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Does -Butyl Alcohol Really Terminate the Oxidative Activity of OH in Inorganic Redox Chemistry?

Environ Sci Technol 2021 Jul 22. Epub 2021 Jul 22.

Department of Energy, Environmental and Chemical Engineering, Washington University in St. Louis, St. Louis, Missouri 63130, United States.

The hydroxyl radical, OH, is one of the most reactive free radicals and plays significant roles in the oxidative degradation of organic pollutants and the electron transfer of inorganic ions in natural and engineered environmental processes. To quantitatively determine the contribution of OH to oxidative reactions, a specific scavenger, such as -butyl alcohol (TBA), is usually added to eliminate OH effects. Although TBA is commonly assumed to transform OH into oxidatively inert products, this study demonstrates that utilizing TBA as an OH scavenger generates the secondary peroxyl radical (ROO), influencing the oxidation of transition metals, such as Mn. Read More

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Malignant Sinonasal Tumors: Update on Histological and Clinical Management.

Curr Oncol 2021 Jul 1;28(4):2420-2438. Epub 2021 Jul 1.

Sarcomas and Rare Tumors Unit, Istituto Nazionale Tumori, IRCCS-Fondazione "G. Pascale", 80131 Naples, Italy.

Tumors of nasal cavity and paranasal sinuses (TuNSs) are rare and heterogeneous malignancies, presenting different histological features and clinical behavior. We reviewed the literature about etiology, biology, and clinical features of TuNSs to define pathologic features and possible treatment strategies. From a diagnostic point of view, it is mandatory to have high expertise and perform an immunohistochemical assessment to distinguish between different histotypes. Read More

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Perfluoro--butanol: a cornerstone for high performance fluorine-19 magnetic resonance imaging.

Chem Commun (Camb) 2021 Jul 20. Epub 2021 Jul 20.

Group of Lead Compound, Department of Pharmacy, Hunan Provincial Key Laboratory of Tumor Microenvironment Responsive Drug Research, Hunan Province Cooperative Innovation Center for Molecular Target New Drug Study, University of South China, Hengyang 421001, Hunan, China. and Hubei Province Engineering and Technology Research Center for Fluorinated Pharmaceuticals, School of Pharmaceutical Sciences, Wuhan University, Wuhan 430071, China.

As a versatile quantification and tracking technology, 19F magnetic resonance imaging (19F MRI) provides quantitative "hot-spot" images without ionizing radiation, tissue depth limit, and background interference. However, the lack of suitable imaging agents severely hampers its clinical application. First, because the 19F signals are solely originated from imaging agents, the relatively low sensitivity of MRI technology requires high local 19F concentrations to generate images, which are often beyond the reach of many 19F MRI agents. Read More

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Exercise training increases telomerase reverse transcriptase gene expression and telomerase activity: A systematic review and meta-analysis.

Ageing Res Rev 2021 Jul 17;70:101411. Epub 2021 Jul 17.

Qatar University, College of Arts and Sciences (CAS), Sport Science Program (SSP), Doha, Qatar.

Telomeres protect genomic stability and shortening is one of the hallmarks of ageing. Telomerase reverse transcriptase (TERT) is the major protein component of telomerase, which elongates telomeres. Given that short telomeres are linked to a host of chronic diseases and the therapeutic potential of telomerase-based therapies as treatments and a strategy to extend lifespan, lifestyle factors that increase TERT gene expression and telomerase activity could attenuate telomere attrition and contribute to healthy biological ageing. Read More

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Total thyroidectomy can still remain the method of choice in some Bethesda III cases.

Biomed Pap Med Fac Univ Palacky Olomouc Czech Repub 2021 Jul 20. Epub 2021 Jul 20.

Institute of Pathology, 1st Faculty of Medicine, Charles University, Prague, Czech Republic.

Background: The latest WHO classification of tumours of endocrine organs defines new units of borderline thyroid tumours (BTT). The aim of our study was to evaluate ultrasonographic and cytological features, mutation profile and surgery treatment in rare thyroid tumours.

Methods: An analysis of 8 BTT out of 487 patients, who underwent thyroid surgery between June 2016 and June 2020. Read More

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Isolation of a triplet benzene dianion.

Nat Chem 2021 Jul 19. Epub 2021 Jul 19.

Department of Chemistry, University of California, Berkeley, CA, USA.

Baird's rule predicts that molecules with 4n π electrons should be aromatic in the triplet state, but the realization of simple ring systems with such an electronic ground state has been stymied by these molecules' tendency to distort into structures bearing a large singlet-triplet gap. Here, we show that the elusive benzene diradical dianion can be stabilized through creation of a binucleating ligand that enforces a tightly constrained inverse sandwich structure and direct magnetic exchange coupling. Specifically, we report the compounds [K(18-crown-6)(THF)][M(BzN-Mes)] (M = Y, Gd; BzN-Mes = 1,3,5-tris[2',6'-(N-mesityl)dimethanamino-4'-tert-butylphenyl]benzene), which feature a trigonal ligand that binds one trivalent metal ion on each face of a central benzene dianion. Read More

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Potential of Telomerase in Age-Related Macular Degeneration-Involvement of Senescence, DNA Damage Response and Autophagy and a Key Role of PGC-1α.

Int J Mol Sci 2021 Jul 3;22(13). Epub 2021 Jul 3.

Department of Ophthalmology, University of Eastern Finland, 70210 Kuopio, Finland.

Age-related macular degeneration (AMD), the main cause of vision loss in the elderly, is associated with oxidation in the retina cells promoting telomere attrition. Activation of telomerase was reported to improve macular functions in AMD patients. The catalytic subunit of human telomerase (hTERT) may directly interact with proteins important for senescence, DNA damage response, and autophagy, which are impaired in AMD. Read More

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NDMA formation during ozonation of metformin: Roles of ozone and hydroxyl radicals.

Sci Total Environ 2021 Jul 13;796:149010. Epub 2021 Jul 13.

State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, China. Electronic address:

Metformin, a high-consumed pharmaceutical for diabetes, has been reported to generate carcinogenic nitroso-dimethylamine (NDMA) during treatment of its containing wastewater. However, whether it would produce NDMA during ozonation or not is unclear, let alone discriminate roles of ozone (O) and hydroxyl radicals (OH). In this paper, effects of ozonation on NDMA formation from metformin were investigated, roles of O and OH were also distinguished by adding tert-butyl alcohol (tBA) as OH scavenger. Read More

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Copper-Catalyzed Aminosulfonylation of -Homoallyl Benzimidates with Sodium Sulfinates to Access Sulfonylated 1,3-Oxazines.

Org Lett 2021 Jul 19. Epub 2021 Jul 19.

College of Chemistry & Environmental Science, Hebei University, 180 Wusi Donglu, Baoding 071002, P. R. China.

A facile copper-catalyzed aminosulfonylation of homoallyl benzimidates with sodium sulfinates in the presence of -butyl peroxybenzoate (TBPB) and XPhos ligand has been developed. By using this protocol, a variety of potentially bioactive 1,3-oxazines were directly synthesized. This method has the merits of a cheap catalyst, easily available and stable sulfone reagents, and simple operation. Read More

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On-Surface Alcohol Oxidation Monitored by Paper Spray Mass Spectrometry: The Role of Ruthenium as Catalyst.

J Am Soc Mass Spectrom 2021 Jul 19. Epub 2021 Jul 19.

Department of Chemistry, Federal University of Minas Gerais, Belo Horizonte 31270-901, MG, Brazil.

Paper spray ionization mass spectrometry (PS-MS) is employed herein as a convenient platform to investigate an on-surface catalytic process, that is, the oxidation of alcohols induced by ruthenium salts. The tag-charged benzyl alcohol (/ 166), used as a suitable prototype starting substrate, is quickly oxidized by -butyl hydroperoxide (TBHP) in an on-surface process catalyzed by ruthenium trichloride (RuCl). The PS(+)-MS revealed the formation of products from the oxidation of alcohol . Read More

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Antioxidant Serine-(NSAID) Hybrids with Anti-Inflammatory and Hypolipidemic Potency.

Molecules 2021 Jul 2;26(13). Epub 2021 Jul 2.

Department of Pharmaceutical Chemistry, School of Pharmacy, Aristotelian University of Thessaloniki, 54124 Thessaloniki, Greece.

A series of L-serine amides of antioxidant acids, such as Trolox, ()-3-(3,5-di--butyl-4-hydroxyphenyl)acrylic acid (phenolic derivative of cinnamic acid) and 3,5-di--butyl-4-hydroxybenzoic acid (structurally similar to butylated hydroxytoluene), was synthesized. The hydroxy group of serine was esterified with two classical NSAIDs, ibuprofen and ketoprofen. The Trolox derivatives with ibuprofen (7) and ketoprofen (10) were the most potent inhibitors of lipid peroxidation (IC 3. Read More

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Tumorigenic effect of and its potential therapeutic target in NSCLC (Review).

Oncol Rep 2021 Aug 19;46(2). Epub 2021 Jul 19.

Department of Oncology, First Affiliated Hospital of Yangtze University, Jingzhou, Hubei 434023, P.R. China.

Non‑small cell lung cancer (NSCLC), which accounts for ~85% of all lung cancer cases, is commonly diagnosed at an advanced stage and has a high patient mortality rate. Despite the increasing availability of treatment strategies, the prognosis of patients with NSCLC remains poor, with a low 5‑year survival rate. This poor prognosis may be associated with the tumor heterogeneity of NSCLC, as well as its acquisition and intrinsic resistance to therapeutic drugs. Read More

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Synthesis and Study of a New Type of Nonanionic Demulsifier for Chemical Flooding Emulsion Demulsification.

ACS Omega 2021 Jul 2;6(27):17709-17719. Epub 2021 Jul 2.

School of Petroleum Engineering, Northeast Petroleum University, Daqing 163318, China.

The application of chemical flooding improves the stability of the produced emulsion, which reduces the demulsification efficiency of conventional demulsifiers. To improve the demulsification effect, in this paper, a new multibranched nonanionic polyether demulsifier, FYJP, was prepared by grafting carboxylate based on a nonionic demulsifier. The FYJP demulsifier could generate an initiator through --butylphenol, triethylenetetramine, and methanol, which was polymerized with ethylene oxide (EO) and propylene oxide (PO) to produce a nonionic polyether demulsifier. Read More

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Influence of Terminal Functionality on the Crystal Packing Behaviour and Cytotoxicity of Aromatic Oligoamides.

Front Chem 2021 30;9:709161. Epub 2021 Jun 30.

School of Chemistry and Biosciences, University of Bradford, Bradford, United Kingdom.

The synthesis and characterization of three aromatic oligoamides, constructed from the same pyridyl carboxamide core but incorporating distinct end groups of acetyl (Ac) , -butyloxycarbonyl (Boc) and amine is reported. Single crystal X-ray diffraction analysis of - and a dimethylsulfoxide (DMSO) solvate of (-DMSO), has identified the presence of a range of intra- and intermolecular interactions including N-H⋯N, N-H⋯O=C and N-H⋯O=S(CH) hydrogen-bonding interactions, C-H⋯π interactions and off-set, face-to-face stacking π-π interactions that support the variety of slipped stack, herringbone and cofacial crystal packing arrangements observed in -. Additionally, the cytotoxicity of this series of aromatic oligoamides was assessed against two human ovarian (A2780 and A2780cisR), two human breast (MCF-7 and MDA-MB-231) cancerous cell lines and one non-malignant human epithelial cell line (PNT-2), to investigate the influence of the terminal functionality of these aromatic oligoamides on their biological activity. Read More

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Differential Response of Oral Mucosal and Gingival Cells to , , and Multispecies Biofilms.

Front Cell Infect Microbiol 2021 1;11:686479. Epub 2021 Jul 1.

Department of Restorative Dentistry, School of Dentistry, Oregon Health & Science University, Portland, OR, United States.

Polymicrobial interactions with oral mucosal surfaces determine the health status of the host. While a homeostatic balance provides protection from oral disease, a dysbiotic polymicrobial community promotes tissue destruction and chronic oral diseases. How polymicrobial communities transition from a homeostatic to a dysbiotic state is an understudied process. Read More

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Metabolic Reprogramming Drives Pituitary Tumor Growth through Epigenetic Regulation of TERT.

Acta Histochem Cytochem 2021 Jun 23;54(3):87-96. Epub 2021 Jun 23.

Division of Pathological Neuroscience, Department of Pathology, Tokyo Women's Medical University, Shinjuku, Tokyo 162-8666, Japan.

Pituitary adenomas are common, benign brain tumors. Some tumors show aggressive phenotypes including early recurrence, local invasion and distant metastasis, but the underlying mechanism to drive the progression of pituitary tumors has remained to be clarified. Aerobic glycolysis known as the Warburg effect is one of the emerging hallmarks of cancer, which has an impact on the tumor biology partly through epigenetic regulation of the tumor-promoting genes. Read More

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The donor-acceptor dyad based on high substituted fullero[70]pyrrolidine-coordinated manganese (III) phthalocyanine for photoinduced electron transfer.

Spectrochim Acta A Mol Biomol Spectrosc 2021 Jul 9;263:120166. Epub 2021 Jul 9.

G. A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences, 1 Akademicheskaya Str., 153045 Ivanovo, Russian Federation.

Donor-acceptor dyads based on manganese porphyrins/phthalocyanines and fullerene derivatives with N-basicity centers have proved as promising photoinduced electron-transfer systems for photovoltaic devices, biologically active compounds, and molecular magnetic materials. The macroheterocyclic chromophore characterized by rich UV-visible-near IR absorption is the basis for the applications above. The problem of the synthesis and the characterization of new effective dyads was solved in this work on the example of the self-organizing system consisting of (octakis-3,5-di-tert-butylphenoxy)phthalocyaninato)manganese(III) acetate, (AcO)MnPc(3,5-di-BuPhO), 2',5-di(pyridin-2'-yl)-3,4-fullero[70]pyrrolidine, PyC, and toluene. Read More

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Clinical implications of molecular analysis in diffuse glioma stratification.

Brain Tumor Pathol 2021 Jul 15. Epub 2021 Jul 15.

Department of Neuropathology, Graduate School of Medical Sciences, Kyushu University, Fukuoka, Japan.

The revised 4th edition of the 2016 World Health Organization Classification of Tumors of the Central Nervous System (2016 CNS WHO) has introduced the integrated diagnostic classification that combines molecular and histological diagnoses for diffuse gliomas. In this study, we evaluated the molecular alterations for consecutive 300 diffuse glioma cases (grade 2, 56; grade 3, 62; grade 4, 182) based on this classification. Mutations in the isocitrate dehydrogenase (IDH) genes were common in lower grade glioma (LGG: grade2-3), and when combined with 1p/19q status, LGGs could be stratified into three groups except for four cases (Astrocytoma, IDH-mutant: 44; Oligodendroglioma, IDH-mutant and 1p/19q codeleted: 37; Astrocytoma, IDH-wildtype: 33). Read More

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Lead (Pb) sorption to hydrophobic and hydrophilic zeolites in the presence and absence of MTBE.

J Hazard Mater 2021 Jun 29;420:126528. Epub 2021 Jun 29.

Department of Engineering, University of Cambridge, Cambridge CB2 1PZ, United Kingdom.

The co-contamination of the environment by metals and organic pollutants is a significant concern, and one such example is lead (Pb) and methyl tert-butyl ether (MTBE) due to their historic use as fuel additives. Clinoptilolite is an abundant and efficient zeolite for metal removal, but the potential interference of co-existing organic pollutants on metal removal, such as MTBE, have rarely been discussed. In this study, a combination of batch sorption tests and synchrotron-based X-ray absorption spectroscopic analyses were employed to investigate Pb sorption mechanism(s) onto clinoptilolite in the presence and absence of MTBE. Read More

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Contributions of methionine to recognition of trimethyllysine in aromatic cage of PHD domains: implications of polarizability, hydrophobicity, and charge on binding.

Chem Sci 2021 Jul 2;12(25):8900-8908. Epub 2021 Jun 2.

Department of Chemistry, University of North Carolina at Chapel Hill CB 3290 Chapel Hill NC 27599 USA

Recognition of trimethyllysine (Kme3) by reader proteins is an important regulator of gene expression. This recognition event is mediated by an aromatic cage made up of 2-4 aromatic residues in the reader proteins that bind Kme3 cation-π interactions. A small subset of reader proteins contain a methionine (Met) residue in place of an aromatic sidechain in the binding pocket. Read More

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-aryl substituted DPEphos ligands: rhodium complexes featuring C-H anagostic interactions and B-H agostic bonds.

Chem Sci 2021 Jul 25;12(25):8832-8843. Epub 2021 May 25.

Department of Chemistry, University of York Heslington York YO10 5DD UK

The synthesis of new Schrock-Osborn Rh(i) pre-catalysts with -substituted DPEphos ligands, [Rh(DPEphos-R)(NBD)][BAr ] [R = Me, OMe, Pr; Ar = 3,5-(CF)CH], is described. Along with the previously reported R = H variant, variable temperature H NMR spectroscopic and single-crystal X-ray diffraction studies show that these all have axial (C-H)⋯Rh anagostic interactions relative to the d pseudo square planar metal centres, that also result in corresponding downfield chemical shifts. Analysis by NBO, QTAIM and NCI methods shows these to be only very weak C-H⋯Rh bonding interactions, the magnitudes of which do not correlate with the observed chemical shifts. Read More

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Prognostic stratification for IDH-wild-type lower-grade astrocytoma by Sanger sequencing and copy-number alteration analysis with MLPA.

Sci Rep 2021 Jul 13;11(1):14408. Epub 2021 Jul 13.

Department of Biomedical Research and Innovation, Institute for Clinical Research, National Hospital Organization Osaka National Hospital, Osaka, 540-0006, Japan.

The characteristics of IDH-wild-type lower-grade astrocytoma remain unclear. According to cIMPACT-NOW update 3, IDH-wild-type astrocytomas with any of the following factors show poor prognosis: combination of chromosome 7 gain and 10 loss (+ 7/- 10), and/or EGFR amplification, and/or TERT promoter (TERTp) mutation. Multiplex ligation-dependent probe amplification (MLPA) can detect copy number alterations at reasonable cost. Read More

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Solvent-Minimized Synthesis of 4CzIPN and Related Organic Fluorophores via Ball Milling.

J Org Chem 2021 Jul 14. Epub 2021 Jul 14.

Department of Pharmaceutical and Biological Chemistry, University College London School of Pharmacy, 29-39 Brunswick Square, Bloomsbury, London W1CN 1AX, United Kingdom.

The mechanochemical synthesis of 2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile and related organic fluorophores/photocatalysts via a solvent-minimized four-fold SAr pathway is herein described. Employing sodium -butoxide as base, and negating the need for any air/moisture-sensitive reaction set-ups, a selection of organic dyes was synthesized in just 1 h using this ball-milling technique. Furthermore, the transformation was then showcased on a multigram scale. Read More

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Anisotropic Evolution of Nanoclusters from Ag to Ag: Halogen- and Defect-Induced Epitaxial Growth in Nanoclusters.

J Phys Chem Lett 2021 Jul 13;12(28):6654-6660. Epub 2021 Jul 13.

Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Institute of Physical Science and Information Technology, Anhui University, Hefei, Anhui 230601, P. R. China.

Halogens have widely served as handles for regulating the growth of nanoparticles and the control of their physicochemical properties. However, their regulatory mechanism is poorly understood. Nanoclusters are the early morphology of nanoparticles and play an important role in revealing the formation and growth of nanoparticles due to their precise structures. Read More

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The dual distinct role of telomerase in repression of senescence and myofibroblast differentiation.

Aging (Albany NY) 2021 07 12;13(13):16957-16973. Epub 2021 Jul 12.

Department of Pathology, University of Michigan Medical School, Ann Arbor, MI 48109, USA.

Many aging related diseases such as cancer implicate the myofibroblast in disease progression. Furthermore genesis of the myofibroblast is associated with manifestation of cellular senescence of unclear significance. In this study we investigated the role of a common regulator, namely telomerase reverse transcriptase (TERT), in order to evaluate the potential significance of this association between both processes. Read More

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Metal Ion Control of Photoinduced Electron Spin Polarization in Electronic Ground States.

J Am Chem Soc 2021 Jul 12;143(28):10519-10523. Epub 2021 Jul 12.

Department of Chemistry, Brock University, St. Catharines, Ontario, Canada L2S 3A1.

Both the sign and intensity of photoinduced electron spin polarization (ESP) in the electronic ground state doublet (S/D) of chromophore-radical complexes can be controlled by changing the nature of the metal ion. The complexes consist of an organic radical (nitronyl nitroxide, NN) covalently attached to a donor-acceptor chromophore via a -phenylene bridge, (bpy)M(CAT--Ph-NN) () (bpy = 4,4'-di--butyl-2,2'-bipyridine, M = Pd () or Pt (), CAT = 3--butylcatecholate, -Ph = -phenylene). In both complexes, photoexcitation with visible light produces an initial exchange-coupled, three-spin (bpy, CAT = semiquinone (SQ), and NN), charge-separated doublet S (S = chromophore excited spin singlet configuration) excited state that rapidly decays to the ground state via a T (T = chromophore excited spin triplet configuration) state. Read More

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Optimized MALDI-TOF MS Strategy for Characterizing Polymers.

Front Chem 2021 24;9:698297. Epub 2021 Jun 24.

Institutes of Biomedical Sciences of Shanghai Medical School, Fudan University, Shanghai, China.

In recent years, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) plays an essential role in the analysis of polymers. To acquire a more reliable strategy for polymer profiling, we characterized four representative polymers including polyethylene glycol 6000, polyvinylpyrrolidone K12, polymer polyol KPOP-5040, and polyether polyol DL-4000. The preparation methods of these four polymer samples have been optimized from six aspects, including matrix, cationization reagent, solvent, mixing ratio of cationization reagent to polymer, mixing ratio of matrix to polymer, and laser intensity. Read More

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Selective and Additive-Free Hydrogenation of Nitroarenes Mediated by a DMSO-Tagged Molecular Cobalt Corrole Catalyst.

European J Org Chem 2021 Apr 2;2021(14):2114-2120. Epub 2021 May 2.

Institute of Catalysis (INCA) Johannes Kepler University (JKU) 4040 Linz Austria.

We report on the first cobalt corrole that effectively mediates the homogeneous hydrogenation of structurally diverse nitroarenes to afford the corresponding amines. The given catalyst is easily assembled prior to use from 4--butylbenzaldehyde and pyrrole followed by metalation of the resulting corrole macrocycle with cobalt(II) acetate. The thus-prepared complex is self-contained in that the hydrogenation protocol is free from the requirement for adding any auxiliary reagent to elicit the catalytic activity of the applied metal complex. Read More

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Reusable TsOH-HSO Mixed Catalysis for Tandem Synthesis of Biodiesel and Oxygenated Fuel Additives, tert-Butyl Glycerol Ethers.

J Oleo Sci 2021 Jul 9. Epub 2021 Jul 9.

Research Centre for Bioorganic Chemistry, Department of Chemistry, Faculty of Science, Chulalongkorn University.

A mixture of p-toluenesulfonic acid and sulfuric acid (TsOH-HSO) was used as a catalyst with a good performance in transesterification of palm oil (PO) with methanol and etherification of crude glycerol with isobutylene (tandem synthesis). For TsOH-HSO catalyzed biodiesel production, the reaction noticeably ran faster in comparison with TsOH or HSO alone and also gave up to 99.9% of the conversion using MeOH/PO molar ratio 9:1 at 80℃, in the period of 4 h. Read More

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A simple LC-MS/MS method for simultaneous determination of cilostazol and ambroxol in Sprague-Dawley rat plasma and its application to drug-drug pharmacokinetic interaction study following oral delivery in rats.

J Chromatogr B Analyt Technol Biomed Life Sci 2021 May 21;1179:122766. Epub 2021 May 21.

Department of Pharmaceutical Analysis, School of Pharmacy, Shenyang Pharmaceutical University, No. 103 Wenhua Road, Shenhe District, Shenyang 110016, PR China. Electronic address:

Recently, a combination of cilostazol and ambroxol has been used in the clinical treatment of stroke-associated pneumonia (SAP). However, the pharmacokinetic drug-drug interaction (DDI) of cilostazol and ambroxol has not been reported. In this paper, a rapid, reproducible and sensitive liquid chromatography tandem mass spectrometry (LC-MS/MS) method for simultaneous determination of cilostazol and ambroxol in Sprague-Dawley (SD) rat plasma was established and validated for the first time. Read More

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