Thermally Crosslinkable and Chemically Modifiable Aromatic Polyesters Possessing Pendant Propargyloxy Groups

New aromatic (co)polyesters containing pendant propargyloxy groups were synthesized by phase transfer‐catalyzed interfacial polycondensation of 5‐(propargyloxy)isophthaloyl chloride (P‐IPC) and various compositions of P‐IPC and isophthaloyl chloride with bisphenol A. FTIR and NMR spectroscopic data, respectively, revealed successful incorporation of pendant propargyloxy groups into (co)polyesters and formation of (co)polyesters with desired compositions. (Co)polyesters exhibited good solubility in common organic solvents such as chloroform, dichloromethane, and tetrahydrofuran and could be cast into transparent, flexible, and tough films from chloroform solution. Inherent viscosities and number average molecular weights of (co)polyesters were in the range 0.77–1.33 dL/g and 43,600–118,000 g/mol, respectively, indicating the achievement of reasonably high‐molecular weights. The 10% weight loss temperatures of (co)polyesters were in the range 390–420 °C, demonstrating their good thermal stability. (Co)polyesters exhibited T_g in the range 146–170 °C and T_g values decreased with increase in mol % incorporation of P‐IPC. The study of non‐isothermal curing by DSC indicated thermal crosslinking of (co)polyesters via propargyloxy groups. The utility of pendant propargyloxy group was demonstrated by post‐modification of the selected copolyester with 1‐(4‐azidobutyl)pyrene, 9‐(azidomethyl)anthracene, and azido‐terminated poly(ethyleneglycol) monomethyl ether via copper(I)‐catalyzed Huisgen 1,3‐dipolar cycloaddition reaction. FTIR and ¹H NMR spectra confirmed that click reaction was quantitative. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 588–597     

Efficient synthesis of 1,4-dihydronaphthalenelignans from 5-methylene-4-substituted-2(5H)-furanones and a concise synthesis of solafuranone

A short synthetic strategy for synthesis of lignan analogues involving 5-methylene-4-substituted-2(5H)-furanones as the key intermediates has been developed. Various lignans including the natural product solafuranone and analogues of dihydrotaiwanin C and deoxydehydropodophyllotoxin were synthesized in good yields.     

Working group report: Neutrino and astroparticle physics

This is the report of neutrino and astroparticle physics working group at WHEPP-7. Discussions and work on CP violation in long baseline neutrino experiments, ultra high energy neutrinos, supernova neutrinos and water Cerenkov detectors are discussed.     

Density dependence of electron mobility in dense gases

The density (N) dependence of electron mobility (μ) in various dense gases (H₂, N₂, O₂, CO₂ and rare gases) has been calculated using a multiple-scattering approach. Deviation of the high density gas from its perfect gas behaviour has been taken into account through the temperature-dependent second virial coefficient. Multiple scattering of electrons leads to shifts in their kinetic energy and it also changes their distribution functions. This unified approach predicts both positive and negative effects. The positive (negative) effect entails on increase (decrease) of μ withN. We have assessed the available data on momentum transfer cross-sections by comparing the mobility at very low densities (Nμ)₀ with experimental results. The density dependence is studied by comparing the calculated ratioNμ)/Nμ)₀ with the observed values and other theoretical work. The Legler model which assumes a constant cross-section is inadequate for predicting the observed density dependence. We obtain good agreement with available experimental work for all the atomic and molecular species studied here.     

Enantioselective Preparation of 2‐Aminomethyl Carboxylic Acid Derivatives: Solving the β2‐Amino Acid Problem with the Chiral Auxiliary 4‐Isopropyl‐5,5‐diphenyloxazolidin‐2‐one (DIOZ). Preliminary Communication

Multigram amounts of suitably protected β²‐amino acids with 17 of the 20 proteinogenic side chains are prepared by diastereoselective reactions of Li, B, or Ti enolates of the corresponding 3‐acyl‐4‐isopropyl‐5,5‐diphenyloxazolidin‐2‐ones (acyl‐DIOZ; 1 ) with appropriate electrophiles (amidomethylation, hydroxyalkylation, (benzyloxycarbonyl)methylation) in yields of 55–90% and with diastereoselectivities of 80 to >97% (Scheme). The primary products 2 – 8 thus obtained are converted to protected β²‐amino acids by standard procedures (Table 1). Many of the DIOZ derivatives are highly crystalline compounds (31 X‐ray crystal structures in Table 2). The chiral auxiliary DIOZ, readily prepared in either enantiomeric form, is recovered with high yield.     

Extraction of uranium(VI) and plutonium(IV) with dihexylbutyramide and dihexylisobutyramide from nitric acid medium

The extraction of uranium(VI) and plutonium(IV) was carried out with two isomeric monoamides, dihexylbutyramide (DHBA) and dihexylisobutyramide (DHIBA) from nitric acid medium, usingn-dodecane as diluent. The possibility of separation of the two metal ions from each other without valency adjustment was attempted. U(VI) was extracted as its disolvate, while Pu(IV) was extracted as its trisolvate. From the variation of distribution ratio with temperature, it was shown that the extraction reaction was enthalpy controlled in all the cases.     

Di(2-ethyl hexyl) butyramide and di(2-ethyl hexyl)isobutyramide as extractants for uranium(VI) and plutonium(IV)

The extraction of uranium(VI) and plutonium(IV) from nitric acid into n-dodecane was studied using two isomeric branched alkyl amides, di(2-ethyl hexyl) butyramide (DEHBA) and di(2-ethyl hexyl) isobutyramide (DEHIBA). The extraction ratios of Pu(IV) at relatively high acidities were higher than the corresponding values for U(VI) in the case of DEHBA. However, with DEHIBA the values for Pu(IV) were negligibly small. Pu(IV) was found to be extracted as trisolvate by DEHBA and as disolvate by DEHIBA. U(VI) was extracted by both the amides. From the study of the extraction reactions at different temperatures, it was shown that all the reactions in the present investigation were enthalpy favoured and entropy disfavoured. Separation of Pu(IV) from bulk of U(VI) was feasible. However, the purity of the separated plutonium was not satisfactory in batch extraction studies.     

The versatility of salicylaldehyde thiosemicarbazone in the determination of copper in blood using adsorptive stripping voltammetry

The adsorptive cathodic stripping voltammetry technique (AdCSV) is used to determine copper(II) using salicylaldehyde thiosemicarbazone (N, S- donor) as a complexing agent on hanging mercury drop electrode at pH 9.3. Variable factors affecting the response, i.e. the concentration of ligand, pH, adsorption potential and adsorption time are assessed and optimized. The adsorbed complex of copper(II) and salicylaldehyde thiosemicarbazone gives a well defined cathodic stripping peak current at −0.35 V, which has been used for the determination of copper in the concentration range of 7.85 × 10⁻⁹ to 8.00 × 10⁻⁶ M with accumulation time of 360 s at −0.1 V versus Ag/AgCl. This technique has been applied for the determination of copper in various digested samples of whole blood at trace levels.     

Line strengths and transition probabilities for allowed transitions in Fe XXI

Configuration interaction wavefunctions, transition energies, line strengths and transition probabilities for allowed transitions within then=2 complex of C-like Fe XXI have been calculated in the LS coupling scheme. We included internal, semi-internal, and all-external types of correlations. We compare our non-relativistic line strengths values with those of relativistic calculations in the Breit-Pauli approximation. The relativistic effects on line strengths are negligible for all transitions except for the transition¹ D ^e →¹ D ⁰. Experimental wavelengths are used in the calculation of transition probabilities.