Synthesis and trans-cis isomerization of azobenzene dendrimers incorporating 1,2-isopropylidenefuranose rings

Azobenzene dendrimer 2 was synthesized from a known dendritic azo-tetracarboxylic acid and a dendritic amine incorporating 1,2-isopropylidenefuranose rings, and its trans-cis isomerization was studied by UV-vis absorption spectroscopy.     

Altered Membrane Mechanics Provides a Receptor-Independent Pathway for Serotonin Action

Serotonin, an important signaling molecule in humans, has an unexpectedly high lipid membrane affinity. The significance of this finding has evoked considerable speculation. Here we show that membrane binding by serotonin can directly modulate membrane properties and cellular function, providing an activity pathway completely independent of serotonin receptors. Atomic force microscopy shows that serotonin makes artificial lipid bilayers softer, and induces nucleation of liquid disordered domains inside the raft-like liquid-ordered domains. Solid-state NMR spectroscopy corroborates this data at the atomic level, revealing a homogeneous decrease in the order parameter of the lipid chains in the presence of serotonin. In the RN46A immortalized serotonergic neuronal cell line, extracellular serotonin enhances transferrin receptor endocytosis, even in the presence of broad-spectrum serotonin receptor and transporter inhibitors. Similarly, it increases the membrane binding and internalization of oligomeric peptides. Our results uncover a mode of serotonin–membrane interaction that can potentiate key cellular processes in a receptor-independent fashion.     

Contaminant detection in treated water using Optiqua’s MiniLab™ biosensing system: a case study for Bisphenol A

An inhibition assay for detection of Bisphenol A (BPA) in treated water has been developed and validated for the MiniLab? system from Optiqua Technologies. This biosensor-based analytical system can be used for detection of specific contaminants in solution. The system uses an integrated optic Mach-Zehnder interferometer chip that is functionalised with a biochemical interface layer. The sensor chip surface was first coated with aminodextran which formed a hydrophilic layer suitable for further modification. 4,4-bis(4-hydroxyphenyl) valeric acid (BVA), which is a structural analogue of BPA, was then successfully coupled to the aminodextran layer. This surface chemistry was used in a qualitative inhibition assay format for the selective detection of the presence of BPA. The assay was developed and optimised using a polyclonal anti-BPA antibody. Samples from 12 different water matrices of Singapore were spiked with known amounts of BPA and tested with the MiniLab? system. The working range of the BPA inhibition assay is from 0.5 to 5 µg/L. Intra- and inter-assay variations were measured, with calculated relative standard deviation averaging of about 15%. BPA concentrations of the spiked samples were also verified and confirmed with LC-MS. Such functionalised biosensor chip can be reused for more than 200 sample injections over a period longer than 6 months. Developed as a robust, user-friendly and cost-effective system that can be field deployed, the MiniLab? system enables target-specific assays currently only available in the lab to become available in the field.     

Large Ultrathin Shelled Drops Produced via Non‐Confined Microfluidics

We present a facile approach for producing large and monodisperse core–shell drops with ultrathin shells using a single‐step process. A biphasic compound jet is introduced into a quiescent third (outer) phase that ruptures to form core–shell drops. Ultrathin shelled drops could only be produced within a certain range of surfactant concentrations and flow rates, highlighting the effect of interfacial tension in engulfing the core in a thin shell. An increase in surfactant concentrations initially resulted in drops with thinner shells. However, the drops with thinnest shells were obtained at an optimum surfactant concentration, and a further increase in the surfactant concentrations increased the shell thickness. Highly monodisperse (coefficient of variation smaller than 3 %) core–shell drops with diameter of ～200 μm–2 mm with shell thickness as small as ～2 μm were produced. The resulting drops were stable enough to undergo polymerisation and produce ultrathin shelled capsules.     

Size control and quantum confinement in Cu2ZnSnS4 nanocrystals

Starting with metal dithiocarbamate complexes, we synthesize colloidal Cu(2)ZnSnS(4) (CZTS) nanocrystals with diameters ranging from 2 to 7 nm. Structural and Raman scattering data confirm that CZTS is obtained rather than other possible material phases. The optical absorption spectra of nanocrystals with diameters less than 3 nm show a shift to higher energy due to quantum confinement.     

Heterocyclic carbenes of diverse flexibility: A theoretical insight

A systematic density functional investigation has been carried out on the structure, stability and reactivity of heterocyclic carbenes of diverse flexibility, i.e., carbenes with different modes of binding specially normal and remote mode of binding. Ligating properties of these carbenes have been assessed by virtue of their HOMO energies and verified further by inspection of the symmetric CO frequencies of their respective palladium carbonyl complexes. All the remote carbenes were found to have higher σ-donating abilities compared to their normal analogs. N-heterocyclic carbenes 1 and 5 are found to be electrophilic in nature while the remote carbene 3 and P-heterocyclic carbene 6 are found to be nucleophilic. Quantum theory of atoms in molecules (QTAIM) reveals significant covalent character in the C_carbene-Pd bonds.     

Condensation Product of 1-Naphthaldehyde and 3-Aminophenol: Fluorescent “on” Probe for Ce3+and “off” Probe for Dichromate (Cr2O72−)

A new probe (Z)-3-((naphthalen-1-ylmethylene)amino)phenol has been synthesized by condensation reaction between 1-naphthaldehyde and 3-aminophenol for the fluorescent sensing of Ce³⁺ by “on” mode and dichromate (Cr₂O₇^2?) by “off” mode. Metal ions—Ag⁺, Al³⁺, As³⁺, Ba²⁺, Ca²⁺, Cd²⁺, Ce⁴⁺, Co²⁺, Cr³⁺, Cr⁶⁺, Cu²⁺, Fe²⁺, Fe³⁺, Hg²⁺, K⁺, La⁺, Li⁺, Mg²⁺, Mn²⁺, Na⁺, Ni²⁺, Pb²⁺, Zn²⁺and anions Br^?, C₂O₄^2?, CH₃COO^?, Cl^?, CO₃^2?, F^?, H₂PO₄^?, HCO₃^?, HF₂^?, HPO₄^2?, I^?, MnO₄^?, NO₃^?, OH^?, S^2?, S₂O₃^2?, SCN^?, SO₄^2? do not interfere. The limit of detection (LOD) for sensing Ce³⁺ and Cr₂O₇^2? ions are 1.286?×?10^–7 M and 6.425?×?10^–6 M, respectively.

     

Quantum confinement in silver selenide semiconductor nanocrystals

We prepare Ag(2)Se nanocrystals with average diameters between 2.7 and 10.4 nm that exhibit narrow optical absorption features in the near to mid infrared. We demonstrate that these features are broadly tunable due to quantum confinement. They provide the longest wavelength absorption peaks (6.5 μm) yet reported for colloidal nanocrystals.     

NO-NSAIDs. Part 3: nitric oxide-releasing prodrugs of non-steroidal anti-inflammatory drugs

In continuation of our efforts to discover novel nitric oxide-releasing non-steroidal anti-inflammatory drugs (NO-NSAIDs) as potentially "Safe NSAIDs," we report herein the design, synthesis and evaluation of 21 new NO-NSAIDs of commonly used NSAIDs such as aspirin, diclofenac, naproxen, flurbiprofen, ketoprofen, sulindac, ibuprofen and indomethacin. These prodrugs have NO-releasing disulfide linker attached to a parent NSAID via linkages such as an ester (compounds 9-16), a double ester (compounds 17-24), an imide (compounds 25-30) or an amide (compounds 31-33). Among these NO-NSAIDs, the ester-containing NO-aspirin (9), NO-diclofenac (10), NO-naproxen (11), and the imide-containing NO-aspirin (25), NO-flurbiprofen (27) and NO-ketoprofen (28) have shown promising oral absorption, anti-inflammatory activity and NO-releasing property, and also protected rats from NSAID-induced gastric damage. NO-aspirin compound 25, on further co-evaluation with aspirin at equimolar doses, exhibited comparable dose-dependent pharmacokinetics, inhibition of gastric mucosal prostaglandin E(2) (PGE(2)) synthesis and analgesic properties to those of aspirin, but retained its gastric-sparing properties even after doubling its oral dose. These promising NO-NSAIDs could therefore represent a new class of potentially "Safe NSAIDs" for the treatment of arthritic pain and inflammation.     

Jointly optimized spatial prediction and block transform for video and image coding

This paper proposes a novel approach to jointly optimize spatial prediction and the choice of the subsequent transform in video and image compression. Under the assumption of a separable first-order Gauss-Markov model for the image signal, it is shown that the optimal Karhunen-Loeve Transform, given available partial boundary information, is well approximated by a close relative of the discrete sine transform (DST), with basis vectors that tend to vanish at the known boundary and maximize energy at the unknown boundary. The overall intraframe coding scheme thus switches between this variant of the DST named asymmetric DST (ADST), and traditional discrete cosine transform (DCT), depending on prediction direction and boundary information. The ADST is first compared with DCT in terms of coding gain under ideal model conditions and is demonstrated to provide significantly improved compression efficiency. The proposed adaptive prediction and transform scheme is then implemented within the H.264/AVC intra-mode framework and is experimentally shown to significantly outperform the standard intra coding mode. As an added benefit, it achieves substantial reduction in blocking artifacts due to the fact that the transform now adapts to the statistics of block edges. An integer version of this ADST is also proposed.