Titration of thiol groups in non-aqueous solvents

Thiols are titrated in acetone or dimethylformamide with sodium methoxide, employing visual end-point detection with Thymol Blue, Victoria Blue, p-hydroxyazobenzene or Azo Violet. Aromatic thiols are titrated in the presence of aliphatic thiols in acetone, with Thymol Blue as indicator.     

Analysis of the conformational dependence of mass-metric tensor determinants in serial polymers with constraints

It is well known that mass-metric tensor determinants det(G(s)) influence the equilibrium statistics and the rates of conformational transitions for polymers with constrained bond lengths and bond angles. It is now standard practice to include a Fixman-style compensating potential of the form U(c)(q(s)) proportional, variant(-k(B)T/2)ln[det(G(s))] as part of algorithms for torsional space molecular dynamics. This elegant strategy helps eliminate unwarranted biases that arise due to the imposition of holonomic constraints. However, the precise nature and extent of variation of det(G(s)) and hence ln[det(G(s))] with chain conformation and chain length has never been quantified. This type of analysis is crucial for understanding the nature of the conformational bias that the introduction of a Fixman potential aims to eliminate. Additionally, a detailed analysis of the conformational dependence of det(G(s)) will help resolve ambiguities regarding suggestions for incorporating terms related to det(G(s)) in the design of move sets in torsional space Monte Carlo simulations. In this work, we present results from a systematic study of the variation of det(G(s)) for a serial polymer with fixed bond lengths and bond angles as a function of chain conformation and chain length. This analysis requires an algorithm designed for rapid computation of det(G(s)) which simultaneously allows for a physical/geometric interpretation of the conformational dependence of det(G(s)). Consequently, we provide a detailed discussion of our adaptation of an O(n) algorithm from the robotics literature, which leads to simple recursion relations for direct evaluation of det(G(s)). Our analysis of the conformational dependence of det(G(s)) yields the following insights. (1) det(G(s)) is maximized for spatial conformers and minimized for planar conformations. (2) Previous work suggests that it is logical to expect that the conformational dependence of det(G(s)) becomes more pronounced with increase in chain length. Confirming this expectation, we provide systematic quantification of the nature of this dependency and show that the difference in det(G(s)) between spatial and planar conformers, i.e., between the maxima and minima of det(G(s)) grows systematically with chain length. Finally, we provide a brief discussion of implications of our analysis for the design of move sets in Monte Carlo simulations.     

Self-aggregation of reverse bis peptide conjugate derived from the unstructured region of the prion protein

A novel bis scaffold containing a pentapeptide PHGGG, derived from the prion octarepeat, forms fibrils of nanometric dimensions, thus indicating that certain segments in the unstructured region of the prion protein may facilitate an initial fibrillation event.     

Rheological microscopy: local mechanical properties from microrheology

We demonstrate how tracer microrheology methods can be extended to study submicron scale variations in the viscoelastic response of soft materials; in particular, a semidilute solution of lambda-DNA. The polymer concentration is depleted near the surfaces of the tracer particles, within a distance comparable to the polymer correlation length. The rheology of this microscopic layer alters the tracers' motion and can be precisely quantified using one- and two-point microrheology. Interestingly, we found this mechanically distinct layer to be twice as thick as the layer of depleted concentration, likely due to solvent drainage through the locally perturbed polymer structure.     

Versatile and facile synthesis of diverse semisynthetic tetracycline derivatives via Pd-catalyzed reactions

A diverse collection of tetracycline derivatives has been synthesized utilizing Heck, Suzuki, and other palladium-coupling reactions via tetracycline arenediazonium and iodoarene salts. Large numbers of tetracyclines are now possible via these reactions, including numerous upper periphery derivatives of doxycycline, minocycline, sancycline, and methacycline modified at positions C7, C9, and C6-C13 on the tetracycline naphthacene ring. Application of palladium-coupling reactions to the tetracyclines has yielded new tetracycline classes with differing structural attributes, greatly increasing the structural diversity of this family of antibiotics, one of the last of the early antibiotic families to be expanded by organic and medicinal chemistry.     

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Trap elimination and reduction of size dispersion due to aging in CdS<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Se<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript> quantum dots

Quantum Dots of CdS _x Se_1−x embedded in borosilicate glass matrix have been grown using Double-Step annealing method. Optical characterization of the quantum dots has been done through the combinative analysis of optical absorption and photoluminescence spectroscopy at room temperature. Decreasing trend of photoluminescence intensity with aging has been observed and is attributed to trap elimination. The changes in particle size, size distribution, number of quantum dots, volume fraction, trap related phenomenon and Gibbs free energy of quantum dots, has been explained on the basis of the diffusion-controlled growth process, which continues with passage of time. For a typical case, it was found that after 24 months of aging, the average radii increased from 3.05 to 3.12 nm with the increase in number of quantum dots by 190% and the size-dispersion decreased from 10.8% to 9.9%. For this sample, the initial size range of the quantum dots was 2.85 to 3.18 nm. After that no significant change was found in these parameters for the next 12 months. This shows that the system attains almost a stable nature after 24 months of aging. It was also observed that the size-dispersion in quantum dots reduces with the increase in annealing duration, but at the cost of quantum confinement effect. Therefore, a trade off optimization has to be done between the size-dispersion and the quantum confinement.     

Suppressed ion chromatography for monitoring chemical impurities in steam for geothermal power plants

A suppressed ion chromatography (IC) technique has been evaluated as a chemical monitoring tool for detecting major anions (F-, Cl-, NO3- and SO4(2-)) of condensed steam in geothermal power plants. It is shown that the suppressed IC technique provides a suitable means for preventing possible damage to generating equipment in the geothermal industry. An electrical conductivity detector (0.1 microS sensitivity) with an anion-exchange column (IonPac AS4A-SC), a micro-membrane suppressor (AMMS II), and an isocratic high-pressure pump system were successfully used for detecting low concentrations of inorganic anions. Method detection limits for the anions of interest were <0.184 mg/L. Details of the IC methodology as well as some experimental results obtained during its application for the chemical monitoring of geothermal steam pipes are also described.     

Influence of the addition of aluminium nanoparticles on thermo-rheological properties of hydroxyl-terminated polybutadiene-based composite propellant and empirical modelling

The heat transfer performance and entropy analysis are done in a compact loop heat pipe (CLHP) with Al₂O₃/water and Ag/water nanofluid. A compact loop heat pipe having a flat square evaporator with dimensions of 34 mm (L)?×?34 mm (W)?×?19 mm (H) has been fabricated and tested for the heat load ranging from 30 to 500 W. The experimental tests are conducted by keeping the CLHP in the vertical orientation with distilled water, silver (Ag)/water and aluminium oxide (Al₂O₃)/water nanofluid having low volume concentrations of (0.09% and 0.12%). The effect of wall and vapour temperature, evaporator and condenser heat transfer coefficient, thermal resistance on the applied heat loads is experimentally investigated and compared. The experimental results showed that the evaporator thermal resistance is reduced by 34.70% and 20.21%, respectively, for 0.12 vol% of Ag, Al₂O₃ nanoparticles when compared with that of the distilled water. For the same volume concentrations of Ag, Al₂O₃ nanoparticles, an enhancement of 34.52%, 23.7%, 39.27% and 30.8%, respectively, observed for the convective heat transfer coefficients at the evaporator and condenser. The entropy is also reduced by 19.08% and 11.58% when Ag and Al₂O₃ nanofluids are used as the operating fluid. From the experimental tests, it is found that the addition of small amount of Ag nanoparticles in the working fluid enhanced the operating range by 15% when compared with that of Al₂O₃/water nanofluid without the occurrence of any dry-out conditions.