A mechanistic study of chiral manganese porphyrin-catalyzed enantioselective C-H hydroxylation reaction.

We employed density functional theory (DFT) calculations to elucidate the mechanism and origin of enantioselectivity in the C-H hydroxylation reaction catalyzed by a chiral manganese porphyrin complex. Our study reveals that the chiral manganese porphyrin forms a two-point hydrogen bonding interaction with the substrate. Specifically, the hydrogen atom abstraction of the methylene -() C-H bond at the heterocyclic C-3 position is 1.

Synthesis, Structural Characterization, and Hirschfeld Surface Analysis of a New Cu(II) Complex and Its Role in Photocatalytic CO Reduction.

A new Cu(II) complex, [CuLL(CHCOO)(HO)]·HO, was synthesized by the reaction of Cu(CHCOO)·HO, 6-phenylpyridine-2-carboxylic acid (HL), and 4-[5-(pyridin-4-yl)-1,3,4-oxadiazol-2-yl]pyridine (L) in ethanol-water (: = 1:1) solution. The Cu(II) complex was characterized using elemental analysis, IR, UV-vis, TG-DTA, and single-crystal X-ray analysis. The fluorescence properties of the copper complex were also evaluated.

Synthesis, Structural Characterization, Hirschfeld Surface Analysis, Density Functional Theory, and Photocatalytic CO Reduction Activity of a New Ca(II) Complex with a Bis-Schiff Base Ligand.

A new bis-Schiff base (L) Ca(II) complex, CaL, was synthesized by the reaction of calcium perchlorate tetrahydrate, 1,3-diamino-2-hydroxypropane, and 2-formyl phenoxyacetic acid in an ethanol-water (v:v = 2:1) solution and characterized by IR, UV-vis, TG-DTA, and X-ray single crystal diffraction analysis. The structural analysis indicates that the Ca(II) complex crystallizes in the monoclinic system, space group 12/1, and the Ca(II) ions are six-coordinated with four O atoms (O8, O9, O11, O12, or O1, O2, O4, O6) and two N atoms (N1, N2, or N3, N4) of one bis-Schiff base ligand. The Ca(II) complex forms a tetramer by intermolecular O-HO hydrogen bonds.

Synthesis, Structural Characterization, Hirschfeld Surface Analysis and Photocatalytic CO Reduction Activity of a New Dinuclear Gd(III) Complex with 6-Phenylpyridine-2-Carboxylic Acid and 1,10-Phenanthroline Ligands.

A new dinuclear Gd(III) complex was synthesized and named [Gd(L)(Phen)(HO)(DMF)]·2HO·2Cl (). Here, L is the 6-phenylpyridine-2-carboxylate anion, Phen represents 1,10-phenanthroline, DMF is called -dimethylformamide, and Cl is the chloride anion, which is characterized by IR and single crystal X-ray diffraction analysis. The structural analysis reveals that complex () is a cation-anion complex, and each Gd(III) ion is eight-coordinated with four O atoms (O1, O5, O2a, O4a, or O1a, O2, O4, O5a) of four different bidentate L ligands, two O atoms (O6, or O6a) of DMF molecules, two N atoms (N1, N2, or N1a, N2a) of Phen ligands, and two O atoms (O3 or O3a) of coordinated water molecules.

A Phase II Study of Osimertinib in Patients with Advanced-Stage Non-Small Cell Lung Cancer following Prior Epidermal Growth Factor Receptor Tyrosine Kinase Inhibitor (EGFR TKI) Therapy with EGFR and T790M Mutations Detected in Plasma Circulating Tumour DNA (PLASMA Study).

Epidermal growth factor receptor () T790M mutations drive resistance in 50% of patients with advanced non-small cell lung cancer (NSCLC) who progress on first/second generation (1G/2G) EGFR tyrosine kinase inhibitors (TKIs) and are sensitive to Osimertinib. Tissue sampling is the gold-standard modality of T790M testing, but it is invasive. We evaluated the efficacy of Osimertinib in patients with EGFR mutant NSCLC and T790M in circulating tumour DNA (ctDNA).

Evaluation of a Sample-to-Result POCKIT Central SARS-CoV-2 PCR System.

The emergence of COVID-19 has caused unprecedented impacts on global public health and many other aspects. Meanwhile, many types of methods have been developed to detect the causative agent, SARS-CoV-2; this has greatly advanced the technologies in the diagnostic field. Here, we describe the development and validation of a sample-in-result-out POCKIT Central SARS-CoV-2 PCR system for detecting SARS-CoV-2 in comparison with a commercial reference real-time RT-PCR assay (TaqPath COVID-19 Combo Kit).

Mechanism of Preferential Hydrogenation of Hydroxymethyl Group to Aldehyde Group in 5-Hydroxymethylfurfural over W C-Based Catalyst.

A W C cluster was used to model a W C catalyst with the armchair model of activated carbon support, noted as W C /AC. Over W C /AC, the mechanism for the hydrogenation of both -H OH and -CHO groups in 5-hydroxymethylfurfural (HMF) was theoretically studied in tetrahydrofuran at GGA-PBE/DNP level. 5-Methylfurfural was the major product from only hydrodehydration of the -CH OH group, whereas 2,5-dihydroxymethylfuran was the minor product from the hydrogenation of both -CH OH and -CHO groups.

Long-term efficacy and safety of eladocagene exuparvovec in patients with AADC deficiency.

Aromatic L-amino acid decarboxylase deficiency results in decreased neurotransmitter levels and severe motor dysfunction. Twenty-six patients without head control received bilateral intraputaminal infusions of a recombinant adeno-associated virus type 2 vector containing the human aromatic L-amino acid decarboxylase gene (eladocagene exuparvovec) and have completed 1-year evaluations. Rapid improvements in motor and cognitive function occurred within 12 months after gene therapy and were sustained during follow-up for >5 years.

CXCL2 combined with HVJ-E suppresses tumor growth and lung metastasis in breast cancer and enhances anti-PD-1 antibody therapy.

Breast cancer has a high risk of metastasis; however, no effective treatment has been established. We developed a novel immunotherapy for breast cancer to enhance cytotoxic T lymphocytes against cancer cells using N1-type neutrophils with anti-tumor properties. For this purpose, we combined CXCL2 (CXC chemokine ligand 2) plasmid DNA with inactivated Sendai virus (hemagglutinating virus of Japan)-envelope (HVJ-E).

Exploiting the Reactivity of Fluorinated 2-Arylpyridines in Pd-Catalyzed C-H Bond Arylation for the Preparation of Bright Emitting Iridium(III) Complexes.

Pd-catalyzed C-H bond arylation applied to 2-(2,4-difluorophenyl)-5-(trifluoromethyl)pyridine () and 2-(3,5-difluorophenyl)-5-(trifluoromethyl)pyridine () allows the access to two families of Ir(III) complexes, charge-neutral and cationic species. The reaction is regioselective since only the C3- or C4-position of the fluorinated phenyl ring of or is readily functionalized - namely the C-H bond flanked by the two fluorine atoms which is the most acidic - which allows the electronic control of the reactive site. A range of electron-withdrawing (CN, COEt, C(O)Me) substituents on the aryl group has been incorporated leading to the pro-ligands (, Ar-2,4-dFppy; , Ar = -CH-CN; , Ar = -CH-COEt; , Ar = -CH-C(O)Me; , and Ar-3,5-dFppy; , Ar = -CH-COEt).

Enantiomeric chromene derivatives with anticancer effects from Mallotus apelta.

Mallotusapelta(Lour.) Müll.Arg has been used in traditional medicine for the treatment of chronic hepatitis.

Unsupported Ni metal catalyst in hydrothermal liquefaction of oak wood: Effect of catalyst surface modification.

Hydrothermal liquefaction of oak wood was carried out in tubular micro reactors at different temperatures (280-330 °C), reaction times (10-30 min), and catalyst loads (10-50 wt%) using metallic Ni catalysts. For the first time, to enhance the catalytic activity of Ni particles, a coating technique producing a nanostructured surface was used, maintaining anyway the micrometric dimension of the catalyst, necessary for an easier recovery. The optimum conditions for non-catalytic liquefaction tests were determined to be 330 °C and 10 min with the bio-crude yield of 32.

Contact Lens Versus Non-Contact Lens-Related Corneal Ulcers at an Academic Center.

Purpose: To compare the infectious contact lens-related corneal ulcer (CLRU) and non-CLRU cases at Saint Louis University.

Methods: Retrospective review of corneal ulcer cases identified by search of the ophthalmology and microbiology department databases between 1999 and 2016.

Results: Six hundred seventy-seven cases of corneal ulcers were identified, of which 46% were CLRU.

Genome-Wide Association Study Meta-Analysis of Long-Term Average Blood Pressure in East Asians.

Background: Genome-wide single marker and gene-based meta-analyses of long-term average (LTA) blood pressure (BP) phenotypes may reveal novel findings for BP.

Methods And Results: We conducted genome-wide analysis among 18 422 East Asian participants (stage 1) followed by replication study of ≤46 629 participants of European ancestry (stage 2). Significant single-nucleotide polymorphisms and genes were determined by a <5.

Obstructive Sleep Apnea and Cardiovascular Events After Percutaneous Coronary Intervention.

Background: There is a paucity of data from large cohort studies examining the prognostic significance of obstructive sleep apnea (OSA) in patients with coronary artery disease. We hypothesized that OSA predicts subsequent major adverse cardiac and cerebrovascular events (MACCEs) in patients undergoing percutaneous coronary intervention.

Methods And Results: The Sleep and Stent Study was a prospective, multicenter registry of patients successfully treated with percutaneous coronary intervention in 5 countries.

Peroxisome Proliferator-Activated Receptor γ Level Contributes to Structural Integrity and Component Production of Elastic Fibers in the Aorta.

Loss of integrity and massive disruption of elastic fibers are key features of abdominal aortic aneurysm (AAA). Peroxisome proliferator-activated receptor γ (PPARγ) has been shown to attenuate AAA through inhibition of inflammation and proteolytic degradation. However, its involvement in elastogenesis during AAA remains unclear.

Differential Potency of 2,6-Dimethylcyclohexanol Isomers for Positive Modulation of GABAA Receptor Currents.

GABAA receptors meet all of the pharmacological requirements necessary to be considered important targets for the action of general anesthetic agents in the mammalian brain. In the following patch-clamp study, the relative modulatory effects of 2,6-dimethylcyclohexanol diastereomers were investigated on human GABAA (α1β3γ2s) receptor currents stably expressed in human embryonic kidney cells. Cis,cis-, trans,trans-, and cis,trans-isomers were isolated from commercially available 2,6-dimethylcyclohexanol and were tested for positive modulation of submaximal GABA responses.

Efficacy of Selective Brain Cooling Using a Nasopharyngeal Method in Piglets.

Background: Mild hypothermia is an effective neuroprotective strategy for a variety of acute brain injuries. Cooling the nasopharynx may offer the capability to cool the brain selectively due to anatomic proximity of the internal carotid artery to the cavernous sinus. This study investigated the feasibility and efficiency of nasopharyngeal brain cooling by continuously blowing room temperature or cold air at different flow rates into the nostrils of normal newborn piglets.

Differences in liver fibrosis between patients with chronic hepatitis B and C: evaluation by acoustic radiation force impulse measurements at 2 locations.

Objectives: The purpose of this study was to evaluate liver fibrosis by acoustic radiation force impulse (ARFI) measurements at 2 locations in patients with chronic hepatitis B and C.

Methods: A total of 204 consecutive patients (146 male and 58 female) with chronic hepatitis B (n = 121) and C (n = 83) who underwent liver biopsy were enrolled. All patients received ARFI measurements at 2 locations in the right intercostal space on the same day as biopsy.

Coherent anti-Stokes Raman scattering microscopy using a single-pass picosecond supercontinuum-seeded optical parametric amplifier.

We have demonstrated coherent anti-Stokes Raman scattering (CARS) microscopy with a single-pass picosecond supercontinuum-seeded optical parametric amplifier (SCOPA). The SCOPA was pumped by a frequency-doubled picosecond passively mode-locked Nd:YVO(4) laser, and was seeded by a supercontinuum light source. Compared with the conventional experimental setups of CARS microscopy, our exposition is substantially simpler because the pump and Stokes lasers are overlapped in the SCOPA automatically and thus steered into a microscope coherently.

1,3,4,6,7,9-Hexamethylbenzo[1,2-c:3,4-c':5,6-c'']trithiophene: a twisted heteroarene.

1,3,4,6,7,9-Hexamethylbenzo[1,2-c:3,4-c':5,6-c'']trithiophene (C-Me) was prepared by palladium-catalyzed methylations of the corresponding hexabromide C-Br. The twisted structure of C-Me has been confirmed by X-ray crystal analysis. The physical properties of twisted C-Me and planar benzo[1,2-c:3,4-c':5,6-c'']trithiophene (C-H) were studied and compared.

Depth distribution of irradiation-induced cross-linking in aromatic self-assembled monolayers.

Pristine and strongly irradiated self-assembled monolayers of [1,1':4',1' '-terphenyl]-4,4' '-dimethanethiol (TPDMT) on Au have been characterized by near-edge X-ray absorption fine structure spectroscopy using partial electron yield acquisition mode. The TPDMT films were found to be extremely stable toward electron irradiation, which is explained by cross-linking between the aromatic backbones. In addition, we assume that a large delocalization and a strong relaxation of the initial electronic excitations in the densely packed film contributed to the film stability.