Substituent electrophilicities in the NMR spectra of barbituric derivatives

Comparison of the ¹H and ¹³ C NMR spectra of a series of substituted 5‐benzylidene‐N,N′‐dimethylbarbituric acids (1) revealed chemical‐shift variations of different centers that correlated with the theoretical electrophilicities or with the substituent electrophilic constant σ_ω , in an example of the usefulness of these DFT‐based indices. Copyright © 2012 John Wiley & Sons, Ltd.     

Polymer electrolyte membranes based on polystyrenes with phosphonic acid via long alkyl side chains

A series of polystyrenes with phosphonic acid ( 5 ) via long alkyl side chains (4, 6, and 8 methylene units) were prepared by the radical polymerization of the corresponding diethyl ω‐(4‐vinylphenoxy)alkylphosphonates, followed by the hydrolysis with trimethylsilyl bromide. The resulting phosphonated polystyrene membranes had a high oxidative stability against Fenton's reagent at room temperature. The membranes prepared from 5 exhibited a very low water uptake, similar to that of Nafion 117 over the wide range of 30 to 80% relative humidity (RH). The proton conductivities of these membranes are lower than that of Nafion 117 in the range of 30 to 90% RH, but comparable or higher than those of the reported phosphonated polymers with higher IEC values, such as the phosphonated poly(N‐phenylacrylamide) (PDPAA, IEC: 6.72 mequiv/g) and fluorinated polymers with pendant phosphonic acids (M47, IEC: 8.5 mequiv/g), at low RH conditions despite the much lower IEC values (3.0–3.8 mequiv/g) of these membranes. These results suggest that the flexible pendant side chains of 5 would contribute to the formation of hydrogen‐bonding networks by considering the very low water uptake of these polymers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Interaction of dipropyltin(IV) with amino acids,peptides, dicarboxylic acids and DNA constituents

Interaction of dipropyltin(IV) with selected amino acids, peptides, dicarboxylic acids or DNA constituents was investigated using potentiometric techniques. Amino acids form 1?:?1 and 1?:?2 complexes and, in some cases, protonated complexes. The amino acid is bound to dipropyltin(IV) by the amino and carboxylate groups. Serine is complexed to dipropyltin(IV) with ionization of the alcoholic group. A relationship exists between the acid dissociation constant of the amino acids and the formation constants of the corresponding complexes. Dicarboxylic acids form both 1?:?1 and 1?:?2 complexes. Diacids forming five- and six-membered chelate rings are the most stable. Peptides form complexes with stoichiometric coefficients 111(MLH), 110(ML) and 11-1(MLH_?1)(tin: peptide: H⁺). The mode of coordination is discussed based on existing data and previous investigations. DNA constituents inosine, adenosine, uracil, uridine, and thymine form 1?:?1 and 1?:?2 complexes and the binding sites are assigned. Inosine 5′-monophosphate, guanosine 5′-monophosphate, adenosine 5′-monophosphate and adenine form protonated species in addition to 1?:?1 and 1?:?2 complexes. The protonation sites and tin-binding sites were elucidated. Cytosine and cytidine do not form complexes with dipropyltin(IV) due to low basicity of the donor sites. The stepwise formation constants of the complexes formed in solution were calculated using the non-linear least-square program MINIQUAD-75. The concentration distribution of the various complex species was evaluated as a function of pH.     

Palladium‐catalyzed carbonylative cyclization of β‐bromo‐α,β‐unsaturated carboxylic acids with primary amines leading to N‐alkylmaleimides

Cyclic β‐bromo‐α,β‐unsaturated carboxylic acids are carbonylatively cyclized with primary amines under carbon monoxide pressure in MeCN in the presence of a catalytic amount of PdCl₂(PPh₃)₂ to give N‐alkylmaleimides. Copyright © 2012 John Wiley & Sons, Ltd.     

Cyclopalladated ferrocenylimine as an efficient catalyst for the syntheses of diarylmethane derivatives

The cyclopalladated ferrocenylimine adducts Ia , Ib , Ic were evaluated in the Suzuki cross‐coupling reaction of benzyl halides with arylboronic acids. The tricyclohexylphosphine adduct Ia exhibited highly catalytic activity for the coupling of aryl and heteroaryl boronic acids containing various functional groups with benzylic bromides and chlorides (up to 99% yield), furnishing diarylmethane derivatives with low catalyst loading (1 mol%). It is worth noting that catalyst Ia can be reused eight times without losing its catalytic activity. Copyright © 2012 John Wiley & Sons, Ltd.     

脂肪胺类化合物氨基15N NMR化学位移规律的研究

提出了计算脂肪胺类化合物的¹⁵N NMR化学位移的经验公式：δ_cal（¹⁵N）=-380.2+ΣΔα+ΣΔβ+ΣΔγ+ΣΔδ+ΣC,结合最小二乘法通过线性回归得到了11种取代基参数,计算结果以133种化合物的133个¹⁵N NMR化学位移数据为样本点进行回归检验,置信度为99.5 %,约有94.7 %的¹⁵N NMR化学位移计算值的计算误差小于5.0（相对误差小于0.5 %）.     

Acoustic and hydrodynamic cavitation assisted hydrolysis and valorisation of waste human hair for the enrichment of amino acids

Hair waste in large amount is produced in India from temples and saloons, India alone exported approximately 1 million kg of hair in 2010. Incineration and degradation of waste human hair leads to environmental concerns. The hydrothermal process is a conventional method for the production of hair hydrolysate. The hydrothermal process is carried out at a very high temperature and pressure, which causes the degradation of heat-sensitive essential amino acids, thereby depleting the nutritional value. This work deals with alkaline hydrolysis of human hair using acoustic and hydrodynamic cavitation, and comparison with the conventional method. The optimal operating conditions for highest efficiency was observed, for the hydrolysis of 1 g of sample hairs in 100 mL of solution, at 4:1 (KOH: hair) ratio, soaking time of 24 h, the ultrasonic power density of 600 W dm⁻³ (20 KHz frequency and input power 200 W) or hydrodynamic cavitation inlet pressure of 4 or 7 bars. Cavitation results in rupture of disulfide linkages in proteins and mechanical effects lead to cleavage of several hydrogen bonds breaking the keratin sheet structure in hair. Breakdown of bonds leads to a decrease in viscosity of the solution. 10% and 6% reduction in viscosity is obtained at optimal conditions for ultrasonic and hydrodynamic cavitation treatment, respectively. FTIR analysis of produced hair hydrolysate confirmed that the disulfide bonds in hair proteins are broken down during cavitation. The amino acid of hair hydrolysate, prepared using cavitation, has a relatively higher digestibility and nutritional value due to the enhancement of amino-acid content, confirmed using amino acid analysis. Cavitation assisted hair hydrolysate has a potential application in agricultural engineering as a fertilizer for improvement of the quality of the soil and land. Cavitation based hair hydrolysate can also be used as an environmentally friendly and economical source of essential amino acids and digestibles for animal or poultry feed.     

Effect of halogen atom on electron spin polarization studied by CIDEP,using halogen substituted aromatic acyl compounds

The reaction and spin dynamics of the photocleavage reaction of 2-chloro-2′-acetylnaphthalene were studied by time-resolved FT-EPR and transient absorption (TA) spectroscopy. The photocleavage reaction from both singlet and triplet states was observed by TA and EPR experiments, although the radical cleavage reaction in the excited triplet state is energetically unfavourable. This feature has been explained by the ionic cleavage reaction due to the electro-negativity of the chlorine atoms. The time-resolved FT-EPR spectra were similar to those observed in the bromine substituted compound, 2-BAN, reported in a previous paper. The origin of the electron spin polarization was assigned to the radical triplet pair mechanism (RTPM) and free radical pair mechanism (F-pair RPM) from analysis of the time profiles of the spin polarization.     

Relationship between experimental pKa values in aqueous solution and a gas phase bond length in bicyclo[2.2.2]octane and cubane carboxylic acids

Linear correlations were established between the calculated bond lengths and the pK_a or σ_I values for a series of 4‐substituted bicyclo[2.2.2]octane‐1‐carboxylic acid and 4‐cubane‐1‐carboxylic acid derivatives. The bond lengths have been calculated at a modest computational level, HF/6‐31G(d), both in the gas phase and with the continuum solvation model, polarisable continuum model (PCM). In general, the best correlations are obtained when the PCM model is taken into account, especially when neutral and charged molecules are considered together. The best models in each case show square correlation coefficients (R²) larger than 0.9 and indicate that they can be used as predictive tools. These results expand previous results that indicate the possibility of a relationship between gas phase bond length and pK_a values in aqueous solution and indicate that such relationships are more general than hitherto expected. Copyright © 2013 John Wiley & Sons, Ltd.     

Combined effects of high pressure and sodium hydrogen carbonate treatment on pork ham: improvement of texture and palatability

In this study, the combined effects of high pressure and sodium hydrogen carbonate (NaHCO₃) treatment on the physical and chemical properties, and palatability of pork ham, a tough and under-utilized meat, were investigated. Assessment of meat properties with heat treatment, after exposure to NaHCO₃ and high pressure treatment, revealed an increase in water content, and decreased weight reduction and rupture stress. The free amino acid content of meat samples increased with NaHCO₃ and high pressure treatment. The effect of high pressure processing was especially notable at a pressure of 300 MPa. Sensory evaluation showed that meat subjected to high pressure processing after NaHCO₃ treatment was tender and juicy. In addition, the sample produced minimal residue in the mouth and was characterized by a good taste.