Measurement of residual wedge angle with a reversal shear interferometer

A technique for determination of residual wedge angle of high optical quality transparent parallel plate using a reversal shear interferometer-based optical system has been discussed. In this technique the parallel plate to be tested is used to introduce angular tilt in the preset two-beam interference fringes of a reversal shear interferometer. The parallelism is calculated from the angular tilt of the fringes. The technique is more sensitive compared to techniques using Fizeau interferometer and is most suitable for highly parallel transparent plate with very low residual wedge angle.     

Selective and unusual fluoride ion complexation by a steroidal receptor using OH...F- and CH...F- interactions: a new motif for anion coordination?

[structure: see text] A novel cholaphane has been synthesized from a naturally occurring bile acid in just two steps. It has an ability to bind two fluoride ions selectively utilizing the glycolate motif in chloroform. This "inside-out" cyclodextrin analogue encapsulates fluoride through O-H...F(-) and C-H...F(-) interaction.     

Charge transfer complex formation between TX-100/CCl4 reverse micelle and a series of π-electron acceptors: determination of cmc and aggregation number

Electron donor–acceptor interaction of the reverse micelle (RM) of TX-100 in CCl₄ medium with a number of π-acceptors has been established by analysing the charge transfer (CT) absorption bands in the light of Mulliken's theory. Aggregation number (n) and operational critical micellisation concentration of the RM and formation constants of the RM–p-chloranil and RM-o-chloranil complexes have been determined by UV-visible spectrophotometry. Values of n thus obtained (20–30) are close to that of TX-100/cyclohexane dry reverse micelles determined by other methods and also to a theoretically calculated value of n for AOT/CCl₄ dry RM.     

Environment-Sensitive Fluorescence of 7-Nitrobenz-2-oxa-1,3-diazol-4-yl (NBD)-Labeled Ligands for Serotonin Receptors

Serotonin is a neurotransmitter that plays a crucial role in the regulation of several behavioral and cognitive functions by binding to a number of different serotonin receptors present on the cell surface. We report here the synthesis and characterization of several novel fluorescent analogs of serotonin in which the fluorescent NBD (7-nitrobenz-2-oxa-1,3-diazol-4-yl) group is covalently attached to serotonin. The fluorescent ligands compete with the serotonin_1A receptor specific radiolabeled agonist for binding to the receptor. Interestingly, these fluorescent ligands display a high environmental sensitivity of their fluorescence. Importantly, the human serotonin_1A receptor stably expressed in CHO-K1 cells could be specifically labeled with one of the fluorescent ligands with minimal nonspecific labeling. Interestingly, we show by spectral imaging that the NBD-labeled ligand exhibits a red edge excitation shift (REES) of 29 nm when bound to the receptor, implying that it is localized in a restricted microenvironment. Taken together, our results show that NBD-labeled serotonin analogs offer an attractive fluorescent approach for elucidating the molecular environment of the serotonin binding site in serotonin receptors. In view of the multiple roles played by the serotonergic systems in the central and peripheral nervous systems, these fluorescent ligands would be useful in future studies involving serotonin receptors.     

Measurement of wedge angle of a transparent parallel plate using quasi-monochromatic light source and phase shifting interferometry

A new technique (to our knowledge), for the measurement of residual wedge angle (RWA) of high optical quality transparent nearly parallel plate (PP), using a quasi-monochromatic light source, is presented. Advantages and drawbacks of the technique and the results obtained for a PP, using a filtered white light source, is discussed. A slightly modified optical setup for accurate determination of RWA, using phase shifting interferometry (PSI), has been described. Results obtained, applying PSI, for a validation experiment and for the determination of RWA of a quasi-PP is presented. The PSI based technique does not suffer from any measurement ambiguities due to limitation in effective beam aperture. Hence the technique is suitable for high accuracy measurement of RWA of PP. In both the optical setups, presented in this paper, the respective interfering beams travel the same optical circuit and are thus subject to same perturbation in optical path, due to external mechanical vibration, which finally cancels out. Thus the measurements are much less affected by external vibrations. Since the respective interfering beams undergo identical reflections and transmissions, the visibility or contrast of the interference fringes is very good.     

The biological buffer bicarbonate/CO2 potentiates H2O2-mediated inactivation of protein tyrosine phosphatases

Hydrogen peroxide is a cell signaling agent that inactivates protein tyrosine phosphatases (PTPs) via oxidation of their catalytic cysteine residue. PTPs are inactivated rapidly during H(2)O(2)-mediated cellular signal transduction processes, but, paradoxically, hydrogen peroxide is a rather sluggish PTP inactivator in vitro. Here we present evidence that the biological buffer bicarbonate/CO(2) potentiates the ability of H(2)O(2) to inactivate PTPs. The results of biochemical experiments and high-resolution crystallographic analysis are consistent with a mechanism involving oxidation of the catalytic cysteine residue by peroxymonocarbonate generated via the reaction of H(2)O(2) with HCO(3)(-)/CO(2).     

Silver Corrole Complexes: Unusual Oxidation States and Near‐IR‐Absorbing Dyes

Macrocycles such as porphyrins and corroles have important functions in chemistry and biology, including light absorption for photosynthesis. Generation of near‐IR (NIR)‐absorbing dyes based on metal complexes of these macrocycles for mimicking natural photosynthesis still remains a challenging task. Herein, the syntheses of four new Ag^III corrolato complexes with differently substituted corrolato ligands are presented. A combination of structural, electrochemical, UV/Vis/NIR‐EPR spectroelectrochemical, and DFT studies was used to decipher the geometric and electronic properties of these complexes in their various redox states. This combined approach established the neutral compounds as stable Ag^III complexes, and the one‐electron reduced species of all the compounds as unusual, stable Ag^II complexes. The one‐electron oxidized forms of two of the complexes display absorptions in the NIR region, and thus they are rare examples of mononuclear complexes of corroles that absorb in the NIR region. The appearance of this NIR band, which has mixed intraligand charge transfer/intraligand character, is strongly dependent on the substituents of the corrole rings. Hence, the present work revolves round the design principles for the generation of corrole‐based NIR‐absorbing dyes and shows the potential of corroles for stabilizing unusual metal oxidation states. These findings thus further contribute to the generation of functional metal complexes based on such macrocyclic ligands.     

Oximato bridged RhIII2MII and RhIIIMI species (MII = Mn, Co, Ni; MI = Cu, Ag)

The reaction of [RhCl₂(HPhL)(PhL)] with M^II(ClO₄)₂·6H₂O in presence of alkali has furnished trinuclear [RhCl₂(PhL)₂]₂M(H₂O)₂·H₂O (HPhL is phenylazobenzaldoxime; M = Mn, Co, Ni). A similar reaction with M^I(PPh₃)₂NO₃ yielded binuclear [RhCl₂(PhL)₂]M(PPh₃)₂ (M = Cu, Ag). In these molecules the oximato group acts as a bridge between Rh^III (bonded at N) and M^II or M^I (bonded at O). In structurally characterized [Rh^IIICl₂(PhL)₂]₂Mn(H₂O)₂.H₂O the centrosymmetric distorted octahedral MnO₆ coordination sphere is spanned by four oximato oxygen atoms and two water molecules lying in trans position. In the lattice the neighbouring molecules are held together by H₂O⋯H₂O⋯H₂O hydrogen bonds generating infinite zigzag chains. The manganese atoms lie parallel to the C-axis, the shortest Mn...Mn distance being 7.992 ?. Magnetic exchange interactions if any are small as seen in room temperature magnetic moments. The manganese system displays a strong EPR signal near g = 2.00. In the complex [RhCl₂(PhL)₂]Cu(PPh₃)₂ the copper atom is coordinated to two oximato oxygen atoms and the two phosphorus atoms in a distorted tetrahedral geometry. The softness of the phosphine ligand is believed to sustain the stable coordination of hard oximato oxygen to soft Cu^I. The coordination sphere of the RhIII atom in both the complexes is uniformly trans-RhN₄Cl₂.     

Self-assembled reverse micelles in supercritical CO2 entrap protein in native state

Molecular dynamics simulations of random quaternary mixtures of protein-water-CO2-fluorosurfactants show the self-assembly of reverse micelles in supercritical carbon dioxide where the protein becomes entrapped inside the aqueous pool. Analyses show that the protein native state remains intact in the water pool. This is because of the bulk nature of the enclosed water that provides a suitable environment for the extracted protein. Results from ab initio calculations imply that the existing fluorosurfactants can be made more effective in stabilizing water-in-CO2 microemulsions by a partial hydrogenation in their tails. A Lewis acid-Lewis base interaction among CO2 and the surfactant tails enhances the stability of the aqueous droplets substantially. The study can help accelerate the search for surfactant process for environmentally benign applications in dense CO2.