONCLUSIONS: DEX did not affect the wake-up time and increased the wake-up quality.

Simultaneous Modulation of Magnetic and Dielectric Transition via Spin-Crossover-Tuned Spin Arrangement and Charge Distribution.

Magnetic and dielectric properties have been tuned simultaneously by external stimuli with rapid and sensitive response, which is crucial to monitor the magnetic state via capacitive measurement. Herein, positive charged FeII ions were linked via negative charged [(Tp)FeIII (CN)3 ]- (Tp=hydrotris(pyrazolyl)borate) units to form a neutral chain. The spin-crossover (SCO) on FeII sites could be sensitively triggered via thermal treatment, light irradiation, and pressure. SCO switched the spin state of the FeII ions and antiferromagnetic interactions between FeIII and FeII ions, resulting in significant change in magnetization. Moreover, SCO induced rotation of negative charged [(Tp)FeIII (CN)3 ]- units, generating dielectric anomaly due to geometric change of charges distribution. This work provides a rational way to manipulate simultaneous variations in magnetic and dielectric properties utilizing SCO as an actuator to tune spin arrangement, magnetic coupling, and charge distribution.

Impact of dexmedetomidine on amino acid contents and the cerebral ultrastructure of rats with cerebral ischemia-reperfusion injury.

PURPOSE:: To investigate the effects of dexmedetomidine (DEX) on amino acid contents and the cerebral ultrastructure of rats with cerebral ischemia-reperfusion injury (I/R). METHODS:: Thirty-six, male, Wistar rats were randomly divided into three groups: the sham operation group (group C), the ischemia-reperfusion group (group I/R), and the DEX group (group D). The middle cerebral artery occlusion model was prepared by the modified Longa method. The time of ischemia was 180 min, and 120 min after reperfusion, the amount of glutamate (Glu), and γ-aminobutyric acid (GABA) in the brain were measured, and the ultrastructure-level changes in the cerebral cortex were examined using electron microscopy. RESULTS:: Compared to group C, Glu contents in group D, and I/R significantly increased. Compared to group I/R, Glu contents in group D significantly decreased. Compared to group C, GABA contents in group D, and I/R significantly increased, and those in group D significantly increased, as compared to group I/R. The cerebral ultrastructure was normal in group C. Vacuolar degeneration in the plastiosome and nervous processes, was more critical than in group D. Vascular endothelial cells (VEC) were damaged. On the contrary, these changes in group D significantly improved. CONCLUSION:: Dexmedetomidine is capable of decreasing glutamergic content, and increasing GABAergic content, in order to decrease the injury of the cerebral ultrastructure, following cerebral ischemia-reperfusion injury.

Impact of dexmedetomidine on amino acid contents and the cerebral ultrastructure of rats with cerebral ischemia-reperfusion injury

Abstract Purpose: To investigate the effects of dexmedetomidine (DEX) on amino acid contents and the cerebral ultrastructure of rats with cerebral ischemia-reperfusion injury (I/R). Methods: Thirty-six, male, Wistar rats were randomly divided into three groups: the sham operation group (group C), the ischemia-reperfusion group (group I/R), and the DEX group (group D). The middle cerebral artery occlusion model was prepared by the modified Longa method. The time of ischemia was 180 min, and 120 min after reperfusion, the amount of glutamate (Glu), and γ-aminobutyric acid (GABA) in the brain were measured, and the ultrastructure-level changes in the cerebral cortex were examined using electron microscopy. Results: Compared to group C, Glu contents in group D, and I/R significantly increased. Compared to group I/R, Glu contents in group D significantly decreased. Compared to group C, GABA contents in group D, and I/R significantly increased, and those in group D significantly increased, as compared to group I/R. The cerebral ultrastructure was normal in group C. Vacuolar degeneration in the plastiosome and nervous processes, was more critical than in group D. Vascular endothelial cells (VEC) were damaged. On the contrary, these changes in group D significantly improved. Conclusion: Dexmedetomidine is capable of decreasing glutamergic content, and increasing GABAergic content, in order to decrease the injury of the cerebral ultrastructure, following cerebral ischemia-reperfusion injury.

Enantioselective α-Hydroxylation by Modified Salen-Zirconium(IV)-Catalyzed Oxidation of ß-Keto Esters.

The highly enantioselective α-hydroxylation of ß-keto esters using cumene hydroperoxide (CHP) as the oxidant was realized by a chiral (1S,2S)-cyclohexanediamine backbone salen-zirconium(IV) complex as the catalyst. A variety of corresponding chiral α-hydroxy ß-keto esters were obtained in excellent yields (up to 99%) and enantioselectivities (up to 98% ee). The zirconium-catalyzed enantioselective α-hydroxylation of ß-keto esters was scalable, and the zirconium catalyst was recyclable. The reaction can be performed in gram scale, and corresponding chiral products were acquired in 95% yield and 99% ee.

DFT Studies on cis-1,4-Polymerization of Dienes Catalyzed by a Cationic Rare-Earth Metal Complex Bearing an Ancillary PNP Ligand.

Dnsity functional theory (DFT) calculations have been carried out for the highly selective cis-1,4-polymerization of butadiene catalyzed by a cationic rare-earth metal complex bearing an ancillary PNP ligand. It has been found that the chain initiation and propagation of butadiene polymerization occurs via the favorable cis-1,4-insertion route. The trans-1,4 and 1,2-insertion are unfavorable both kinetically and thermodynamically. The chain growth follows the π-allyl-insertion mechanism. The analyses of energy decomposition of transition states indicate that the likelihood of rival insertion pathways is predominantly controlled by the interaction energy of butadiene with a metal center and the deformation energy of butadiene moiety. The electronic factor of the central metal has a decisive influence on the cis- vs. trans-insertion and the regioselectivity (cis-1,4- vs. cis-1,2-insertion) is mainly determined by steric hindrance. Tetrahydrofuran (THF) coordination made monomer insertion less favorable compared with THF-free case and had more noticeable impact on the trans-monomer insertion compared with the cis case. During the chain propagation, cis-insertion of monomer facilitates THF de-coordination and the THF molecule could therefore dissociate from the central metal.

Chiral Phosphorus-Olefin Ligands for the Rh(I) -Catalyzed Asymmetric Addition of Aryl Boronic Acids to Electron-Deficient Olefins.

New chiral phosphorus-olefin hybrid ligands derived from the rigid "privileged" l-proline have been conveniently prepared and applied in the rhodium-catalyzed asymmetric arylation of electron-deficient olefins with arylboronic acids at room temperature; this reaction provides the desired products in excellent yields and high enantioselectivities. The origin of observed stereoselectivity has been investigated by density functional theory (DFT) calculations.