Dielectric relaxation analysis of starch oligomers and polymers with respect to their chain length

Starch belongs to the polyglucan group. This type of polysaccharide shows a broad β-relaxation process in dielectric spectra at low temperatures, which has its molecular origin in orientational motions of sugar rings via glucosidic linkages. This chain dynamic was investigated for α(1,4)-linked starch oligomers with well-defined chain lengths of 2, 3, 4, 6, and 7 anhydroglucose units (AGUs) and for α(1,4)-polyglucans with average degrees of polymerization of 5, 10, 56, 70, and so forth (up to 3000; calculated from the mean molecular weight). The activation energy (E_a) of the segmental chain motion was lowest for dimeric maltose (E_a = 49.4 ± 1.3 kJ/mol), and this was followed by passage through a maximum at a degree of polymerization of 6 (E_a = 60.8 ± 1.8 kJ/mol). Subsequently, E_a leveled off at a value of about 52 ± 1.5 kJ/mol for chains containing more than 100 repeating units. The results were compared with the values of cellulose-like oligomers and polymers bearing a β(1,4)-linkage. Interestingly, the shape of the E_a dependency on the chain length of the molecules was qualitatively the same for both systems, whereas quantitatively the starch-like substances generally showed higher E_a values. Additionally, and for comparison, three cyclodextrins were measured by dielectric relaxation spectroscopy. The ringlike molecules, with 6, 7, and 8 α(1,4)-linked AGUs, showed moderately different types of dielectric spectra. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 188–197, 2004     

On the computation of scaling coefficients of Daubechies' wavelets

In the present paper, Daubechies' wavelets and the computation of their scaling coefficients are briefly reviewed. Then a new method of computation is proposed. This method is based on the work [7] concerning a new orthonormality condition and relations among scaling moments, respectively. For filter lengths up to 16, the arising system can be explicitly solved with algebraic methods like Gröbner bases. Its simple structure allows one to find quickly all possible solutions.     

Synthese de composes dihydro-2,3 furanniques par hydroboration d'alcools β-acetyleniques

Hydroboration of β-acetylenic alcohols followed by NaOH/H₂O₂ oxidation leads to hemiacetals of γ-aldols which are easily dehydrated to 2,3-dihydrofuran compounds. The reaction gives good yields with hindered alcohols and its stereochemistry may be controlled during the organometallic synthesis of the starting alcohol.     

Chalcogenide derivatives of imidotin cage complexes

Reaction of the secocubane [Sn3(mu2-NHtBu)2(mu2-NtBu)(mu3-NtBu)] (1) with dibutylmagnesium produces the heterobimetallic cubane [Sn3Mg(mu3-NtBu)4] (4) which forms the monochalcogenide complexes of general formula [ESn3Mg(mu3-NtBu)4] (5a, E = Se; 5b, E = Te) upon reaction with elemental chalcogens in THF. By contrast, the reaction of the anionic lithiated cubane [Sn3Li(mu3-NtBu)4]- with the appropriate quantity of selenium or tellurium leads to the sequential chalcogenation of each of the three Sn(II) centres. Pure samples of the mono- or dichalcogenides are, however, best obtained by stoichiometric redistribution reactions of [Sn3Li(mu3-NtBu)4]- and the trichalcogenides [E3Sn3Li(mu3-NtBu)4]- (E = Se, Te). These reactions are conveniently monitored by using 119Sn NMR spectroscopy. The anion [Sn3Li(mu3-NtBu)4]- also acts as an effective chalcogen-transfer reagent in reactions of selenium with the neutral cubane [{Snmu3-N(dipp)}4] (8) (dipp = 2,6-diisopropylphenyl) to give the dimer [(thf)Sn{mu-N(dipp)}2Sn(mu-Se)2Sn{mu-N(dipp)}2Sn(thf)] (9), a transformation that results in cleavage of the Sn4N4 cubane into four-membered Sn2N2 rings. The X-ray structures of 4, 5a, 5b, [Sn3Li(thf)(mu3-NtBu)4(mu3-Se)(mu2-Li)(thf)]2 (6a), [TeSn3Li(mu3-NtBu)4][Li(thf)4] (6b), [Te2Sn3Li(mu3-NtBu)4][Li([12]crown-4)2] (7b') and 9 are presented. The fluxional behaviour of cubic imidotin chalcogenides and the correlation between NMR coupling constants and tin-chalcogen bond lengths are also discussed.     

Structure and mechanical properties of poly(l-lactide)/layered silicate nanocomposites

Poly(ε-caprolactone) (PCL) masterbatches with the intercalated and the exfoliated morphology were prepared by ring opening polymerization of ε-caprolactone in the presence of organomodified montmorillonite (MMT) Cloisite 30B. Poly(l-lactide) (PLLA) nanocomposites with Cloisite 30B or PCL masterbatches were prepared by melt blending. The effects of the silicate type, MMT content and the nanocomposite morphology on thermal and mechanical properties of PLLA nanocomposites were examined. The montmorillonite particles in PLLA/Cloisite 30B and PLLA/intercalated masterbatch nanocomposites were intercalated. In contrary to expectations, the exfoliated silicate layers of exfoliated masterbatch were not transferred into the PLLA matrix. Due to a low miscibility of PCL and PLLA, MMT remained in the phase-separated masterbatch domains. The stress-strain characteristics of PLLA nanocomposites, Young modulus E, yield stress σ_y and yield strain ε_y, decreased with increasing MMT concentration, which is associated with the increase in PCL content. The expected stiffening effect of MMT was low due to a low aspect ratio of its particles and was obscured by both plastifying effects of PCL and low PLLA crystallinity. Interestingly, in contrast to the neat PLLA, ductility was enhanced in all PLLA/Cloisite 30B materials and in PLLA/masterbatch nanocomposites with low MMT concentrations.     

Gene expression analysis for high throughput screening applications

To meet growing needs for high throughput gene expression profiling, we established a new automated high throughput TaqMan RT-PCR method for quantitative mRNA expression analysis. In this method, the Allegro( trade mark ) (Zymark) system conducts all sample tracking and liquid handling steps, and ABI PRISM 7900 HT (Applied Biosystems) is used to conduct real-time determination of the C(t) value when amplification of PCR products is first detected and accumulation of inhibitory PCR products is unlikely to occur. The ABI PRISM 7900 HT Sequence Detection System features a real-time PCR instrument with 384-well-plate compatibility and robotic loading, and continuous wavelength detection, which enables the use of multiple fluorophores in a single reaction. The Allegro System offers an assembly line approach with a modular design that allows reconfiguration of the components to accommodate variations in the assay flow. In the present study, we have established and validated a new automated High Throughput (HT) TaqMan RT-PCR- based method for quantitative mRNA expression analysis. The data demonstrate that HT-Taqman PCR is a powerful tool that can be used for measuring low concentrations of mRNA, and is highly accurate, reproducible, and amenable to high throughput analysis. Results suggest that HT-TaqMan is a reliable method for the quantification of low-expression genes and a powerful tool with HT capability for target identification/validation, structure-activity relationship (SAR) study, compound selection for efficacy studies, and biomarker identification in drug discovery and development.     

Thermal behaviour of new N,N-dimethylbiguanide complexes having selective and effective antibacterial activity

The complexes of the type M(HDMBG)₂(CH₃COO)₂·nH₂O ((1) M:Mn, n=1.5; (2) M:Ni, n=0; (3) M:Cu, n=2; (4) M:Zn, n=2; DMBG: N,N-dimethylbiguanide) present in vitro antimicrobial activity. The thermal analysis has evidenced the thermal intervals of stability and also the thermodynamics effects that accompany them. The different nature of the ligands generates a different thermal behaviour for the complexes. The thermal transformations are complex processes according to TG and DTG curves including dehydration, oxidative condensation of –C=N– units as well as thermolysis processes. The final products of decomposition are the most stable metal oxides.     

Remarkably large remote-stereocenter-induced chromatographic differences: azulenyl 1,5-diols

A series of four new azulene-1,5-diol diastereomers were prepared and found to exhibit large differences (ΔR_f 0.22–0.46) in silica TLC mobilities despite having stereocenters four bonds apart. The stereoisomers were identified by X-ray crystallography, and in all cases the RR/SS diastereomers were less strongly retained than the RS/SR diastereomers. The crystal structures suggested that this is due to a conformational preference for the CF₃ groups to be nearly perpendicular to the plane of the azulene ring, which caused the dihedral angle between the OH groups to be larger (in the RR/SS diastereomers) or smaller (in the RS/SR diastereomers). The smaller dihedral angles allow the RS/SR diastereomers to simultaneously bind to a silica surface and thus be more strongly retained. Two similar benzene derivatives and several cycloalkanediols with more proximate stereocenters showed little or no difference in mobilities between diastereomers, though the NMR differences were greater. Thus, the azulene ring is an important factor in enforcing the conformational preferences, either through steric interactions with the 4/8 substituents (H or methyl) or its significant dipole moment, or both.     

Surface energy gradient driven convection for generating nanoscale and microscale patterned polymer films using photosensitizers

The Marangoni effect describes how fluid flows in response to gradients in surface energy. This phenomenon could be broadly harnessed to pattern the surface topography of polymer films if generalizable techniques for programming surface energy gradients existed. Here, a near UV–visible light (NUV–vis) photosensitizer, 9,10‐dibromo‐anthracene (DBA), was doped into thin films of a model polymer, poly(isobutyl methacrylate). After exposure to light through a photomask and heating above the glass transition, thermolysis of photo‐oxidized DBA and grafting to the polymer promoted flow of the film material into the exposed regions. This mechanism did not significantly alter the molecular weight of PiBMA or the film's glass transition temperature, but resulted in an increase in film surface energy as indicated by a decrease in water contact angle. Film height variations of 580 nm were produced using a mask with 12.5 μm features; a mask with 800 nm features was also employed to generate topographic features of corresponding width without expensive contacting equipment. Due to the broad absorbance spectra of DBA, highly accessible and/or unconventional light sources may be employed in this process; this advantage was demonstrated by patterning with sunlight. The nonspecific radical‐mediated nature of the DBA grafting reaction makes this a promising approach for many classes of polymers. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1195–1202