"Fluorine Effects" in Conformational Orchestration of α/ß Hybrid Peptide with a 9-membered Pseudo ß-Turn Motif.

Fluorine, the tiny robust atom, with its unique features has captured the attention of scientists in recent times, especially in drug discovery with its integration in small molecules, peptides, and proteins. However, studies to understand the 'fluorine effects' on the conformation of molecules that follow 'beyond the rule of 5' are in the infancy yet significant in molecular design and function. For the first time, using short hybrid peptide sequence as an appropriate model, we examined the substitution effect (size, stereoelectronic effect, and hydrogen bonding) using X-ray diffraction, 2D-NMR, and CD studies. The comparative study on their folding patterns with hydrogen-substituted analogs can provide valuable insights into fluorinated substrates' design.

A new aggregation induced emission enhancement (AIEE) dye which self-assembles to panchromatic fluorescent flowers and has application in sensing dichromate ions.

We report for the very first time the crystal structure and self-assembly of a new aggregation-induced emission enhancement (AIEE) dye 4-(5-methoxythiazolo[4,5-b]pyridin-2-yl)-N,N-dimethylaniline (TPA) and its application in sensing dichromate ions. TPA reveals cyan blue emission under UV and visible light. The self-assembly properties of TPA were studied extensively by scanning electron microscopy (SEM) which revealed the formation of beautiful flower-like morphologies. These structures revealed both green and red fluorescence under FITC and rhodamine filters respectively when observed through fluorescence microscopy connoting the panchromatic emission properties of TPA from blue to red. The interactions which cause self-assembled structure formation in TPA were also validated theoretically using density functional theory (DFT) calculations. Crystal and molecular structure analysis of TPA was carried out via single-crystal X-ray diffraction to visualize the intermolecular interactions occurring in the solid-state and to study the structure-photophysical property relationship in the aggregated state. The photophysical properties of TPA were also studied extensively by UV-visible and fluorescence spectroscopy and its quantum yield and fluorescence lifetime were calculated by time-correlated single-photon counting (TCSPC). Interestingly, TPA could efficiently sense dichromate (Cr2O72-) ions in an acidic medium and an interesting morphological transition from a fluorescent flower to non-fluorescent disassembled structures could also be observed. The limit of detection of TPA for Cr2O72- ions was found to be as low as 5.5 nM, suggesting its exceptional sensitivity. More importantly, TPA could selectively sense Cr2O72- ions in real water samples even in the presence of other metal ions routinely present in polluted water, hence making it practically useful for water quality monitoring.

Fluorescence based miniaturized microfluidic and nanofluidic systems for biomedical applications.

Over the last two decades miniaturized microfluidic and nanofluidic systems with fluorescence setup emerged as a powerful technological platform for diverse biomedical applications. Bio-macromolecules such as nucleic acids and proteins are the core cellular components, their single molecule analysis allow us to understand biological processes, disease creation and progression, and development of novel treatment policies. Design and development of foolproof treatment methods requires rigorously analysis of nucleic acids and proteins such as length quantifications, sequence profiling, sequence mapping, analysis of conformational changes, analysis and recognition of epigenetic changes, and their interactions with other biomolecules. Miniaturized microfluidic and nanofluidic systems with fluorescence spectroscopy enable worldwide researchers to perform nucleic acids and proteins extractions and single molecule analysis from the trace amount of biological samples. In the present chapter we mostly highlighted over one decade applications of microfluidic and nanofluidic systems for single cell micro ribonucleic acid (miRNA) isolation and detection, deoxyribonucleic acid (DNA) mapping, DNA barcoding, identification of epigenetic mark on single DNA molecule, DNA-protein interactions study, protein sensing, protein sequencing, protein binding kinetics and many other applications. We also presented the recently reported microfluidic platform for the preparation of reproducible unisize aggregation induced emission (AIE) active nanomaterials and their biological applications.

AIE-MOF materials for biological applications.

Metal-Organic Frameworks (MOFs), coming under the realm of coordination chemistry, are unparalleled and the most studied among the group of porous materials. Structurally, these are well-defined three-dimensional crystalline products that can be tuned for various potential applications with a range of physico-chemical properties. More recently, aggregation-induced emission (AIE) and AIE of MOF material has attracted tremendous attention due to promising applications in biology. However, a chapter summarizing the work in AIE-MOFs materials has never been reported till date. A comprehensive review on the AIE and MOFs separately is beyond the reach of this chapter. Hence, we have summarized overview of recent developments in the syntheses and biological applications such as cell imaging, heparin detection, and drug delivery. In the end, conclusion, prospects and challenges in the arena of AIE-MOF materials are also highlighted.

Bis(2-methyl-pyridinium) tetra-chlorido-cuprate(II): synthesis, structure and Hirshfeld surface analysis.

The title compound, (C6H8N)2[CuCl4], crystallizes in the monoclinic space group I2/c. The coordination around the copper atom is a distorted tetra-hedron. The 2-methyl-pyridinium ion (C6H8N+) inter-acts with the tetra-chloro-cuprate anion through N-H⋯Cl and C-H(phen-yl)⋯Cl contacts, forming a hydrogen-bonded layer-like structure. The supra-molecular structure is further stabilized by C-H(meth-yl)⋯Cl inter-actions between the layers.

Crystal structure and Hirshfeld surface analysis of di-chlorido-(methanol-κO)bis-(2-methyl-pyridine-κN)copper(II).

In the title complex, [CuCl2(C6H7N)2(CH3OH)], the copper atom is five-coordinated by two nitro-gen atoms of 2-methyl-pyridine ligands, two chloro ligands and an oxygen atom of the methanol mol-ecule, being in a tetra-gonal-pyramidal environment with N and Cl atoms forming the basal plane. In the crystal, complex mol-ecules related by the twofold rotation axis are joined into dimeric units by pairs of O-H⋯Cl hydrogen bonds. These dimeric units are assembled through C-H⋯Cl inter-actions into layers parallel to (001).