Real‐time monitoring by proton relaxometry of radical polymerization reactions of acrylamide in aqueous solution

The potential of time‐domain nuclear magnetic resonance (TD‐NMR) for the real‐time monitoring of solution radical polymerizations is demonstrated. A model system composed of a redox‐pair initiator system, acrylamide as monomer and water as solvent was investigated. A second‐generation continuous wave free precession technique was employed to measure the longitudinal relaxation time constant (T₁) of the samples throughout the polymerization reactions. This parameter was shown to be sensitive to the reactant feed free‐radical enhancement of the water molecule relaxation time, making it a good probe to monitor monomer conversion in real time in an automated, non‐destructive fashion. It was found that the T₁ value was better than the transverse relaxation time constant (T₂) for describing the evolution of the polymerization reactions, due to its greater sensitivity to paramagnetic effects. The TD‐NMR signal variation observed was linked to the formation, propagation and termination steps of the radical polymerization kinetics scheme. These first results may contribute to the application of real‐time monitoring of radical polymerization reactions employing low‐cost and robust TD‐NMR spectrometers. © 2018 Society of Chemical Industry     

Synthesis of chiral stationary phase via surface‐initiated atom transfer radical polymerization of vinylated cellulose 3,5‐dimethylphenylcarbamate

A polysaccharide‐immobilized chiral stationary phase (CSP) was prepared by the surface‐initiated atom transfer radical polymerization (SI‐ATRP), in pyridine, of cellulose 2,3‐bis(3,5‐dimethylphenylcarbamate), having a polymerizable vinyl group, on the surface of SiO₂ support. The successful preparation of the CSP was confirmed via Fourier transform infrared spectroscopy, field‐emission scanning electron microscopy, X‐ray photoelectron spectroscopy, elemental analysis and thermal analysis. The chiral recognition ability of the prepared CSP was evaluated with high‐performance liquid chromatography using 10 racemates with various mobile phases of hexane/alcohol, hexane/tetrahydrofuran and hexane/chloroform. As a result, this CSP prepared using SI‐ATRP can be used in tetrahydrofuran and chloroform solutions as eluents. Copyright © 2011 Society of Chemical Industry     

High resolution NMR study of tropical fruit seed starches

The nuclear magnetic resonance spectroscopy (NMR) studies of starches obtained by fruit seeds such as melon and watermelon were carried out as an analytical methodology to understand the molecular dynamic behavior. This study was also accompanied by the conventional X‐ray diffraction and thermal analysis. The NMR results give us a complete behavior of the samples at the molecular level. Thus, the information obtained from NMR will complement the data obtained from X‐ray and thermal analysis allowing us having responses on samples structure and dynamical behavior. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Role of Serum Cholesterol and Statin Use in the Risk of Prostate Cancer Detection and Tumor Aggressiveness

The aim of this study was to analyze the relationship between statin use along with serum cholesterol levels and prostate cancer (PCa) detection and aggressiveness. Statin users of three years or more and serum cholesterol levels (SC) were assessed in 2408 men scheduled for prostate biopsy. SC was classified as normal (NSC: <200 mg/dL) or high (HSC: >200 mg/dL). High-grade PCa (HGPCa) was considered if the Gleason score was greater than 7. Statin users comprised 30.9% of those studied. The PCa detection rate was 31.2% of men on statins and 37% of non-statin users (p < 0.006). The PCa detection rate was 26.3% in men with NSC and 40.6% in those with HSC (p < 0.001). In the subset of NSC men, the PCa rate was 26.5% for statin users and 26.2% for non-users (p = 0.939), while in men with HSC, the PCa rate was 36.4% for statin users and 42.0% for non-statin users (p = 0.063). The HGPCa rate was 41.8% for statin users and 32.5% for non-users (p = 0.012). NSC men had a 53.8% rate of HGPCa, while the rate was only 27.6% in HSC men (p < 0.001). NSC men on statins had an HGPCa rate of 70.2%, while non-statin users had a rate of 41.2% (p < 0.001). The HGPCa rate for HSC men on statins was 18.8%, while the rate was 30.0% (p = 0.011) for non-users. Logistic regression analysis suggested that serum cholesterol levels could serve as an independent predictor of PCa risk, OR 1.87 (95% CI 1.56–2.24) and HGPCa risk, OR 0.31 (95% CI 0.23–0.44), while statin usage could not. Statin treatment may prevent PCa detection through serum cholesterol-mediated mechanisms. A disturbing increase in the HGPCa rate was observed in statin users who normalized their serum cholesterol.     

Three-zone simulated moving-bed (SMB) for separation of cytosine and guanine

Separation of guanine and cytosine base pairs in nucleotide is an interesting topic for investigation of DNA structure. Therefore, an understanding of nucleotide separation by chromatography is necessary to prepare DNA molecules. Guanine and cytosine separation in SMB was simulated by Aspen chromatography and it was experimented by assembled 3-zone simulated moving bed (SMB) with change of stream flow rates, sample concentration, and desorbent flow rate. The simulation of batch chromatography was also confirmed by HPLC experiments. Based on these, good operating conditions of SMB chromatography were determined. Three-zone SMB equipment was set up by connecting three C₁₈-HPLC columns, four HPLC pumps, and six multiposition valves. Batch chromatography of cytosine and guanine was conducted to determine the isotherms of the two nucleotides. The outlet streams of SMB, raffinate and extract were sampled and analyzed by analytical HPLC system. The adsorption isotherms of cytosine and guanine were H_C= 0.5 and H _G =1.05. The highest experimental purity of cytosine and guanine in SMB was obtained as 94.9% and 89.8% with operating parameters of Q _feed =0.2 mL/min, Q _desorbent =0.6 mL/min, Q _extract =0.2 mL/min, Q _raffinate =0.6 mL/min, and switching time=7 min.     

Physicochemical properties and bioactivity of brown seaweed fucoidan prepared by ultra high pressure-assisted enzyme treatment

The effects of ultra-high pressure (UHP, 100 MPa, 40, 24 h) processing and enzyme treatment on the physicochemical properties and anticoagulant activity of fucoidan obtained from Undaria pinnatifida sporophyll (UPS) were investigated. Crude UPS fucoidan (F _UPS ) with an average MW of 877 kDa was slightly depolymerized by UHPassisted Tunicase treatment, yielding fucoidan with a lower MW (600–800 kDa). UHP-enzyme treatment decreased the sulfate, fucose and galactose contents of F _UPS but increased its glucose content. From FT-IR spectrum, UHP-enzyme treatment was found not to cause a structural change on S=O and C-O-S. After UHP-enzyme treatment, the sulfate content and average MW of F _UPS decreased with the increase of Tunicase concentration. It was found that among the UHP-enzyme-treated fucoidans, F _UPS -T0.3-U (Tunicase 0.3% treatment+UHP treatment) possessed the highest anticoagulant activity. F _UPS -T0.3-U appeared to inhibit blood coagulation via intrinsic pathway. With the increase of sulfate content in F _UPS , activated partial thromboplastin time (APTT) and thrombin time (TT) showed a tendency of increase. APTT and TT had the highest values in F _UPS -T0.3-U in which the sulfate concentration was 24%, but on the contrary decreased at a sulfate concentration of above 24%. This result indicates that there is an optimum sulfate concentration for the anticoagulant activity of fucoidan. Consequently, UHP-assisted enzymatic treatment was found to be helpful for the improvement of anticoagulant activities of fucoidan.     

Hydrogenation of carbon monoxide to methane over mesoporous nickel-M-alumina (M = Fe,Ni, Co,Ce, and La) xerogel catalysts

Mesoporous nickel(30 wt%)-M(10 wt%)-alumina xerogel (30Ni10MAX) catalysts with different second metal (M = Fe, Ni, Co, Ce, and La) were prepared by a single-step sol–gel method for use in the methane production from carbon monoxide and hydrogen. In the methanation reaction, yield for CH₄ decreased in the order of 30Ni10FeAX > 30Ni10NiAX > 30Ni10CoAX > 30Ni10CeAX > 30Ni10LaAX. Experimental results revealed that CO dissociation energy of the catalyst and H₂ adsorption ability of the catalyst played a key role in determining the catalytic performance of 30Ni10MAX catalyst in the methanation reaction. Optimal CO dissociation energy of the catalyst and large H₂ adsorption ability of the catalyst were favorable for methane production. Among the catalysts tested, 30Ni10FeAX catalyst with the most optimal CO dissociation energy and the largest H₂ adsorption ability exhibited the best catalytic performance in terms of conversion of CO and yield for CH₄ in the methanation reaction. The enhanced catalytic performance of 30Ni10FeAX was also due to a formation of nickel–iron alloy and a facile reduction.     

Diluent filler particle size effect for thermal stability of epoxy type resin

Epoxy resin is used as a material for electrical and electronics molding in various forms but its thermal conductivity must be controlled with various additives on account of its lower conductivity than metal or ceramics. Silicon dioxide (SiO₂) and silica were selected as the reinforcement and diluent filler for epoxy resins, respectively. The optimum amount of reinforcement filler, SiO₂, was 50 wt%. The thermal properties and thermal stability were observed according to silica ratio and particle size. An epoxy modified with a polyamide type hardener showed superior thermal conductivity to that modified with a cyclo-aliphatic amine type hardener. The thermal conductivity increased with increasing silica ratio and particle size. The thermal stability evaluation based on the particle size of silica was in the order of 14/18 mesh (1.00–1.16 mm) > 8/10 mesh (1.65–2.36 mm) > 28/35 mesh (0.42–0.59 mm). The optimum silica size of the diluent filler was 14/18 mesh (1.00–1.16 mm). An epoxy type resin transformer with excellent thermal properties and thermal stability could be designed when the mixing weight of epoxy resin was equal to that of the hardener.