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https://www.readbyqxmd.com/read/28440592/sequential-reactions-of-alkynes-on-an-ir-iii-single-site
#1
Miguel A Sierra, Mar Gómez-Gallego, Luis Casarrubios, Carmen Ramírez de Arellano, Elena A Giner, Alba D Merinero
Sequential insertion of terminal alkynes on Ir(III) cyclometallated complexes allow the formation of novel metallapolycycles in controlled and efficient manner. ortho-Methylarylethynyl derivatives led to an unprecedented cascade combination of three fundamental processes (C-C bond formation, Csp3-H activation and reductive elimination) on a single Ir(III) center, in a process compatible with functionalized biomolecules and photoactive substrates. The reaction with tert-butylacetylene led to a [6,5,4]-polycycle that incorporates an iridacyclobutenylidene in its structure...
April 25, 2017: Chemistry: a European Journal
https://www.readbyqxmd.com/read/28437101/ground-state-and-excited-state-tuning-in-ferric-dipyrrin-complexes-promoted-by-ancillary-ligand-exchange
#2
Claudia Kleinlein, Shao-Liang Zheng, Theodore A Betley
Three ferric dipyrromethene complexes featuring different ancillary ligands were synthesized by one electron oxidation of ferrous precursors. Four-coordinate iron complexes of the type ((Ar)L)FeX2 [(Ar)L = 1,9-(2,4,6-Ph3C6H2)2-5-mesityldipyrromethene] with X = Cl or (t)BuO were prepared and found to be high-spin (S = (5)/2), as determined by superconducting quantum interference device magnetometry, electron paramagnetic resonance, and (57)Fe Mössbauer spectroscopy. The ancillary ligand substitution was found to affect both ground state and excited properties of the ferric complexes examined...
April 24, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28436530/solvent-free-uncatalyzed-asymmetric-ene-reactions-of-n-tert-butylsulfinyl-3-3-3-trifluoroacetaldimines-a-general-approach-to-enantiomerically-pure-%C3%AE-trifluoromethyl-tryptamines
#3
Giuseppe Mazzeo, Giovanna Longhi, Sergio Abbate, Martina Palomba, Luana Bagnoli, Francesca Marini, Claudio Santi, Jianlin Han, Vadim A Soloshonok, Emilio Di Crescenzo, Renzo Ruzziconi
A novel approach to regioselectively substituted and stereoselectively α-trifluoromethylated tryptamines is reported based on the ene reaction of Boc-protected 3-methyleneindolines with optically pure (R)- or (S)-tert-butanesulfinyltrifluoroacetaldimine. Boc- and sulfinylamido-protected α-trifluoromethyltryptamines are obtained in 60-70% yield and 85/15 dr by just heating equimolar amounts of the two reaction partners at 80-90 °C for 2-3 h without a solvent. The absolute configuration of the amino α-carbon has been assigned based on the vibrational circular dichroism (VCD) spectral analysis...
April 24, 2017: Organic & Biomolecular Chemistry
https://www.readbyqxmd.com/read/28435721/structure-of-2-2-5-tert-butyl-1-3-phenyl-ene-bis-1-pentyl-1h-benzimidazol-3-ium-tetra-chlorido-mercurate-ii
#4
Varsha Rani, Harkesh B Singh, Ray J Butcher
In the title salt, (C34H44N4)[HgCl4], the [C34H44N4](2+) cations and [HgCl4](2-) anions are linked by N-H⋯Cl hydrogen bonds. One of the two n-pentyl side chains was refined as disordered over two sets of sites, with occupancies of 0.733 (18) and 0.267 (18). The geometry around the Hg(II) atom in the [HgCl4](2-) anion is distorted tetra-hedral, with bond angles ranging from 98.16 (3) to 120.68 (3)°. In the [HgCl4](2-) anion, there are two short Hg-Cl bonds [2.4120 (9) and 2.4171 (11) Å], one inter-mediate Hg-Cl bond [2...
April 1, 2017: Acta Crystallographica. Section E, Crystallographic Communications
https://www.readbyqxmd.com/read/28434709/target-analysis-of-tert-butyldimethylsilyl-derivatives-of-nerve-agent-hydrolysis-products-by-selectable-one-dimensional-or-two-dimensional-gas-chromatography-mass-spectrometry
#5
Yasuo Seto, Masumi Tachikawa, Mieko Kanamori-Kataoka, Kikuo Sasamoto, Nobuo Ochiai
A target analysis method for the sensitive and discriminative determination of the nerve agent hydrolysis products alkyl methylphosphonic acids as their tert-butyldimethylsilyl (TBDMS) derivatives was developed using a combination of selectable one- and two-dimensional ((1)D/(2)D) GC-MS, and applied to the analysis of samples with significant interfering matrices. After sample drying, the alkylmethylphosphonic acids and methylphosphonic acid (MPA) were converted to TBDMS derivatives by addition of N-methyl-N-(tert-butyldimethylsilyl)trifluoroacetamide with heating, and subjected to (1)D/(2)D GC-MS...
April 13, 2017: Journal of Chromatography. A
https://www.readbyqxmd.com/read/28434530/accelerated-cellular-senescence-as-underlying-mechanism-for-functionally-impaired-bone-marrow-derived-progenitor-cells-in-ischemic-heart-disease
#6
Evelien Nollet, Vicky Y Hoymans, Inez R Rodrigus, Dina De Bock, Marc Dom, Viviane O M Van Hoof, Christiaan J Vrints, Emeline M Van Craenenbroeck
BACKGROUND AND AIMS: Bone marrow (BM)-derived progenitor cells are functionally impaired in patients with ischemic heart disease (IHD), thereby hampering the outcome of autologous stem cell therapy. In search for underlying mechanisms for this BM dysfunction, accelerated cellular senescence was explored. METHODS: We analysed telomere length of BM-derived mononuclear cells (MNC) by MMqPCR in patients with coronary artery disease (n = 12), ischemic heart failure (HF; n = 9), non-ischemic HF (n = 7) and controls (n = 10), and related it to their myeloid differentiation capacity...
May 2017: Atherosclerosis
https://www.readbyqxmd.com/read/28434171/peroxidatic-cysteine-residue-of-peroxiredoxin-2-separated-from-human-red-blood-cells-treated-by-tert-butyl-hydroperoxide-is-hyperoxidized-into-sulfinic-and-sulfonic-acids
#7
Yo-Ichi Ishida, Mariko Aki, Sohta Fujiwara, Masami Nagahama, Yuki Ogasawara
Peroxiredoxin 2 (Prx2) is a redox enzyme that is abundantly expressed in red blood cells (RBCs) and has been the focus of clinical attention for monitoring the oxidative status. We previously developed a method to quantify the reduced and hyperoxidized forms of Prx2 in human RBCs using reverse-phase high-performance liquid chromatography (HPLC). In the present study, we investigated the hyperoxidative status of Prx2 at the molecular level in a post-translational modification analysis using a liquid chromatography-tandem mass spectrometry (LC-MS/MS) system...
April 22, 2017: Human Cell
https://www.readbyqxmd.com/read/28432770/chiral-separation-of-aryloxyphenoxy-propionate-herbicides-in-a-permethyl-%C3%AE-cyclodextrin-based-column-influence-of-temperature-and-mobile-phase-composition-on-enantioselectivity
#8
Ester Lubomirsky, Héctor Di Loreto, Juan M Padró, Cecilia B Castells
We used a permethyl-β-cyclodextrin chiral stationary phase under reversed-phase conditions for the chiral separation of four aryloxyphenoxy-propionate herbicides (fenoxaprop-p-ethyl, quizalofop-p-ethyl and tefuryl and haloxyfop-p-methyl) with mixtures of methanol, ethanol, 2-propanol, n-propanol, tert-butanol, or acetonitrile and water as mobile phases and investigated the influence of mobile phase composition and column temperature (from 0 to 50 °C) on the separation. The retention factors (k) and selectivity factors (α) of all the herbicides investigated decreased with increasing temperature...
April 22, 2017: Electrophoresis
https://www.readbyqxmd.com/read/28429424/palladium-catalyzed-carbonylation-of-sec-and-tert-alcohols
#9
Kaiwu Dong, Rui Sang, Jie Liu, Rauf Razzaq, Robert Franke, Ralf Jackstell, Matthias Beller
A general palladium-catalyzed synthesis of linear esters directly from sec- and tert-alcohols is described. Compared to the classic Koch-Haaf reaction, which leads to branched products, this new transformation gives the corresponding linear esters in high yields and selectivity. Key for this protocol is the use of an advanced palladium catalyst system with L2 (py(t) bpx) as the ligand. A variety of aliphatic and benzylic alcohols can be directly used and the catalyst efficiency for the benchmark reaction is outstanding (turnover number up to 89 000)...
April 21, 2017: Angewandte Chemie
https://www.readbyqxmd.com/read/28429024/a-highly-efficient-cu-catalyst-system-for-the-radical-reactions-of-%C3%AE-bromocarbonyls
#10
Yushi Noda, Takashi Nishikata
In this communication, we established highly efficient Cu-catalyzed ARGET-ATRS (atom-transfer radical substitution) of alpha-bromocarbonyls with styrenes to produce tert-alkylated styrenes. The maximum TON was up to 12 000. Hünig's base was very important to regenerate active Cu(I). Moreover, a Cu-catalyzed C-C cleavage reaction via SH2' and intermolecular C-H cyclization of α-bromoimide was found.
April 21, 2017: Chemical Communications: Chem Comm
https://www.readbyqxmd.com/read/28426214/calix-5-arene-through-the-annulus-threading-of-dialkylammonium-guests-weakly-paired-to-the-tfpb-anion
#11
Margherita De Rosa, Carmen Talotta, Carmine Gaeta, Annunziata Soriente, Placido Neri, Sebastiano Pappalardo, Giuseppe Gattuso, Anna Notti, Melchiorre F Parisi, Ilenia Pisagatti
The through-the-annulus threading of calix[5]arene penta-O-ethers by dialkylammonium cations coupled to the loosely coordinating superweak TFPB- anion has been successfully accomplished. 1H NMR titration data show that the preorganization of the calix[5]arene scaffold leads to great thermodynamic stability of the pseudorotaxane complexes as well as to a favorable kinetic of threading. Accordingly, calix[5]arene 1c, bearing tert-butyl groups at the wide rim, was threaded by all the cations under study (with the exception of the dibenzylammonium 2b+) more tightly than the other derivatives under investigation (Kas up to 2...
April 20, 2017: Journal of Organic Chemistry
https://www.readbyqxmd.com/read/28425285/directed-evolution-of-carbonyl-reductase-from-rhodosporidium-toruloides-and-its-application-in-stereoselective-synthesis-of-tert-butyl-3r-5s-6-chloro-3-5-dihydroxyhexanoate
#12
Zhi-Qiang Liu, Lin Wu, Xiao-Jian Zhang, Ya-Ping Xue, Yu-Guo Zheng
tert-Butyl (3R,5S)-6-chloro-3,5-dihydroxyhexanoate ((3R,5S)-CDHH) is a key intermediate of atorvastatin and rosuvastatin synthesis. Carbonyl reductase RtSCR9 from Rhodosporidium toruloides exhibited excellent activity toward tert-butyl (S)-6-chloro-3-hydoxy-5-oxohexanoate ((S)-CHOH). To improve the activity of RtSCR9, random mutagenesis and site-saturation mutagenesis were performed. Three positive mutants were obtained (mut-Gln95Asp, mut-Ile144Lys and mut-Phe156Gln). These mutants exhibited 1.94-, 3.03- and 1...
April 20, 2017: Journal of Agricultural and Food Chemistry
https://www.readbyqxmd.com/read/28424246/enteropathy-associated-t-cell-lymphoma-subtypes-are-characterized-by-loss-of-function-of-setd2
#13
Andrea B Moffitt, Sarah L Ondrejka, Matthew McKinney, Rachel E Rempel, John R Goodlad, Chun Huat Teh, Sirpa Leppa, Susanna Mannisto, Panu E Kovanen, Eric Tse, Rex K H Au-Yeung, Yok-Lam Kwong, Gopesh Srivastava, Javeed Iqbal, Jiayu Yu, Kikkeri Naresh, Diego Villa, Randy D Gascoyne, Jonathan Said, Magdalena B Czader, Amy Chadburn, Kristy L Richards, Deepthi Rajagopalan, Nicholas S Davis, Eileen C Smith, Brooke C Palus, Tiffany J Tzeng, Jane A Healy, Patricia L Lugar, Jyotishka Datta, Cassandra Love, Shawn Levy, David B Dunson, Yuan Zhuang, Eric D Hsi, Sandeep S Dave
Enteropathy-associated T cell lymphoma (EATL) is a lethal, and the most common, neoplastic complication of celiac disease. Here, we defined the genetic landscape of EATL through whole-exome sequencing of 69 EATL tumors. SETD2 was the most frequently silenced gene in EATL (32% of cases). The JAK-STAT pathway was the most frequently mutated pathway, with frequent mutations in STAT5B as well as JAK1, JAK3, STAT3, and SOCS1 We also identified mutations in KRAS, TP53, and TERT Type I EATL and type II EATL (monomorphic epitheliotropic intestinal T cell lymphoma) had highly overlapping genetic alterations indicating shared mechanisms underlying their pathogenesis...
April 19, 2017: Journal of Experimental Medicine
https://www.readbyqxmd.com/read/28423629/polymorphisms-in-human-telomerase-reverse-transcriptase-htert-gene-gene-gene-and-gene-smoking-interaction-with-susceptibility-to-gastric-cancer-in-chinese-han-population
#14
Jian Zhang, Hui Ju, Jun-Ru Gao, Xue-Long Jiao, Yun Lu
AIMS: To investigate the association of telomerase reverse transcriptase (TERT) gene polymorphisms and additional gene-gene and gene- environment interaction with gastric cancer (GC) risk. RESULTS: GC risk was significantly higher in carriers of G allele of rs2736100 than those with TT genotype (TG+ GG versus TT), adjusted OR (95%CI) =1.68 (1.26-2.17), and higher in carriers of G allele of rs2853669 than those with AA genotype (AG+ GG versus AA), adjusted OR (95%CI) = 1...
March 21, 2017: Oncotarget
https://www.readbyqxmd.com/read/28423545/hobnail-variant-of-papillary-thyroid-carcinoma-molecular-profiling-and-comparison-to-classical-papillary-thyroid-carcinoma-poorly-differentiated-thyroid-carcinoma-and-anaplastic-thyroid-carcinoma
#15
Lianghong Teng, Wanglong Deng, Junliang Lu, Jing Zhang, Xinyu Ren, Huanli Duan, Shannon Chuai, Feidie Duan, Wei Gao, Tao Lu, Huanwen Wu, Zhiyong Liang
BACKGROUND: As a rare but aggressive papillary thyroid carcinoma (PTC) variant, the genetic changes of hobnail variant of PTC (HVPTC) are still unclear. RESULTS: The prevalence of HVPTC was 1.69% (18/1062) of all PTC diagnosed in our cohort. 73 samples from 55 patients (17 HVPTC, 26 CPTC, 7 PDTC and 5 ATC) were successfully analyzed using targeted NGS with an 18-gene panel. Thirty-seven mutation variant types were identified among 11 genes. BRAF V600E mutation was the most common mutation, which is present in almost all HVPTC samples (16/17, 94%), most CPTC samples (20/26, 77%), and none of the ATC and PDTC samples...
March 28, 2017: Oncotarget
https://www.readbyqxmd.com/read/28421982/simultaneous-determination-of-volatile-organic-compounds-in-commercial-alcoholic-beverages-by-gas-chromatography-with-flame-ionization-detection
#16
Hyung Min Kim, Gun Yang, Jung Yoon Kim, Sang Jun Yoon, Byong-Kyu Shin, Jeongmi Lee, Jeong Hill Park, Sung Won Kwon
A simple and fast method was developed for the determination of volatile organic compounds in alcoholic beverages. Eleven volatile organic compounds (acetaldehyde, methanol, 2-propanol, <italic>tert</italic>-butanol, 1-propanol, ethyl acetate, 2-butanol, isobutanol, 1-butanol, 3-methyl-1butanol, and 2-methyl-1-butanol) in alcoholic beverages were analyzed with a simple direct-injection method using GC with flame ionization detection. These compounds should be monitored in the QC of production processes because they are detrimental to human health...
April 18, 2017: Journal of AOAC International
https://www.readbyqxmd.com/read/28421196/synthesis-of-l-ascorbyl-flurbiprofenate-by-lipase-catalyzed-esterification-and-transesterification-reactions
#17
Jia-Ying Xin, Li-Rui Sun, Shu-Ming Chen, Yan Wang, Chun-Gu Xia
The synthesis of L-ascorbyl flurbiprofenate was achieved by esterification and transesterification in nonaqueous organic medium with Novozym 435 lipase as biocatalyst. The conversion was greatly influenced by the kinds of organic solvents, speed of agitation, catalyst loading amount, reaction time, and molar ratio of acyl donor to L-ascorbic acid. A series of solvents were investigated, and tert-butanol was found to be the most suitable from the standpoint of the substrate solubility and the conversion for both the esterification and transesterification...
2017: BioMed Research International
https://www.readbyqxmd.com/read/28420995/quantum-dots-sirna-nanoplexes-for-gene-silencing-in-central-nervous-system-tumor-cells
#18
Guimiao Lin, Ting Chen, Jinyun Zou, Yucheng Wang, Xiaomei Wang, Jiefeng Li, Qijun Huang, Zicai Fu, Yingying Zhao, Marie Chia-Mi Lin, Gaixia Xu, Ken-Tye Yong
RNA interfering (RNAi) using short interfering RNA (siRNA) is becoming a promising approach for cancer gene therapy. However, owing to the lack of safe and efficient carriers, the application of RNAi for clinical use is still very limited. In this study, we have developed cadmium sulphoselenide/Zinc sulfide quantum dots (CdSSe/ZnS QDs)-based nanocarriers for in vitro gene delivery. These CdSSe/ZnS QDs are functionalized with polyethyleneimine (PEI) to form stable nanoplex (QD-PEI) and subsequently they are used for siRNA loading which specially targets human telomerase reverse transcriptase (TERT)...
2017: Frontiers in Pharmacology
https://www.readbyqxmd.com/read/28420174/an-expedient-total-synthesis-of-triciribine
#19
Chen Hu, Zhizhong Ruan, Haixin Ding, Yirong Zhou, Qiang Xiao
In the present paper, we report an expedient total synthesis of triciribine, a tricyclic 7-deazapurine nucleoside and protein kinase B (AKT ) inhibitor, in 35% overall yield. Our synthesis route features a highly regioselective substitution of 1-N-Boc-2-methylhydrazine and a trifluoroacetic acid catalyzed one-pot transformation which combined the deprotection of the tert-butylcarbonyl (Boc) group and ring closure reaction together to give a tricyclic nucleobase motif.
April 17, 2017: Molecules: a Journal of Synthetic Chemistry and Natural Product Chemistry
https://www.readbyqxmd.com/read/28420072/reduction-of-nitric-oxide-and-dna-rna-oxidation-products-are-associated-with-active-disease-in-systemic-lupus-erythematosus-patients
#20
T M V Iriyoda, N Stadtlober, M A B Lozovoy, F Delongui, N T Costa, E M V Reiche, I Dichi, A N C Simão
The aims of the present study were to evaluate biomarkers of oxidative and nitrosative stress in systemic lupus erythematosus (SLE) patients, in particular products of DNA/RNA oxidative damage and their correlation with disease activity. This study included 188 controls and 203 patients; 153 with inactive SLE (SLEDAI < 6) and 50 with active SLE (SLEDAI ≥ 6) without renal impairment. Oxidative stress was assessed by tert-butyl hydroperoxide-initiated by chemiluminescence, advanced oxidation protein products (AOPP), total radical-trapping antioxidant parameter (TRAP), nitric oxide metabolites (NOx), and DNA/RNA oxidation products...
January 1, 2017: Lupus
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