Advances in the chemistry of β-lactam and its medicinal applications

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Thermally induced polytype transformations among the layered double hydroxides (LDHs) of Mg and Zn with Al

The hydrotalcite-like layered double hydroxide (LDH) of Mg with Al shows dramatic changes in the peaks arising from the (h0l)/(0kl) family of reflections in its powder X-ray diffraction pattern during thermal treatment. DIFFaX simulations show that these changes arise due to the transformation of the disordered 3R1 polytype into the 1H polytype on dehydration. The 1H polytype is an essential precursor to the decomposition reaction, which results in the formation of an oxide residue with the rock salt structure. In contrast, the LDH of Zn with Al does not undergo any such transformation, retaining the structure of the 3R1 polytype until decomposition into the oxide residue. Given the poor octahedral site preference of the Zn2+ ion, the 1H polytype is neither structurally stable nor is it topochemically necessary for the thermal decomposition of the Zn-Al LDH, the end product of the decomposition reaction being an oxide with the wurtzite structure.     

The effect of copolymer composition on the dynamics of random copolymers in a homopolymer matrix

The effect of copolymer composition on the dynamics of random copolymers in a homopolymer matrix is studied using computer simulations within the framework of the bond-fluctuation model on blends containing low concentrations (10%) of A-B copolymers, where A and B are two different types of monomers, dispersed in a homopolymer matrix of chains with only A-type monomers. Four copolymer compositions were studied, phi(A)=0.33, phi(A)=0.5, phi(A)=0.66, and phi(A)=0.82, while maintaining a statistically random sequence distribution. For this study, we have only included intermolecular interactions between A and B monomers. Our results indicate, in agreement with experimental data, that copolymer composition has an impact on system dynamics. Analysis of the structure reveals that copolymers with majority A content are expanded in the homopolymer matrix, have fewer interchain copolymer-copolymer contacts, and are well dispersed in the homopolymer matrix. On the other hand, copolymers with lower A content form a more compact structure, have more interchain contacts, and form aggregates that are short lived. This in turn leads to slower system dynamics. Both the radius of gyration (Rg) and copolymer end-to-end vectors (Re) increase with increasing A content until phi(A)=0.66 and then decrease. Copolymers with lower A content form more compact structures as the repulsive interactions between unlike species are minimized by the copolymers folding back on themselves and forming aggregates of copolymer chains. Thus, these results provide insight into the variation of copolymer dynamics with composition in the system by documenting the correlation between the thermodynamics of this mixture, the conformation of a copolymer chain in a homopolymer matrix, and the dynamics of both components in this blend.     

Determination of alkali, alkaline earth and transition metal ions in UO2, ThO2 powders and sintered (Th,U)O2 pellets by ion chromatography

An ion chromatographic method has been developed for the determination of traces of Li⁺, Na⁺, K⁺, Ca²⁺, Mg²⁺, Sr²⁺, Fe³⁺, Cu²⁺, Ni^2+, Co²⁺, Zn²⁺, Cd²⁺, Mn²⁺ in UO₂, ThO₂ powders and sintered (Th,U)O₂ pellets. This new method utilizes poly-(butadiene-maleic acid) (PBDMA) coated silica cation exchange column and mixed functionality column of anion and cation exchange to achieve the separation of alkali, alkaline earths and transition metal ions, respectively. It involves matrix separation after sample dissolution by solvent extraction with TBP (tri butyl phosphate)-TOPO (tri octyl phosphine oxide)/CCl₄. Interference of transition metal ions in the determination of alkali, alkaline earth metal ions are removed by using pyridine 2,6-dicarboxylic acid (PDCA) in the tartaric acid mobile phase. Mobile phase composition is optimized for the base line separation of alkali, alkaline earth and transition metal ions. Linear calibration graphs in the range 0.01–20 μg mL⁻¹ were obtained with regression coefficients better than 0.999. The respective relative standard deviations were also determined. Recoveries of the spiked samples are within ±10% of the expected value. The developed method is authenticated by comparison with certified standards of UO₂ and ThO₂ powders.     

Unifying darko-lepto-genesis with scalar triplet inflation

We present a scalar triplet extension of the standard model to unify the origin of inflation with neutrino mass, asymmetric dark matter and leptogenesis. In presence of non-minimal couplings to gravity the scalar triplet, mixed with the standard model Higgs, plays the role of inflaton in the early Universe, while its decay to SM Higgs, lepton and dark matter simultaneously generate an asymmetry in the visible and dark matter sectors. On the other hand, in the low energy effective theory the induced vacuum expectation value of the triplet gives sub-eV Majorana masses to active neutrinos. We investigate the model parameter space leading to successful inflation as well as the observed dark matter to baryon abundance. Assuming the standard model like Higgs mass to be at 125–126 GeV, we found that the mass scale of the scalar triplet to be ?O(10⁹) GeV$?O({10}^9)\text{GeV}$ and its trilinear coupling to doublet Higgs is ?0.09 so that it not only evades the possibility of having a metastable vacuum in the standard model, but also lead to a rich phenomenological consequences as stated above. Moreover, we found that the scalar triplet inflation strongly constrains the quartic couplings, while allowing for a wide range of Yukawa couplings which generate the CP asymmetries in the visible and dark matter sectors.     

Development of liquid chromatography-triple quadrupole mass spectrometric method for the quantitative determination of a novel adjuvant,Imidazoquinoline gallamide in aluminum hydroxide gel-Imidazoquinoline gallamide and COVAXIN

Imidazoquinoline gallamide is a toll-like receptor 7/8 agonist, belongs to the imidazoquinoline class, has the potential to activate antigen-presenting cells, and enhances immune response, primarily Th1 response. The COVAXIN is a whole virion inactivated Coronavirus disease 2019 vaccine formulated with this novel adjuvant called, aluminum hydroxide gel Imidazoquinoline gallamide, wherein, Imidazoquinoline gallamide is chemisorbed onto aluminum hydroxide gel. Herein, an analytical method based on liquid chromatography-tandem mass spectrometry was developed to identify and quantify Imidazoquinoline gallamide in aluminum hydroxide gel Imidazoquinoline gallamide and COVAXIN. The multiple reaction monitoring transitions were optimized for Imidazoquinoline gallamide quantification are [M+H]⁺ ions with 512.24→343.19 m/z (quantifier ion) and 512.24→360.22 m/z (qualifier ion). The developed method was validated as per the international conference on harmonization quality2 revison1 guidelines. The method was linear in the range of 0.025–10 µg/mL with a coefficient of determination of 0.9985 and the limit of quantification is 0.025 µg/mL. The accuracy was in the range of 82–121 % and intra- and inter-day precision was less than 7.1% and 5.39%, respectively. The expanded uncertainty results are 9.2% for Imidazoquinoline gallamide in the sample. The validated method was successfully applied to evaluate Imidazoquinoline gallamide concentration in every batch of COVAXIN.     

Novel 3,3′-(alkanediyl)bis-(2,2,2-triaryl-1-oxa-2-stiba-3-azabenzo[d]cyclohex-5-enes)

The hitherto unreported compounds of general structure 3,3′-(alkanediyl)bis-(2,2,2-triaryl-1-oxa-2-stiba-3-azabenzo[d]cyclohex-5-ene) have been synthesized in 48-56% yields by the cyclization of the tetrasodium salt of N,N′-bis(2-hydroxybenzyl)-1,2-diaminoethane(II) or of N,N′-bis(2-hydroxybenzyl)-1,3-diaminopropane(II*) with R₃SbBr₂ (R = phenyl, p-tolyl, or mesityl). The tetrasodium salts were prepared by the reactions of the corresponding amines with sodium hydride. The amines (II and II*), in turn, were obtained by the sodium borohydride reduction of N,N′-bis(salicylidene)-1,2-diaminoethane and N,N′-bis-(salicylidene)-1,3,-diaminopropane, respectively. The heterocyclic compounds are air stable and moisture insensitive. These compounds have been characterized by elemental analyses, molecular weight determinations, and by IR, far IR, ¹H, and ¹³C NMR spectral studies. © 1996 John Wiley & Sons, Inc.