Tunable Surface Wrinkling by a Bio-Inspired Polyamine Anion Coacervation Process that Mediates the Assembly of Polyoxometalate Nanoclusters

A bio-inspired method is used to render controlled wrinkling surface patterns on supramolecular architectures assembled from polyoxometalate (POM) clusters. It involves a polyamine-multivalent anion interaction generating positively charged coacervates, which while dictating the assembly of POM into spherical structures further facilitate an interesting surface morphogenesis with wrinkling patterns. This spontaneous surface wrinkling depends on the type of multivalent anion and the pH. As the polyamine-anion interaction becomes stronger, the wrinkles turn denser with lesser depth, which eventually undergoes post-buckling to engender a complex surface pattern. Interestingly, the order of influence exerted by different anions on the morphology follows the Hofmeister series. Moreover, the mild synthesis conditions keep the functional POM units dispersed in the sphere with a structural transformability to their lacunary form.     

Synthesis,characterization, in silico and in vitro biological activity studies of Ru(II) (η6-p-cymene) complexes with novel N-dibenzosuberene substituted aroyl selenourea exhibiting Se type coordination

A series of N-dibenzosuberene substituted aroyl selenourea ligands L1–L3 and their Ru(II) (η⁶-p-cymene) complexes 1–3, [Ru(II) (η⁶-p-cymene) L] (L?=?monodentate aroyl selenourea ligand) were synthesized and characterized. The molecular structures of the ligand L3 and complex 3 were confirmed by single-crystal XRD method. The single-crystal XRD study results revealed that aroyl selenourea ligand coordinates with ruthenium via Se neutral monodentate atom. In vitro DNA interaction studies were investigated by UV–Visible and fluorescence spectroscopic methods which showed that the intercalative mode of binding is in the order of 3?>?2?>?1 with the Ru(II) (η⁶-p-cymene) complexes. The binding affinity of the bovine serum albumin with complexes was calculated using spectroscopic methods. Quantum chemical computations were made using DFT (density functional theory), BL3YP; LANL2DZ basis set in order to determine the frontier molecular orbital parameters and MESP for the newly synthesized complexes. The complexes 1–3 have shown intensive cytotoxicity against the cancer lines HepG-2 and A549 under in vitro conditions. Complex 3 (IC₅₀?=?62 μM) has shown significant cytotoxic activity against HepG-2 compared to cisplatin standard drug. The complexes also examined for their antimicrobial activity. The complex 2 exhibited good activity against B. subtilis (MIC: 13.60 μg/mL), E. coli (MIC: 8.01 μg/mL) and A. flavus (MIC?=?15.60 μg/mL), respectively, compared to reference drugs Streptomycin and Ketoconazole.

     

Asymmetric,Three‐Component,One‐Pot Synthesis of Spiropyrazolones and 2,5‐Chromenediones from Aldol Condensation/NHC‐Catalyzed Annulation Reactions

A novel one‐pot, three‐component diastereo‐ and enantioselective synthesis of spiropyrazolones has been developed involving the aldol condensation of an enal to generate α,β‐unsaturated pyrazolones, which react with a second equivalent of enal through an N‐heterocyclic carbene (NHC)‐catalyzed [3+2] annulation. The desired spirocyclopentane pyrazolones are obtained in moderate to good yields and good to excellent stereoselectivities. Alternatively, starting from cyclic 1,3‐diketones, 2,5‐chromenediones are available through [2+4] annulation.     

Insights into two solution procedures for the single machine tardiness problem

This paper explores the well-known modified due date (MDD) rule for minimizing total tardiness on a single machine and shows that it has a decomposition structure. Based on this finding, we propose a decomposition heuristic and draw parallels to the famous optimal decomposition algorithm. We demonstrate that the MDD rule and the decomposition algorithm have striking similarities. We also discuss the key differences between these procedures. Finally, we present a sufficient condition under which the MDD rule is optimal and conclude the paper with some directions for future research.     

Introduction to session 3

Applied Biochemistry and Biotechnology -     

Discrimination of components in atherosclerotic plaques from human carotid endarterectomy specimens by magnetic resonance imaging ex vivo

Specific MRI techniques have been used to determine the dimensional and compositional properties of atherosclerotic lesions in carotid endarterectomy tissues. A quantitative comparison of areas of specific features in typical tissue segments was performed using MR images and histologic images. The mean difference for the measurements by the two methods was 4.5% for the total vessel, 5.3% for the internal carotid artery lumen, and 5.0% for the external carotid lumen. For other less abundant components, the mean difference was 14.2%. For direct characterization, individual tissue components were isolated by microdissection and their T1 and T2 relaxation times measured. Highly calcified areas typically had rather short T1 (452-837 ms) and short T2 (10.4-18.4 ms). In contrast, regions enriched in lipid had much longer T1 (1,380-1,480 ms) and longer T2 (35.3-49.0 ms). Other components such as thrombus had intermediate T1 (1,180 ms) and short T2 (15.4 ms). T2 parametric imaging was used as a complementary approach for segmentation and quantitation of tissue components. In fresh tissue, several different components exhibited different T2 ranges: calcified/solid lipid (13-18 ms). cellular/ECM (9-30 ms), fluid lipid (35-40 ms): fibrous (50-60 ms). These results demonstrate the utility of MRI for identifying and quantifying specific components of atherosclerotic plaque ex vivo, and suggest its value for these measurements in vivo as well.     

Magnetization transfer and T2 quantitation in normal appearing cortical gray matter and white matter adjacent to focal abnormality in patients with traumatic brain injury

Traumatic brain injury (TBI) is one of the commonest causes of morbidity and mortality in the developed countries with posttraumatic epilepsy and functional disability being its major sequelae. The purpose of this study was to test the hypothesis whether the normal appearing adjacent gray and white matter regions on T2 and T1 weighted magnetization transfer (MT) weighted images show any abnormality on quantitative imaging in patients with TBI. A total of 51 patients with TBI and 10 normal subjects were included in this study. There were significant differences in T2 and MT ratio values of T2 weighted and T1 weighted MT normal appearing gray matter regions adjacent to focal image abnormality compared to normal gray matter regions in the normal individuals as corresponding contralateral regions of the TBI patient's group (p < 0.05). However the adjoining normal appearing white matter quantitative values did not show any significant change compared to the corresponding contralateral normal white matter values. We conclude that quantitative T2 and MT ratio values provide additional abnormality in patients with TBI that is not discernable on conventional T2 weighted and T1 weighted MT imaging especially in gray matter. This additional information may be of value in overall management of these patients with TBI.     

A study of damping in fiber-reinforced composites

Damping contributions from the viscoelastic matrix, interphase and the dissipation resulting from damage sites are considered to evaluate composite material damping coefficients in various loading modes. The paper presents the results of the FEM/Strain energy investigations carried out to predict anisotropic-damping matrix comprising of loss factors η₁₁, η₂₂, η₁₂ and η₂₃ considering the dissipation of energy due to fiber and matrix (two phase) and correlate the same with various micromechanical theories. Damping in three phase (i.e., fiber-interphase-matrix) composite is also calculated as an attempt to understand the effect of interphase. The contribution of energy dissipation due to sliding at the fiber-matrix interface is incorporated to evaluate its effect on η₁₁, η₂₂, η₁₂ and η₂₃ in fiber-reinforced composite having damage in the form of hairline debonding. Comparative studies of the various micromechanical theories/models with FEM/Strain energy method for the prediction of damping coefficients have shown consistency when both the effect of variable nature of stress and the fiber interaction is considered. Parametric damping studies for three phase composite have shown that the change in properties of fiber, matrix and interphase leads to a change in the magnitude of effectiveness of interphase, but the manner in which the interphase would affect the various loss factors depends predominately upon whether the hard or soft interphase is chosen. Analysis of the effect of damage on composite damping indicates that it is sensitive to its orientation and type of loading.     

Synthetic studies and structural aspects of novel metallacyclic compoundsof titanium(IV) incorporating nitrogen,oxygen and sulphur: 1. Reactions of cis-dialkoxy-bis(acetylacetonato)titanium(IV) with alkoxyalkanols and the crystal structure of a new modification: di-μ-oxo-bis[diacetylacetonatotitanium(IV)]

Reactions of cis-dialkoxy-bis(acetylacetonato)titanium(IV), [(acac)₂Ti(OR)₂] (R = Et, Pr ⁱ ) with alkoxyalkanols (ROCH₂CH₂OH) (R = Me, Et, n-Bu) in 1:1 and 1:2 molar ratios in refluxing benzene under anhydrous conditions yield [(acac)₂Ti(OR)_2–n (OCH₂CH₂OR) _n ] (n = 1 or 2) complexes, which were purified by distillation under reduced pressure. On the basis of i.r. and n.m.r. (¹H- and ¹³C-) spectral studies, a cis-octahedral environment around Ti^IV is proposed. On keeping the distilled dark brown-red viscous liquid [(acac)₂Ti(OEt)(OCH₂CH₂OBu)] for 2 weeks, orange yellow crystals of [(acac)₂TiO]₂ were obtained. A single crystal X-ray diffraction study suggests the product is a new modification of [(acac)₂TiO]₂.