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41.
42.
Thais R. Cruz Eliada A. Silva Douglas P. Oliveira Daniele M. Martins Patrik D.S. Gois Antonio E.H. Machado Pedro Ivo S. Maia Beatriz E. Goi Benedito S. Lima-Neto Valdemiro P. Carvalho-Jr 《应用有机金属化学》2020,34(5):e5602
Arene ruthenium(II) complexes bearing the cyclic amines RuCl2(η6-p-cymene)(pyrrolidine)] ( 1 ), [RuCl2(η6-p-cymene)(piperidine)] ( 2 ), and [RuCl2(η6-p-cymene)(peridroazepine)] ( 3 ) were successfully synthesized. Complexes 1 – 3 were fully characterized by means of Fourier transform infrared, UV–visible, and NMR spectroscopy, elemental analysis, cyclic voltammetry, computational methods, and one of the complexes was further studied by single crystal X-ray crystallography. These compounds were evaluated as catalytic precursors for ring-opening metathesis polymerization (ROMP) of norbornene (NBE) and atom-transfer radical polymerization (ATRP) of methyl methacrylate (MMA). NBE polymerization via ROMP was evaluated using complexes 1 – 3 as precatalysts in the presence of ethyl diazoacetate (EDA) under different [NBE]/[EDA]/[Ru] ratios, temperatures (25 and 50°C), and reaction times (5–60 min). The highest yields of polyNBE were obtained with [NBE]/[EDA]/[Ru] = 5000/28/1 for 60 min at 50°C. MMA polymerization via ATRP was conducted using 1 – 3 as catalysts in the presence of ethyl-α-bromoisobutyrate (EBiB) as initiator. The catalytic tests were evaluated as a function of the reaction time using the initial molar ratio of [MMA]/[EBiB]/[Ru] = 1000/2/1 at 95°C. The increase in molecular weight as function of time indicates that complexes 1–3 were able to mediate the MMA polymerization with an acceptable rate and some level of control. Differences in the rate of polymerization were observed in the order 3 > 2 > 1 for the ROMP and ATRP. 相似文献
43.
Dr. Karl Kaupmees Robert Järviste Prof. Dr. Ivo Leito 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(48):17445-17449
The basicity scale of very weak bases has been set up in 1,2‐dichloroethane to give, for the first time, reliable quantitative insights into the basic properties of weak bases in a low‐polarity solvent. The scale contains 30 compounds, including anilines; phosphanes, and carbonyl bases, such as esters and amides, linked by 53 relative basicity measurements. The scale spans more than 12 pKip units, expanding to as low pKip values as possible with our current experimental methodology. 相似文献
44.
45.
Cleoci Beninca Tiago André Denck Colman Luiz Gustavo Lacerda Marco Aurélio da Silva Carvalho Filho Ivo Mottin Demiate Gilbert Bannach Egon Schnitzler 《Journal of Thermal Analysis and Calorimetry》2013,111(3):2217-2222
The use of chemically modified starches is widely accepted in various industries, with several applications. In this research, natural cassava starch granules were treated with standard sodium hypochlorite solution at 0.8, 2.0, and 5.0 g Cl/100 g starch. The native and modified starch samples were investigated by means of the following techniques: simultaneous thermogravimetry–differential thermal analysis, which allowed us to verify the thermal decomposition associated with endothermic or exothermic phenomena; and differential scanning calorimetry that was used to determine gelatinization enthalpy as well as the rapid viscoamylographic analysis that provided the pasting temperature and viscosity. By means of non-contact-atomic force microscopy method and X-ray powder patterns diffractometry, it was possible to observe the surface morphology, topography of starch granules, and alterations in the granules’ crystallinity. 相似文献
46.
Dr. Roberta Pievo Brigitta Angerstein Dr. Alistair J. Fielding Dr. Christian Koch Prof. Dr. Ivo Feussner Prof. Dr. Marina Bennati 《Chemphyschem》2013,14(18):4094-4101
Electron paramagnetic resonance (EPR) spectroscopy in combination with the rapid freeze‐quench (RFQ) technique is a well‐established method to trap and characterize intermediates in chemical or enzymatic reactions at the millisecond or even shorter time scales. The method is particularly powerful for mechanistic studies of enzymatic reactions when combined with high‐frequency EPR (ν≥90 GHz), which permits the identification of substrate or protein radical intermediates by their electronic g values. In this work, we describe a new custom‐designed micro‐mix rapid freeze‐quench apparatus, for which reagent volumes for biological samples as small as 20 μL are required. The apparatus was implemented with homemade sample collectors appropriate for 9, 34, and 94 GHz EPR capillaries (4, 2, and 0.87 mm outer diameter, respectively) and the performance was evaluated. We demonstrate the application potential of the RFQ apparatus by following the enzymatic reaction of PpoA, a fungal dioxygenase producing hydro(pero)xylated fatty acids. The larger spectral resolution at 94 GHz allows the discernment of structural changes in the EPR spectra, which are not detectable in the same samples at the standard 9 GHz frequency. 相似文献
47.
Ivana Krausová Jan Kučera Ivo Světlík 《Journal of Radioanalytical and Nuclear Chemistry》2013,295(3):2043-2048
Neutron activation analysis (NAA) was used to determine 129I and the 129I/127I ratio in bovine thyroid, moss, and river sediment samples collected in the vicinity of the Temelín nuclear power plant (NPP) in south Bohemia. The NAA procedures comprised pre-irradiation separation of 129I by combustion of the samples in the stream of oxygen at 1,000 °C and trapping the liberated iodine in a LiOH/(NH4)2SO3 solution. Post-irradiation separation of 130I produced by the reaction 129I(n,γ)130I was carried out by extraction of elementary iodine with chloroform followed by precipitation of PdI2. Nondestructive, epithermal NAA was used to determine 127I employing the 127I(n,γ)128I reaction. The results showed that mean values of 129I and the 129I/127I ratio in the bovine thyroids varied from 22 to 61 mBq kg?1 (dry mass) and 2.8 × 10?9 to 5.4 × 10?9, respectively. These values are close to the lower end of results reported from various regions non-polluted with 129I. No significant differences were found between 129I concentrations and the 129I/127I ratios in the bovine thyroids collected prior to the start and after several years of operation of the NPP. The mean value and standard deviation of 129I in mBq kg?1, dry mass and the 129I/127I ratio in moss Pleurozium schreberi were 23 ± 16 and 2.3 × 10?9, respectively, whereas values of 129I in the river sediments were below 8–10 mBq kg?1 (dry mass) after several years of the NPP operation. 相似文献
48.
The influence of water content at impurity level (5–10,000 ppm) in acetonitrile, on the changes in relative basicity differences (ΔpK a values) of 13 pairs of bases, was studied both experimentally and computationally (COSMO-RS). The ΔpK a values involving smaller bases with localized charge in the cationic form were found to be more affected. A computational parameter, weighted average negative sigma (WANS), was proposed to quantify the charge delocalization in cations and succeeded in describing the observed changes of ΔpK a. The results validate the previously published basicity scale in acetonitrile with respect to solvent dryness and give guidelines for better experimental planning. 相似文献
49.
Matthew M. Wootten Dr. Sofja Tshepelevitsh Prof. Ivo Leito Prof. Jonathan Clayden 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(59):e202202247
A molecular system comprising a cationic zinc complex and an amino acid-derived ambident ligand having phosphate and carboxylate binding sites undergoes a series of rearrangements in which the metal cation migrates autonomously from one site to another. The location of the metal is identified by the circular dichroism spectrum of a ligated bis(2-quinolylmethyl)-(2-pyridylmethyl)amine (BQPA) chromophore, which takes a characteristic shape at each binding site. Migration is fuelled by the decomposition of trichloroacetic acid to CO2 and CHCl3, which progressively neutralises the acidity of the system as a function of time, revealing in sequence binding sites of increasing basicity. The migration rate responds to control by variation of the temperature, water content and triethylamine concentration, while an excess of fuel controls the duration of an induction period before the migration event. 相似文献
50.
Thomas Wiesner Dr. Zhu Wu Dr. Jie Han Prof. Dr. Lei Ji Dr. Alexandra Friedrich Dr. Ivo Krummenacher Michael Moos Prof. Dr. Christoph Lambert Prof. Dr. Holger Braunschweig Benjamin Rudin Dr. Hilmar Reiss Olena Tverskoy Dr. Frank Rominger Prof. Dr. Andreas Dreuw Prof. Dr. Todd B. Marder Dr. Jan Freudenberg Prof. Dr. Uwe H. F. Bunz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(69):e202201919
Tetraiodotetraazapentacene I4TAP , the last missing derivative in the series of halogenated silylated tetraazapentacenes, was synthesized via condensation chemistry from a TIPS-ethynylated diaminobenzothiadiazol in three steps. Single and double reduction furnished its air-stable monoanion and relatively air-stable dianion, both of which were characterized by crystallography. All three species are structurally and spectroscopically compared to non-halogenated TAP and Br4TAP . I4TAP is an n-channel material in thin-film transistors with average electron mobilities exceeding 1 cm2 (Vs)−1. 相似文献