Late-Stage Halogenation of Peptides,Drugs and (Hetero)aromatic Compounds with a Nucleophilic Hydrazide Catalyst

Unlike its other halogen atom siblings, chlorination of a bioactive compound can change its physiological characteristics, improve its pharmacological profile, and function as a point of diversification through cross-coupling reactions. As a result, it has been a crucial strategy for drug discovery and development. However, functional groups such as amines, amides, hydroxy groups, or carboxylic acids trap the Cl⁺, severely limiting the reactivity and making direct chlorination far too difficult to be practical. Herein, we introduce a nucleophilic sulfonohydrazide catalyst for late-stage halogenation of peptides and drugs. This direct, mild and metal-free protocol shows high functional-group tolerance and is compatible with a range of structurally diverse peptides, drugs and aromatic compounds. Furthermore, DFT studies indicate that the reaction most likely proceeds via a cationic transition state. The gram-scale synthesis, high stability and efficiency of the catalyst provide a facile route for late-stage functionalization and intermediates for further derivatization.     

Ag-Doped Free-Standing 2D TiO2 Sheets: Electronic,Optical, Magnetic,and Self-Healing Behaviour

Beyond a critical doping level, Ag–2D TiO₂ sheets (ATO) are deemed to be a flexible transparent conductor, useful for visible-range functional photonic/optoelectronic devices/sensors, sunlight-sensitive catalysis, and light-activated resistive switching. Due to the lack of control of surface energy which often leads to the formation of structural defects and even dimensionality crossover (2D to 0D) of materials during doping reaction, it is challenging to obtain ATO with a controlled doping level. Gauging the urgency, therefore we report the surface energy-controlled synthesis of ATO employing liquid phase exfoliation of TiO₂ and subsequent hydrothermal Ag-doping in the presence of Hexamethylenetetramine (HMTA). Electron microscopy and atomic force microscopy reveal ATO sheets with large lateral dimensions. 6-fold, 4-fold, and strain-mediated crystallographic phases of 2D ATO have been revealed by high-resolution electron imaging. Successful tuning of the band gap down to ~2 eV with Ag doping up to ~10 % is obtained. Synthesized 2D ATO have been investigated for their electrical, optical, optoelectronic, photoluminescence, and ferromagnetic behaviour. Visible light-sensitive thermally/structurally robust semiconductor/conductor via tuneable doping will pave the way for their flexible as well as wearable device applications. Self-healing effect of AFM tip-generated mechanical stress has also been demonstrated.     

Improved bounds for the randomized decision tree Complexity of recursive majority

We consider the randomized decision tree complexity of the recursive 3‐majority function. We prove a lower bound of for the two‐sided‐error randomized decision tree complexity of evaluating height h formulae with error . This improves the lower bound of given by Jayram, Kumar, and Sivakumar (STOC'03), and the one of given by Leonardos (ICALP'13). Second, we improve the upper bound by giving a new zero‐error randomized decision tree algorithm that has complexity at most . The previous best known algorithm achieved complexity . The new lower bound follows from a better analysis of the base case of the recursion of Jayram et al. The new algorithm uses a novel “interleaving” of two recursive algorithms. © 2015 Wiley Periodicals, Inc. Random Struct. Alg., 48, 612–638, 2016     

Discogen-DNA complex films at air-water and air-solid interfaces

We have studied films of an ionic discogenic (discotic mesogenic) molecule (pyridinium salt tethered with hexaalkoxytriphenylene (PyTp)) and DNA complex at air-water (A-W) and air-solid interfaces. We have formed an PyTp monolayer on an aqueous subphase containing a small amount of DNA to obtain a PyTp-DNA complex at the A-W interface. Compared to the pure PyTp monolayer, the PyTp-DNA complex monolayer exhibits a higher collapse pressure and lower limiting area, indicating condensation and better stability. A Brewster angle microscope was used for in situ observation of the morphology of the film at the A-W interface. The PyTp-DNA complex films on silicon wafers were prepared using the Langmuir-Blodgett (LB) technique. We find that several tens of layers of the PyTp-DNA complex monolayer can be transferred with good efficiency. Fourier transform infrared spectroscopy studies confirm the presence of DNA in the LB films of the PyTp-DNA complex. Nanoindentation measurements using atomic force microscope reveal that the PyTp-DNA complex films are about two times harder as compared to the pure PyTp films.     

Synchronized and noise-robust audio recordings during realtime magnetic resonance imaging scans

This letter describes a data acquisition setup for recording, and processing, running speech from a person in a magnetic resonance imaging (MRI) scanner. The main focus is on ensuring synchronicity between image and audio acquisition, and in obtaining good signal to noise ratio to facilitate further speech analysis and modeling. A field-programmable gate array based hardware design for synchronizing the scanner image acquisition to other external data such as audio is described. The audio setup itself features two fiber optical microphones and a noise-canceling filter. Two noise cancellation methods are described including a novel approach using a pulse sequence specific model of the gradient noise of the MRI scanner. The setup is useful for scientific speech production studies. Sample results of speech and singing data acquired and processed using the proposed method are given.     

Synthesis and characterization of spin-coatable tert-amine molecules for hole-transport in organic light-emitting diodes

The synthesis of two tert-amine-based, non-fluorescent, hole-transport molecules (4,4′-[bis-{(4-di-n-hexylamino)benzylideneamino)]stilbene (DHABS) and 4,4′-[bis-{(4-diphenylamino)benzylideneamino}]stilbene) (DPABS) that are suitable for spin coating on indium tin oxide (ITO) for electronic device fabrication is described and compared with the widely used TPD. Electroluminescence occurred at a turn-on voltage of 7-8 V in ITO/hole-transport layer (HTL, spin coated)/Alq₃/Al devices.     

Linkage effects on binding affinity and activation of GPR30 and estrogen receptors ERalpha/beta with tridentate pyridin-2-yl hydrazine tricarbonyl-Re/(99m)Tc(I) chelates

We describe a new structural class of neutral tridentate pyridin-2-yl hydrazine chelates for labeling with tricarbonyl Re/99mTc(I) under aqueous conditions and investigate the receptor binding of synthetic estradiol derivatives with the novel G-protein-coupled receptor GPR30 and estrogen receptors ERalpha/beta. The steroid linkage affected the affinity and selectivity of estrogen binding with these receptors. Fluorescence assays based on calcium signaling demonstrate that membrane-permeable chelates 2 and 3 interact with the receptors in whole cells. These results suggest that in vitro assays will facilitate the development of targeted imaging agents for intracellular receptors and the feasibility of targeting GPR30 and ERalpha/beta for diagnostic tumor imaging.     

Spin‐Polarized Symmetric Electron‐Hole Quantum Bilayers: Finite width Effect

In this paper, the effect of finite width on ground‐state properties of a spin‐polarized symmetric electron‐hole quantum bilayers (EHBL) system is investigated at zero temperature. The quantum self‐consistent mean‐field approximation of Singwi, Tosi, Land and Sjölander (qSTLS) is adopted to explore intra‐ and interlayer properties such as the pair‐correlation function, the static density susceptibility, the local‐field corrections and the ground‐state energy. Interestingly, we noticed that due to the inclusion of finite width, the critical density for the onset of Wigner crystal (WC) phase is now lowered as compared to the recent spin‐polarized EHBL system without finite width and unpolarized EHBL system with finite width. Further, spin‐polarization effect is seem to introduce a marked change in the ground‐state energy of EHBL system as compared to that of unpolarized system. Results of ground‐state energy are also compared with the recent EHBL system without finite width (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)