Sulfur-containing polymers. Synthesis and properties of novel poly(arylene thioether)s based on 2,2-bis(4-mercaptophenyl)propane

Novel poly(arylene thioether)s were synthesised using the one pot polymerisation method from the bis(N,N-dimethyl-S-carbamate) of 2,2-bis(4-mercaptophenyl)propane and activated difluoro aromatic compounds. Each of the polymers, obtained in good yields and with fairly high molecular weights, were characterised by IR, GPC and NMR analyses. In particular, the NMR characterisation was performed using ¹H NMR, ¹³C NMR, DEPT, 2D COSY and 2D HSQC experiments. To study the effect on the thermal properties of replacing the ethereal oxygen atoms with sulfur atoms, we have synthesised the counterparts, the poly(arylene ether)s, with similar molecular weights. We observed that the substitution of the ethereal oxygen atoms with sulfur atoms results in a slightly lower thermal stability for the poly(thioether ketone)s, both under nitrogen and in air, and does not modify the T_g values. For the poly(thioether sulfone), on the other hand, the thermal stability is equal to that of the poly(ether sulfone), while the T_g is 10 °C lower. Furthermore, each sample is completely amorphous, with the exception of one of the poly(thioether ketone)s (sample 1b), which shows the capacity to crystallise, even if with a very slow crystallisation kinetics.     

Column reversed-phase partition chromatography for the isolation of some radionuclides from biological materials

Revised-phase partition chromatography is a very useful tool for selective isolation of radionuclides from biological materials. Some new applications of this technique to the resolution of practical problems in radiation protection are reported. Natural thorium and enriched uranium can be determined separately and together in urine by means of a column of Microthene-710 supporting a solution of tri-n-octyl-phosphine oxide (TOPO) in cyclohexane; batchwise extraction processes with Microthene supporting TOPO are also successful. Strontium-90 is determined in urine by a batch extraction of yttrium-90 with a slurry of Microthene supporting the liquid cation exchanger di-(2-ethylhexyl)phosphoric acid. Only a wet mineralization of the urines is required and the analyses are simple, rapid and sufficiently accurate. A method for the isolation of iodine from foodstuffs with a Microthene-benzene column is also described.     

Regio- and stereoselectivity of the addition of O-, S-, N-, and C-nucleophiles to the beta vinyl oxirane derived from D-glucal

6-O-Trityl- (1a) and 6-(O-benzyl)-substituted epoxide (1b) derived from D-glucal were examined in their addition reactions with O-, C-, N-, and S-nucleophiles. A 1,4-regio- and beta-stereoselective or an anti 1,2-addition pathway is commonly observed depending on the ability of the nucleophile to coordinate with the oxirane oxygen. When TMSN(3) or LiN(3) are used as azide-based nucleophiles, a 1,2-syn-addition pathway is also observed.     

Activation of chlorobenzene as phenylating agent by means of a dinitrogen-molybdenum complex

Bis(dinitrogen)bis[1,2-bis(diphenylphosphino)ethane]molybdenum reacts with chlorobenzene to form molybdenum chloro complexes and phenylated organic products. Benzene, biphenyl, o-, m-, p-chlorobiphenyl, a dihydro derivative of o-chlorobiphenyl, triphenylphosphine and diphenylvinylphosphine were formed. The isomer distribution of the chlorobiphenyls is close to that obtained by decomposition of 0.02 M benzoyl peroxide in chlorobenzene under dinitrogen. The cleavage of the PhCl bond induced by the molybdenum-dinitrogen complex appears to give rise to the same homolytic reaction pattern. Phenylation of anisole and of triethyl phosphite has also been achieved with the same reagent.     

Azido derivatives of dinuclear copper(II) and 1D polynuclear nickel(II) complexes containing an unsymmetrical bidentate amine: synthesis,crystalline architecture,and magnetic behavior

Transition Metal Chemistry - Dinuclear copper(II) complex [Cu2(L)2(μ2-1,1-N3)2(N3)2] (1) with double μ1,1-azido bridges and polynuclear nickel(II) complex...     

Synthesis of 2-[(E)-Hex-1′-enyl]tetrahydropyran Starting from 3-Nitro-4,5-dihydro-6H-pyran

The four steps preparation of 2-[(E)-hex-1′-enyl]tetrahydropyran starting from 3-nitro-4,5-dihydro-6H-pyran has been carried out in 40% overall yield.     

The adjoint representation inside the exterior algebra of a simple Lie algebra

For a simple complex Lie algebra g$\mathfrak{g}$ we study the space of invariants A=(?g^?⊗g^?)^g$A={(?{\mathfrak{g}}^{?}\otimes {\mathfrak{g}}^{?})}^{\mathfrak{g}}$, which describes the isotypic component of type g$\mathfrak{g}$ in ?g^?$?{\mathfrak{g}}^{?}$, as a module over the algebra of invariants (?g^?)^g${(?{\mathfrak{g}}^{?})}^{\mathfrak{g}}$. As main result we prove that A   is a free module, of rank twice the rank of g$\mathfrak{g}$, over the exterior algebra generated by all primitive invariants in (?g^?)^g${(?{\mathfrak{g}}^{?})}^{\mathfrak{g}}$, with the exception of the one of highest degree.     

From the SmA to the Hexatic,Including the SmC*, SmC*A and SmC*re Phases: A 2H NMR Relaxation Study

The molecular dynamics of a ferroelectric liquid crystal, denoted ZLL 7/* , is investigated by means of ²H NMR relaxation. The spin–lattice (T_1Q and T_1Z) and spin–spin (T₂) relaxation times of two isotopomers of ZLL 7/* , labeled on the phenyl and biphenyl fragments, are measured and their behavior upon passing from the SmA to the hexatic phase, through the ferroelectric SmC*, antiferroelectric SmC*_A, and re‐entrant ferroelectric SmC*_re phases, is discussed. A comparison between the measured T₂ and T₂*, directly related to the experimental linewidth, provides information on the heterogeneity of the system, thus allowing confirmation of previous hypotheses concerning the structural and ordering properties of the SmC*_A and SmC*_re phases. The possibility to look at different sites of the core of the ZLL 7/* smectogen reveals a peculiar sensitivity of the phenyl moiety with respect to the biphenyl fragment, which may be justified by its vicinity to the chiral centers. Interestingly, the trend of the longitudinal relaxation times is characterized by a minimum that corresponds to the SmC*_A and SmC*_re phases, which is reproducible for the two isotopomers and at several Larmor frequencies. A quantitative analysis of T_1Q and T_1Z is performed in the SmA and SmC* phases, for which the narrowing regime approximation is valid. A multifrequency approach is applied to self‐consistently determine the diffusion coefficients for the overall molecular motions, namely spinning and tumbling, and the internal rotations around the para axes of the phenyl and biphenyl fragments. The effect of the magnetic field in unwinding the helical structure of the SmC* phase (for H>9 T) allows observation of a sensitive change in the rotational diffusion coefficients in the frustrated unwound SmC* phase with respect to the SmC* phase.