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891.
Dr. Mohsen M. T. El-Tahawy Dr. Irene Conti Dr. Matteo Bonfanti Dr. Artur Nenov Prof. Dr. Marco Garavelli 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(46):20800-20808
Controlling the spectral tunability and isomerization activity is currently one of the hot topics in the design of photoreversible molecular switches for application in optoelectronic devices. The present work demonstrates how to manipulate the absorption of the retinal protonated Schiff base (rPSB) chromophore over the entire visible range by targeted functionalization of the retinal backbone. Moreover, a correlation between the vertical excitation energy and the profile of the potential energy surface of the bright excited state responsible for the photoreactivity of rPSB is established. This correlation was exploited to rank the functionalized rPSBs into different classes with characteristic photoisomerization activity. Eventually, the synergic effects of functionalization and of external electric fields in the range of a few MV cm−1 were applied to achieve reversable and regioselective control of the photoisomerization propensity of selected rPBS derivatives. 相似文献
892.
Andreas Kakouris Victoria Samara Anastasia Kalaskani Irene Panderi 《Chromatographia》2014,77(5-6):447-457
A gradient HPLC method coupled with diode array detection was developed and fully validated for the analysis of impurities in ropinirole using a Kromasil® C8 100 Å (250 × 4.6 mm, 5 μm) column with a flow rate 1.0 mL min?1 and detection at 250 nm. The mobile phase component A consisted of a mixture of 19.6 mM aqueous potassium dihydrogen phosphate–acetonitrile (98:2 v/v), pH adjusted to 7.0 with triethylamine and the mobile phase component B consisted of acetonitrile. The method was validated in terms of linearity, sensitivity, precision, accuracy and stability. The calibration curves for ropinirole and its five impurities showed good linearity (r > 0.998) within the calibration ranges tested. The intra- and inter-day RSD values were <3.9 %, while the relative percentage error E r was <5.8 % for all compounds. Accelerated stability studies performed under various stress conditions including oxidation, hydrolysis and UV light irradiation at 254 nm proved the selectivity of the procedure. Long-term stability studies performed on blistered tablets and under various conditions of heat and humidity indicate the presence of four of the studied impurities in less than 0.07 %. The method was applied successfully to the detection and determination of ropinirole impurities in pharmaceutical formulations. 相似文献
893.
Marta Martin‐Lorenzo Laura Gonzalez‐Calero Irene Zubiri Pedro J. Diaz‐Payno Aroa Sanz‐Maroto Maria Posada‐Ayala Alberto Ortiz Fernando Vivanco Gloria Alvarez‐Llamas 《Electrophoresis》2014,35(18):2634-2641
Urine is a source of potential markers of disease. In the context of renal disease, urine is particularly important as it may directly reflect kidney injury. Current markers of renal dysfunction lack both optimal specificity and sensitivity, and improved technologies and approaches are needed. There is no clear consensus about the best sample pretreatment procedure for 2DE analysis of the urine proteome. Sample pretreatment conditions spots resolution and detection sensitivity, critically. As a first goal, we exhaustively compared eight different sample cleaning and protein purification methodologies for 2DE analysis of urine from healthy individuals. Oasis® HLB cartridges allowed the detection of the highest number of low molecular weight proteins; while PD10 desalting columns resulted in the highest number of detected spots in the high molecular weight area. Sample pretreatment strategies were also explored in the context of proteinuria, a clinical condition often associated to renal damage. Testing of urine samples from 13 patients with hypertension or kidney disease and different levels of proteinuria identified Oasis® HLB cartridge purification in combination with albumin depletion by ProteoPrep kit as the best option for urine proteome profiling from patients with proteinuric (> 30 mg/L albumin in urine) renal disease. 相似文献
894.
High‐resolution high‐performance liquid chromatography with electrospray ionization mass spectrometry and tandem mass spectrometry characterization of a new isoform of human salivary acidic proline‐rich proteins named Roma‐Boston Ser22(Phos) → Phe variant
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Na Tian Tiziana Cabras Irene Messana Eva J. Helmerhorst Frank G. Oppenheim Massimo Castagnola 《Journal of separation science》2014,37(14):1896-1902
During a survey of human saliva by a top‐down reversed‐phase high‐performance liquid chromatography with electrospray ionization mass spectrometry approach, two proteins eluting at 27.4 and 28.4 min, with average masses of 15 494 ± 1 and 11 142 ± 1 Da, were detected in a subject from Boston. The Δmass value (4352 Da) of the two proteins was similar to the difference in mass values between intact (150 amino acids, [a.a.]) and truncated acidic proline‐rich proteins (aPRPs; 106 a.a.) suggesting an a.a. substitution in the first 106 residues resulting in a strong reduction in polarity, since under the same experimental conditions aPRPs eluted at ~22.5 min (intact) and 23.5 min (truncated forms). Manual inspection of the high‐resolution high‐performance liquid chromatography with electrospray ionization tandem mass spectra of the truncated isoform showed the replacement of the phosphorylated Ser‐22 in PRP‐3 with a Phe residue. Inspection of the tandem mass spectra of the intact isoform confirmed the substitution, which is allowed by the code transition TCT→TTT and is in agreement with the dramatic increase in elution time. The isoform was also detected in two other subjects, one from Boston (unrelated to the previous) and one from Rome. For this reason we propose to name this variant PRP‐1 (PRP‐3) RB (Roma‐Boston) Ser22(phos)→Phe. 相似文献
895.
Stéphane Brézillon Valérie Untereiner Lila Lovergne Irene Tadeo Rosa Noguera François-Xavier Maquart Yanusz Wegrowski Ganesh D. Sockalingum 《Analytical and bioanalytical chemistry》2014,406(24):5795-5803
We recently identified vibrational spectroscopic markers characteristic of standard glycosaminoglycan (GAG) molecules. The aims of the present work were to further this investigation to more complex biological systems and to characterize, via their spectral profiles, cell types with different capacities for GAG synthesis. After recording spectral information from individual GAG standards (hyaluronic acid, chondroitin sulfate, dermatan sulfate, heparan sulfate) and GAG-GAG mixtures, GAG-defective mutant Chinese hamster ovary (CHO)-745 cells, wild-type CHO cells, and chondrocytes were analyzed as suspensions by high-throughput infrared spectroscopy and as single isolated cells by infrared imaging. Spectral data were processed and interpreted by exploratory unsupervised chemometric methods based on hierarchical cluster analysis and principal component analysis. Our results showed that the spectral information obtained was discriminant enough to clearly delineate between the different cell types both at the cell suspension and single-cell levels. The abilities of the technique are to perform spectral profiling and to identify single cells with different potentials to synthesize GAGs. Infrared microspectroscopy/imaging could therefore be developed for cell screening purposes and further for identifying GAG molecules in normal tissues during physiological conditions (aging, healing process) and numerous pathological states (arthritis, cancer). Figure
896.
Direct Catalytic Enantio‐ and Diastereoselective Mannich Reaction of Isocyanoacetates and Ketimines
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Dr. Irene Ortín Prof. Dr. Darren J. Dixon 《Angewandte Chemie (International ed. in English)》2014,53(13):3462-3465
A catalytic asymmetric synthesis of imidazolines with a fully substituted β‐carbon atom by a Mannich‐type addition/cyclization reaction of isocyanoacetate pronucleophiles and N‐diphenylphosphinoyl ketimines has been developed. When a combination of a cinchona‐derived aminophosphine precatalyst and silver oxide was employed as a binary catalyst system, good reactivity, high diastereoselectivities (up to 99:1 d.r.), and excellent enantioselectivities (up to 99 % ee) were obtained for a range of substrates. 相似文献
897.
H. Ümit Kaniskan Magdalena M. Szewczyk Zhengtian Yu Mohammad S. Eram Xiaobao Yang Keith Schmidt Xiao Luo Miao Dai Feng He Irene Zang Ying Lin Steven Kennedy Fengling Li Elena Dobrovetsky Aiping Dong David Smil Sun‐Joon Min Melissa Landon Jennifer Lin‐Jones Xi‐Ping Huang Bryan L. Roth Matthieu Schapira Peter Atadja Dalia Barsyte‐Lovejoy Cheryl H. Arrowsmith Peter J. Brown Kehao Zhao Jian Jin Masoud Vedadi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(17):5255-5259
PRMT3 catalyzes the asymmetric dimethylation of arginine residues of various proteins. It is essential for maturation of ribosomes, may have a role in lipogenesis, and is implicated in several diseases. A potent, selective, and cell‐active PRMT3 inhibitor would be a valuable tool for further investigating PRMT3 biology. Here we report the discovery of the first PRMT3 chemical probe, SGC707, by structure‐based optimization of the allosteric PRMT3 inhibitors we reported previously, and thorough characterization of this probe in biochemical, biophysical, and cellular assays. SGC707 is a potent PRMT3 inhibitor (IC50=31±2 nM , KD=53±2 nM ) with outstanding selectivity (selective against 31 other methyltransferases and more than 250 non‐epigenetic targets). The mechanism of action studies and crystal structure of the PRMT3‐SGC707 complex confirm the allosteric inhibition mode. Importantly, SGC707 engages PRMT3 and potently inhibits its methyltransferase activity in cells. It is also bioavailable and suitable for animal studies. This well‐characterized chemical probe is an excellent tool to further study the role of PRMT3 in health and disease. 相似文献
898.
Won Seon Choi Atsushi Mitsumoto Irene E. Kochevar 《Photochemistry and photobiology》2009,85(6):1425-1433
Chronic exposure to solar UV radiation causes marked changes in the dermal extracellular matrix that underlie the loss of resiliency and increased laxity observed in photoaged skin. In particular, the dermal elastin content increases substantially and the normal, well-organized elastic fibers are replaced by amorphous elastotic material. Transforming growth factor-β1 (TGF-β1) stimulates synthesis of elastin by dermal fibroblasts and may mediate the increase in elastin in chronically photodamaged skin. We investigated pathways involved in the TGF–β1-induced increase in tropoelastin (TE), the soluble elastin monomer and assessed the role of reactive oxygen species (ROS) in the regulation of TE mRNA. Antioxidants and an inhibitor of NADPH oxidase blocked TGF–β1-induced TE mRNA increase even when added 1.5 h after TGF-β1, although ROS were detected for only 30 min. The TE mRNA increase required activation of Smad4, shown using Smad4 siRNA, and also involved the ERK1/2, p38 and JNK MAP kinases but not PI3K. ROS did not enhance signaling through Smad2 but did enhance activation of p38 and ERK1/2 at 10 min after TGF-β1. These results indicate that Smad and MAPK pathways mediate TGF–β1-induced TE expression and that ROS are required for both early signal transduction and later steps that increase elastin. 相似文献
899.
900.
Ryan G. Ezell Irene Gorman Brad Lokitz Neil Ayres Charles L. McCormick 《Journal of polymer science. Part A, Polymer chemistry》2006,44(9):3125-3139
Low‐charge density ampholytic terpolymers composed of acrylamide (AM), (3‐acrylamidopropyl)trimethyl ammonium chloride (APTAC), and N‐acryloyl‐valine were prepared via free‐radical polymerization in 0.5 M NaCl to yield terpolymers with random charge distributions. Sodium formate (NaOOCH) was employed as a chain transfer agent during the polymerization to suppress gel effects and broadening of the molecular weight distribution (MWD). Terpolymer compositions were determined by 13C NMR spectroscopy. Terpolymer molecular weights (MWs) and polydispersity indices (PDIs) were obtained via size exclusion chromatography/multi‐angle laser light scattering (SEC‐MALLS). Intrinsic viscosity values determined from SEC‐MALLS data using the Flory–Fox relationship were compared with those determined by low‐shear dilute solution viscometry and found to be in good agreement. SEC‐MALLS experiments allowed examination of radius of gyration‐MW (Rg‐M) relationships and the Mark‐Houwink‐Sakurada intrinsic viscosity‐MW ([η]‐M) relationships for terpolymers. The Rg‐M and [η]‐M relationships indicated little or no excluded volume effects under SEC conditions indicating that the terpolymers were in near theta conditions in an aqueous buffer solution. Potentiometric titration experiments were performed in deionized (DI) water. These studies revealed that the apparent pKa of the AMVALTAC terpolymers increases with increasing VAL content. The solution properties of low‐charge density ampholytic terpolymers have been studied as functions of solution pH, ionic strength, and polymer concentration. The charge‐balanced terpolymers exhibit polyampholyte behavior at pH values ≥ 6.5. As solution pH is decreased, these charge‐balanced terpolymers become increasingly cationic due to the protonation of the VAL repeat units. Charge‐imbalanced terpolymers generally exhibit polyelectrolyte behavior, although the effects of intramolecular electrostatic interactions (e.g., polyampholyte effects) on the hydrodynamic volume are evident at certain values of solution pH and salt concentration. The solution behavior of the terpolymers in the dilute regime correlates well with that predicted by various polyampholyte solution theories. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3125–3139, 2006 相似文献