Synthesis and characterization of benzodioxinone mono-telechelics and their use in block copolymerization.

Poly(methyl methacrylate) (PMMA) and poly(ethylene glycol) methyl ether (mPEG)-based monotelechelics were quantitatively prepared by copper (I)-catalyzed azide/alkyne cycloaddition (CuAAC) click reactions using azido-terminated polymers and alkyne functional benzodioxinones. The monotelechelic containing dimethyl moities (2,2-dimethyl-5-(prop-2-yn-1-yloxy)-4H-benzo[d][1,3]dioxin-4-one) was heat-sensitive, whereas the monotelechelic containing diphenyl moieties (2,2-diphenyl-5-(prop-2-yn-1-yloxy)-4H-benzo[d][1,3]dioxin-4-one) was UV light sensitive. Based on the FT-IR, 1H-NMR, and GPC investigations, the CuAAC click reactions enable the quantitative syntheses of monotelechelics under mild conditions. Moreover, the photosensitive mPEG-based monotelechelic was further utilized for the block copolymer synthesis upon UV-light irradiation. The photoinduced acylation of mPEG monotelechelic consist of (2,2-diphenyl-5-(prop-2-yn-1-yloxy)-4H-benzo[d][1,3]dioxin-4-one) in the presence of hydroxy-terminated poly(epsilon caprolactone) enabled the successful block copolymer formation.

Can Albumin Bilirubin Ratio and Inflammatory Prognostic Index Be A New Marker Determining Survival in Metastatic Pancreatic Cancer?

OBJECTIVE: The main purpose of our study is to analyze the predictive and prognostic value of inflammatory prognostic index (IPI (using albumin, CRP, neutrophils and lymphocytes) and albumin / bilirubin ratio in metastatic pancreatic cancer patients in addition to other markers currently used. MATERIALS AND METHODS: Medical records of patients with pancreatic cancer treated in Celal Bayar University Medical Faculty Hospital Medical Oncology Clinic between February 2012 and April 2020 were retrospectively reviewed. Clinicopathologic variables such as age, gender, performance status (PS), treatments, histopathology type, localization of metastasis, comorbidity were recorded by an electronic medical record system. Patients performance status were recorded according to the Eastern Cooperative Oncology Group (ECOG). A total of 110 pancreatic cancer patients were reviewed. The IPI was calculated as C-reactive protein × NLR (neutrophil/lymphocyte ratio)/serum albumin. Univariate and multivariate analyses were performed to assess the prognostic value of relevant factors. RESULTS: Median OS of all patients was 6 months. The NLR cut off value we calculated was 3,47. The median OS of 47 (49,4%) patients was 8 months (95 % cl. 8,673- 15,383) with NLR < 3,47 and median OS of 48 (50,6%) patients was 4 months (95 % cl. 4,221-7,523) with NLR ≥ 3,47 (P: 0,001). The cut off value calculated for the IPI was 0,79. The median OS of 24 (25,8 %) patients was 8 months (95 % cl. 7,475-18,814) with IPI < 0,79 andmedian OS of 69 (74,2 %) patients was 5 months (95 % cl. 5,774-9,580) with IPI ≥ 0,79 (P: 0,047). The ABR cut off value we calculated was 5,23. The median OS of 45 (47,3 %) patients was 4 months (95 % cl. 8,879- 15,174) with ABR ≥ 5,23 and median OS of 50 (42,7 %) patients was 9 months (95 % cl. 4,015-7,585) with ABR < 5,23 (p< 0.001) (Figure 1). According to this analyses, presenting with jaundice, peritoneum metastasis, CA19.9 and LDH values higher than cut off, high NLR, high IPI and high ABR were also significantly associated with OS. In multivariate analyses, ABR was an independent prognostic factor in PC. Patients with high ABR (> 5,23) had increases in the risk of death compared with those with low ABR (< 5,23) (HR, 0,305; 95 % CI, 0,176-0,531; p: 0.000). Alongside ABR, CA-19.9 (HR, 2,300; 95 % CI, 1,111-4,764; p: 0,025) and LDH (HR, 3,348; 95 % CI, 1,792-6,253; p: 0.000) were an independent prognostic factor in PC. CONCLUSION: In this study, we demonstrated that both IPI and ABR, which were not evaluated in PC before, are non-invasive, cheap, accessible, and easily formulated parameters in determining the prognosis. Especially the fact that ABR is an independent prognostic indicator in multivariate analysis makes it stronger. Although we are aware that our study is retrospective, we hope that the reliability of these scores will increase if it is done with more patient series and if it is done multicenter.

Comparative Relaxant Effects of Ataciguat and Zaprinast on Sheep Sphincter of Oddi.

BACKGROUND: Relaxing the sphincter of Oddi (SO) is an important process during endoscopic retrograde cholangiopancreatography (ERCP) procedures. This issue suggests that the easier the sphincterotomy and cannulation, the more post-ERCP complications decrease. AIMS: To compare the relaxant effects of ataciguat (a novel soluble guanylyl cyclase activator) and zaprinast (an inhibitor of phosphodiesterase 5) on sheep SO in vitro, thus testing whether they can be used during ERCP. STUDY DESIGN: Animal experimentation. METHODS: Sheep SO rings were placed in tissue baths and their isometric tension to ataciguat and zaprinast were tested. We also tested their isometric tension against ataciguat in the presence of 1H-(1,2,4) oxadiazole (4,3-a) quinoxalin-1-one (ODQ) which is a soluble guanylyl cyclase inhibitor. RESULTS: Ataciguat and zaprinast both triggered concentration addicted relaxation on sheep SO rings (p=0.0018, p=0.0025 respectively) but the relaxation of the ataciguat was significantly greater than that of zaprinast at all concentrations (p=0.0024). It was observed that decreased relaxation responses were initiated by ataciguat in the presence of ODQ (p=0.0012). CONCLUSION: Ataciguat and zaprinast both have relaxing effects on sphincter of Oddi, although that of zaprinast is lower. We believe that ataciguat and zaprinast can be used in ERCP procedures in order to relax the sphincter of Oddi and thus can be used locally in order to decrease complications.

Orthogonal Synthesis of Block Copolymer via Photoinduced CuAAC and Ketene Chemistries.

A novel route for the synthesis of poly(ethylene glycol)-b-polystyrene copolymer, starting from commercially available poly(ethylene glycol) methyl ether and azido terminated polystyrene prepared by atom transfer radical polymerization and subsequent nucleophilic substitution, is applied with simplicity and high efficiency. The combination of photoinduced copper (I)-catalyzed alkyne-azide cycloaddition (CuAAC) and ketene chemistry reactions proceeds either simultaneously or sequentially in a one-pot procedure under near-visible light irradiation. In both cases, excellent block copolymer formations are achieved, with an average molecular weight of around 7000 g mo1(-1) and a polydispersity index of 1.20.

Crystal structure of rac-3-hy-droxy-2-(p-tol-yl)-2,3,3a,4,7,7a-hexa-hydro-1H-4,7-methano-isoindol-1-one.

In the title compound, C16H17NO2, the cyclo-hexene ring adopts a boat conformation, and the five-membered rings have envelope conformations with the bridging atom as the flap. Their mean planes are oriented at a dihedral angle of 86.51 (7)°. The mol-ecular structure is stabilized by a short intra-molecular C-H⋯O contact. In the crystal, mol-ecules are linked by O-H⋯O hydrogen bonds forming chains propagating along [100]. The chains are linked by C-H⋯π inter-actions, forming slabs parallel to (001).

Antioxidant, electrochemical, thermal, antimicrobial and alkane oxidation properties of tridentate Schiff base ligands and their metal complexes.

In this study, two Schiff base ligands (HL(1) and HL(2)) and their Cu(II), Co(II), Ni(II), Pd(II) and Ru(III) metal complexes were synthesized and characterized by the analytical and spectroscopic methods. Alkane oxidation activities of the metal complexes were studied on cyclohexane as substrate. The ligands and their metal complexes were evaluated for their antimicrobial activity against Corynebacterium xerosis, Bacillus brevis, Bacillus megaterium, Bacillus cereus, Mycobacterium smegmatis, Staphylococcus aureus, Micrococcus luteus and Enterococcus faecalis (as gram-positive bacteria) and Pseudomonas aeruginosa, Klebsiella pneumoniae, Escherichia coli, Yersinia enterocolitica, Klebsiella fragilis, Saccharomyces cerevisiae, and Candida albicans (as gram-negative bacteria). The antioxidant properties of the Schiff base ligands were evaluated in a series of in vitro tests: 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical scavenging and reducing power activity of superoxide anion radical generated non-enzymatic systems. Electrochemical and thermal properties of the compounds were investigated.

Supramolecular structure of racemic 5-hydroxy-4-(4-methoxyphenyl)-10-oxa-4-azatricyclo[5.2.1.0(2,6)]dec-8-en-3-one.

The structure of the title compound, C(15)H(15)NO(4), comprises a racemic mixture of chiral molecules containing five stereogenic centres. The cyclohexane ring tends towards a boat conformation and the two tetrahydrofuran rings adopt envelope conformations. Molecules are linked into sheets parallel to (100) by a combination of O-H...O, C-H...O and C-H...pi hydrogen bonds, leading to a two-dimensional supramolecular structure.