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71.
72.
Enolesters as chain end-functionalizing agents for the living ring opening metathesis polymerization
Peng Liu Mohammad Yasir Helena Kurzen Nils Hanik Mark Schäfer Andreas F. M. Kilbinger 《Journal of polymer science. Part A, Polymer chemistry》2017,55(18):2983-2990
Functional enolethers have previously been used to introduce functional end groups at the chain end of ruthenium carbene complex initiated living ring opening metathesis polymers. Here, we investigated whether the weaker π-donating enolesters could equally be used in regio selective reactions with ruthenium carbene complexes and thus as polymer end-functionalization reagents. Enolesters such as vinyl acetate, butenyl acetate, 3-(4-(tert-butoxy)phenyl)propenyl acetate and 6-(((benzyloxy)carbonyl)amino)hex-1-en-1-yl acetate were used as living ROMP terminating agents. All gave the expected end groups proving that enolesters are synthetically easily accessible targets for living ROMP end-functionalization. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2983–2990 相似文献
73.
Coro Echeverria Pedro L. Almeida Oscar F. Aguilar Gutierrez Alejandro D. Rey Maria Helena Godinho 《Journal of Polymer Science.Polymer Physics》2017,55(10):821-830
The shear rate dependence of material functions such as shear viscosity (η) and the first normal stress difference (N1) were given and interpreted earlier by Kiss and Porter. Their widely accepted work revealed the possibility of having a negative minimum of N1 for polymeric liquid crystals. In this work, we disclose for the first time the evidence of two negative N1 minima on a sheared cellulosic lyotropic system. The lower shear rate minimum is ascribed to the uncoiling of the cholesteric helix, as theoretically predicted earlier. Our findings contribute also to the understanding of the other minimum already reported in the literature and attributed to the nematic director tumbling mode. Moreover, the elastic change that the LC‐HPC sample undergoes during the helix unwinding of the cholesteric structure is also by means of oscillatory measurements. This study is a contribution for the understanding of the structure‐properties relationship linked with the complex rheological behavior of chiral nematic cellulose‐based systems and may help to improve their further processing. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 821–830 相似文献
74.
75.
Leandro Augusto Gouvêa De Godoi Carla Eloísa Diniz Dos Santos Eugenio Foresti Marcelo Zaiat Márcia Helena Rissato Zamariolli Damianovic 《International journal of environmental analytical chemistry》2019,99(9):809-823
Recent developments in wastewater treatment have led to a renewed interest to obtain elemental sulphur (S°) as a by-product from bioreactors. However, practical studies are limited by the gap of adequate analytical techniques for its determination. This paper provides a statistical study and matrix effect evaluation of an adapted spectrophotometric method for routine S° analyses in aqueous samples, based on a methodology previously described by Hart (1961). Four complex matrices were tested: domestic sewage and effluent samples from three different bioreactors. Tested performance criteria included linearity, matrix effect, limit of detection and quantification and S° recovery. Results were linear (R2 = 0.99994) in the studied range (5 to 100 mg S° L?1) and no matrix effect was observed. The accuracy was based on recovery values that varied from 100% to 106%. The colloidal S° separation and extraction protocol was also considered suitable for aqueous samples, reaching more than 99.0% of S° recovery. 相似文献
76.
Dr. Rianne M. Lord Dr. Markus Zegke Imogen R. Henderson Dr. Christopher M. Pask Dr. Helena J. Shepherd Prof. Patrick C. McGowan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(2):495-500
This report presents a new library of organometallic iridium(III) compounds of the type [Cp*IrCl(L)] (Cp*=pentamethylcyclopentadienyl and L=a functionalized β-ketoiminato ligand) showing moderate to high cytotoxicity against a range of cancer cell lines. All compounds show increased activity towards colorectal cancer, with preferential activity observed against the immortalized p53-null colorectal cell line, HCT116 p53-/-, with sensitivity factors (SF) up to 26.7. Additionally, the compounds have excellent selectivity for cancerous cells when tested against normal cell types, with selectivity ratios (SR) up to 35.6, contrary to that of cisplatin, which is neither selective nor specific for cancerous cells (SF=0.43 and SR=0.7–2.3). This work provides a preliminary understanding of the cytotoxicity of iridium compounds in the absence of p53 and has potential applications in treatment of cancers for which the p53 gene is absent or mutant. 相似文献
77.
Ana Diniz Dr. Helena Coelho Dr. Jorge S. Dias Dr. Sandra J. van Vliet Prof. Dr. Jesús Jiménez-Barbero Prof. Dr. Francisco Corzana Prof. Dr. Eurico J. Cabrita Dr. Filipa Marcelo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(61):13945-13955
The human macrophage galactose-type lectin (MGL), expressed on macrophages and dendritic cells (DCs), modulates distinct immune cell responses by recognizing N-acetylgalactosamine (GalNAc) containing structures present on pathogens, self-glycoproteins, and tumor cells. Herein, NMR spectroscopy and molecular dynamics (MD) simulations were used to investigate the structural preferences of MGL against different GalNAc-containing structures derived from the blood group A antigen, the Forssman antigen, and the GM2 glycolipid. NMR spectroscopic analysis of the MGL carbohydrate recognition domain (MGL-CRD, C181-H316) in the absence and presence of methyl α-GalNAc (α-MeGalNAc), a simple monosaccharide, shows that the MGL-CRD is highly dynamic and its structure is strongly altered upon ligand binding. This plasticity of the MGL-CRD structure explains the ability of MGL to accommodate different GalNAc-containing molecules. However, key differences are observed in the recognition process depending on whether the GalNAc is part of the blood group A antigen, the Forssman antigen, or GM2-derived structures. These results are in accordance with molecular dynamics simulations that suggest the existence of a distinct MGL binding mechanism depending on the context of GalNAc moiety presentation. These results afford new perspectives for the rational design of GalNAc modifications that fine tune MGL immune responses in distinct biological contexts, especially in malignancy. 相似文献
78.
Katerina Kotkova Helena Ticha Ladislav Tichy 《Journal of Raman spectroscopy : JRS》2008,39(9):1219-1226
Five (PbO)x(Bi2O3)0.2(B2O3)0.8−x glasses, where x = 0, 0.2, 0.3, 0.4 and 0.6, were prepared. The dilatometric glass transition temperature (Tg) was found in the region 470 (x = 0)≥ Tg ( °C) ≥ 347 (x = 0.6), and the density (ρ) varied within 4.57 (x = 0) ≤ ρ (g/cm3) ≤ 8.31 (x = 0.6). Raman spectra indicated the conversion of BO3 to BO4 entities for low x values but for x > 0.3, namely, for x → 0.6, back‐conversion occurred, most probably. From the measurements of the optical transmission on very thin bulk samples, the room temperature optical gap values (Eg) were determined to be in the range 4.03 (x = 0)≥ Eg (eV) ≥ 3.08 (x = 0.6). The temperature (T) dependence of the optical gap (Eg(T)) in the region 300 ≤ T(K) ≤ 600 was examined and approximated by a linear relationship of the form of Eg(T) = Eg(0)− γT, where γ × 10−4(eV/K) varied from 5.1 to 6.8. The non‐linear refractive index (n2) was estimated from the optical gap values and it was found to correspond to the n2 values calculated from the experimental third‐order non‐linear optical susceptibility taken from the literature. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
79.
Physical and computer experiments involving systems describable by piecewise smooth continuous maps that are nondifferentiable on some surface in phase space exhibit novel types of bifurcations in which an attracting fixed point exists before and after the bifurcation. The striking feature of these bifurcations is that they typically lead to "unbounded behavior" of orbits as a system parameter is slowly varied through its bifurcation value. This new type of border-collision bifurcation is fundamental and robust. A method that prevents such "dangerous border-collision bifurcations" is given. These bifurcations may be found in a variety of experiments including circuits. 相似文献
80.
Vivian?Regina?Trist?o Fernando?Felippe?de?Carvalho Cinthia?Zanini?Gomes Adriana?Regina?Miranda Cíntia?C.?Vequi-Suplicy Maria?Teresa?Lamy Nestor?Schor Maria?Helena?Bellini 《Journal of fluorescence》2010,20(3):665-669
The progression to end-stage renal failure is independent of the initial pathogenic mechanism. Metabolic acidosis is a common
consequence of chronic renal failure that results from inadequate ammonium excretion and decreased tubular bicarbonate reabsorption.
Protoporphyrin IX (PpIX) is the immediate metabolic precursor of the heme molecule. The purpose of this study was to evaluate
the levels of erythrocytes protoporphyrin IX at an animal model during progressive renal disease. A total of 36 eight-week-old
male Wistar rats were divided into six groups: Normal, 4 and 8 weeks after 5/6 nephrectomy (NX). Renal function was evaluated
by creatinine clearance and plasma creatinine levels. The autofluorescence of erythrocytes porphyrin of healthy and NX rats
was analyzed using fluorescence spectroscopy. Emission spectra were obtained by exciting the samples at 405 nm. Significant
differences between normal and NX rats autofluorescence shape occurred in the 600–700 nm spectral region. A correlation was
observed between emission band intensity at 635 nm and progression of renal disease. 相似文献