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IUCrData Oct 2020The central copper(II) atom of the title salt, {[Cu(CFSO)(CHCN)(CHNO)](CFSO)} or [[Cu(CHCN)(diOMe-bpy)(CFSO)](CFSO)] where diOMe-bpy is...
The central copper(II) atom of the title salt, {[Cu(CFSO)(CHCN)(CHNO)](CFSO)} or [[Cu(CHCN)(diOMe-bpy)(CFSO)](CFSO)] where diOMe-bpy is 4,4'-dimeth-oxy-2,2'-bi-pyridine, CHNO, is sixfold coordin-ated by the N atoms of the chelating bi-pyridine ligand, the N atoms of two aceto-nitrile mol-ecules, and two tri-fluoro-methane-sulfonate O atoms in a tetra-gonally distorted octa-hedral shape. The formation of polymeric chains [Cu(CHCN)(diOMe-bpy)(CFSO)] leaves voids for the non-coordinating tri-fluoro-methane-sulfonate anions that inter-act with the complex through weak hydrogen bonds. The presence of weakly coordinating ligands like aceto-nitrile and tri-fluoro-methane-sulfonate makes the title compound a convenient starting material for the synthesis of novel metal-organic frameworks.
PubMed: 36339021
DOI: 10.1107/S2414314620014078 -
Molecules (Basel, Switzerland) Jul 2020Superelectrophiles are reactive species that often carry multiple positive charges. They have been useful in numerous synthetic methods and they often exhibit highly... (Review)
Review
Superelectrophiles are reactive species that often carry multiple positive charges. They have been useful in numerous synthetic methods and they often exhibit highly unusual reactivities. Recent advances in superelectrophile chemistry are discussed in this review.
Topics: Aza Compounds; Cyclization; Electrochemistry; Mesylates; Quinolones
PubMed: 32707680
DOI: 10.3390/molecules25143281 -
American Journal of Hematology Aug 2022The phase III study was designed to compare event-free survival (EFS) after treosulfan-based conditioning with a widely applied reduced-intensity conditioning (RIC)... (Randomized Controlled Trial)
Randomized Controlled Trial
Treosulfan compared with reduced-intensity busulfan improves allogeneic hematopoietic cell transplantation outcomes of older acute myeloid leukemia and myelodysplastic syndrome patients: Final analysis of a prospective randomized trial.
The phase III study was designed to compare event-free survival (EFS) after treosulfan-based conditioning with a widely applied reduced-intensity conditioning (RIC) busulfan regimen in older or comorbid patients with acute myeloid leukemia (AML) or myelodysplastic syndrome (MDS) undergoing allogeneic hematopoietic cell transplantation (HCT). A previously reported confirmatory interim analysis of the randomized clinical study including 476 patients demonstrated statistically significant noninferiority for treosulfan with clinically meaningful improvement in EFS. Here, the final study results and pre-specified subgroup analyses of all 570 randomized patients with completed longer-term follow-up are presented. Patients presenting HCT-specific comorbidity index >2 or aged ≥50 years were randomly assigned (1:1) to intravenous (IV) fludarabine with either treosulfan (30 g/m IV) or busulfan (6.4 mg/kg IV) after stratification by disease risk group, donor type, and participating institution. The primary endpoint was EFS with disease recurrence, graft failure, or death from any cause as events. EFS of patients (median age 60 years) was superior after treosulfan compared to RIC busulfan: 36-months-EFS rate 59.5% (95% CI, 52.2-66.1) vs. 49.7% (95% CI, 43.3-55.7) with a hazard ratio (HR) of 0.64 (95% CI, 0.49-0.84), p = 0.0006. Likewise, overall survival (OS) with treosulfan was superior compared to busulfan: 36-month-OS rate 66.8% vs. 56.3%; HR 0.64 (95% CI, 0.48-0.87), p = 0.0037. Post hoc analyses revealed that these differences were consistent with the confirmatory interim analysis, and thereby the treosulfan regimen appears particularly suitable for older AML and MDS patients.
Topics: Aged; Busulfan; Graft vs Host Disease; Hematopoietic Stem Cell Transplantation; Humans; Leukemia, Myeloid, Acute; Middle Aged; Myelodysplastic Syndromes; Prospective Studies; Transplantation Conditioning; Vidarabine
PubMed: 35617104
DOI: 10.1002/ajh.26620 -
IUCrData Oct 2021The title mol-ecular salt, CHNOS·CHOS, consists of a cationic sulfonated pyridine -oxide moiety and a methane-sulfonate anion. An N-O bond length of 1.4004 (15) Å...
The title mol-ecular salt, CHNOS·CHOS, consists of a cationic sulfonated pyridine -oxide moiety and a methane-sulfonate anion. An N-O bond length of 1.4004 (15) Å is observed in the cation. In the crystal, weak C-H⋯O inter-actions link the components into a three-dimensional network.
PubMed: 36340987
DOI: 10.1107/S2414314621010269 -
IUCrData Oct 2021In the centrosymmetric title complex, [CuCl(CHN)](CFOS), the Cu metal center is fivefold coordinated by two chloride ions and three nitro-gen atoms of the terpyridine...
In the centrosymmetric title complex, [CuCl(CHN)](CFOS), the Cu metal center is fivefold coordinated by two chloride ions and three nitro-gen atoms of the terpyridine ligand in a distorted square-pyramidal geometry; two tri-fluoro-methane-sulfonate ions complete the outer coordination sphere. stacking inter-actions between the pyridyl rings in adjacent mol-ecules contribute to the alignment of the complexes in columns along the -axis. This structure represents the first example of a binuclear dication of formula [Cu(terpy)Cl] with tri-fluoro-methane-sulfonate as counter-ions.
PubMed: 36340990
DOI: 10.1107/S2414314621010968 -
IUCrData Sep 2020In the title complex, [Zn(CFOS)Cl(CHClN)]·CHCN, the zinc(II) core is fivefold coordinated by one chloride, one tri-fluoro-methane-sulfonate O atom and three terpyridine...
In the title complex, [Zn(CFOS)Cl(CHClN)]·CHCN, the zinc(II) core is fivefold coordinated by one chloride, one tri-fluoro-methane-sulfonate O atom and three terpyridine N atoms in a slightly distorted square-pyramidal geometry. The structure provides a distinct example amongst other zinc(II) 4-chloro-terpyridine complexes because of the unusual planarity of the coordinated chloride, the short length of the Zn-N bond opposite to the chloride ligand [1.9572 (15) Å], and the presence of an elongated Zn-O bond [2.3911 (14) Å] in the coordinated tri-fluoro-methane-sulfonate ion. A molecule of acetonitrile is also found in the asymmetric unit of the title complex.
PubMed: 36338906
DOI: 10.1107/S2414314620012924 -
Plants (Basel, Switzerland) Oct 2022synthesizes bioactive therapeutic metabolites, known as monoterpenoid indole alkaloids (MIAs), including antineoplastic vinblastine and vincristine, which have high...
Ethyl Methane Sulfonate and Sodium Azide-Mediated Chemical and X-ray-Mediated Physical Mutagenesis Positively Regulate Gene Activity and Biosynthesis of Antineoplastic Vinblastine in .
synthesizes bioactive therapeutic metabolites, known as monoterpenoid indole alkaloids (MIAs), including antineoplastic vinblastine and vincristine, which have high global demand, and antihypertensive ajmalicine, a serpentine. However, the in planta biosynthesis and accumulation of these phytopharmaceuticals are very low, attributed to their high cytotoxicity in the plant. Considering the low in planta concentration and over-harvesting of plant resources, biotechnological interventions have been undertaken to enhance the production of MIAs in plant systems. The present study was carried out to mutation through chemical and physical mutagenesis with sodium azide, ethyl methane sulfonate and X-rays, respectively, on to determine their possible effects on the transcriptional modulation of MIA biosynthetic pathways in planta. The chemical mutagenesis resulted in delayed seed pod development in mutated plants, with distinct leaf morphology and flower color. However, X-ray mutagenesis resulted in pollen-less sterile flowers. An HPLC analysis confirmed the higher catharanthine, vindoline and vinblastine content in sodium azide and X-ray mutants, and was further supported by higher transcript levels estimated through real-time PCR analysis. The transcription factors and were found negatively regulated along with major MIA pathway genes in chemical mutants and their M generation, but showed positive regulation in X-ray M mutants. The induced mutagenesis of provides a prospective strategy to modulate plant transcriptomes and enhance the biosynthesis of pharmaceutically important antineoplastic vinblastine in the plant.
PubMed: 36365340
DOI: 10.3390/plants11212885 -
Yakugaku Zasshi : Journal of the... 2021"Retinoid" is the general term for vitamin A derivatives and chemical compounds that act like vitamin A. Vitamin A are composed of four isoprene units and are named... (Review)
Review
"Retinoid" is the general term for vitamin A derivatives and chemical compounds that act like vitamin A. Vitamin A are composed of four isoprene units and are named according to their terminal functional group, such as retinol (OH, 1), retinal (CHO, 2), and retinoic acid (COH, 3). Vitamin A usually refers to retinol. In the past few decades, major advances in research on vitamin A have improved our understanding of its fundamental roles and physiological significance in living cells. In this review, three types of chemical biology studies using vitamin A analogs are described: (1) conformational studies of the chromophore in retinal proteins (rhodopsin, phoborhodopsin, and retinochrome), especially the conformation around the cyclohexene ring; (2) structure-activity relationship studies of retinoic acid analogs to create new signaling molecules for activating nuclear receptors; and (3) development of a new channelrhodopsin with an absorption maximum at longer wavelength to overcome the various demerits of channelrhodopsins used in optogenetics, as well as the stereoselective synthesis of retinoid isomers and their analogs using a diene-tricarbonyliron complex or a palladium-catalyzed cross-coupling reaction between vinyl triflates and stannyl olefins.
Topics: Alkenes; Catalysis; Channelrhodopsins; Cyclohexenes; Eye Proteins; Isomerism; Mesylates; Molecular Conformation; Nuclear Reactors; Palladium; Retinoids; Stereoisomerism; Structure-Activity Relationship; Vinyl Compounds; Vitamin A
PubMed: 33790122
DOI: 10.1248/yakushi.20-00230 -
Biomedicine & Pharmacotherapy =... Sep 2023Male infertility is a global concern, with a noticeable increase in the decline of spermatogenesis and sperm quality. However, there are limited clinically effective...
Male infertility is a global concern, with a noticeable increase in the decline of spermatogenesis and sperm quality. However, there are limited clinically effective treatments available. This study aimed to investigate the potential effectiveness of puerarin in treating male infertility, which leads to gonadal changes. The results obtained from various analyses such as CASA, immunofluorescence, DIFF-Quick, hematoxylin and eosin (H&E), and periodic acid-Schiff (PAS) staining demonstrated that puerarin supplementation significantly alleviated the busulfan-induced reduction in spermatogenesis and sperm quality in both young and adult mice. Furthermore, puerarin exhibited a marked improvement in the damage caused by busulfan to the architecture of seminiferous tubules, causal epididymis, blood-testicular barrier (BTB), as well as spermatogonia and Sertoli cells. Similarly, puerarin significantly reduced the levels of total antioxidant capacity (T-AOC), malondialdehyde (MDA), and caspase-3 in the testes of busulfan-induced mice, as determined by microplate reader analysis. Additionally, RNA-seq data, RT-qPCR, and western blotting revealed that puerarin restored the abnormal gene expressions induced by busulfan to nearly healthy levels. Notably, puerarin significantly reversed the impact of busulfan on the expression of marker genes involved in spermatogenesis and oxidative stress. Moreover, puerarin suppressed the phosphorylation of p38, ERK1/2, and JNK in the testes, as observed through testicular analysis. Consequently, this study concludes that puerarin may serve as a potential alternative for treating busulfan-induced damage to male fertility by inactivating the testicular MAPK pathways. These findings may pave the way for the use of puerarin in addressing chemotherapy- or other factors-induced male infertility in humans.
Topics: Humans; Male; Animals; Mice; Busulfan; Semen; Spermatogenesis; Testis; Infertility, Male
PubMed: 37516022
DOI: 10.1016/j.biopha.2023.115231 -
Science (New York, N.Y.) Nov 2021To date, it remains challenging to selectively migrate a carbonyl oxygen within a given molecular scaffold, especially to an adjacent carbon. In this work, we describe a...
To date, it remains challenging to selectively migrate a carbonyl oxygen within a given molecular scaffold, especially to an adjacent carbon. In this work, we describe a simple one- or two-pot protocol that transposes a ketone to the vicinal carbon. This approach first converts the ketone to the corresponding alkenyl triflate, which can then undergo the palladium- and norbornene-catalyzed regioselective α-amination and ipso-hydrogenation enabled by a bifunctional hydrogen and nitrogen donor. The resulting “transposed enamine” intermediate can subsequently be hydrolyzed to produce the 1,2-carbonyl–migrated product. This method allows rapid access to unusual bioactive analogs through late-stage functionalization.
Topics: Amination; Carbon; Catalysis; Chemistry, Pharmaceutical; Hydrogen; Hydrogenation; Ketones; Mesylates; Molecular Structure; Norbornanes; Oxygen; Palladium; Technology, Pharmaceutical
PubMed: 34735246
DOI: 10.1126/science.abl7854