Ultrafast Processes in Upper Excited Singlet States of Free and Caged 7-Diethylaminothiocoumarin.

The photochemistry and photophysics of thiocarbonyl compounds, analogues of carbonyl compounds with sulfur, have long been overshadowed by their counterparts. However, recent interest in visible light reactions has reignited attention toward these compounds due to their unique excited-state properties. This study delves into the ultrafast dynamics of 7-diethylaminothiocoumarin (TC1), a close analogue of the well-known probe molecule coumarin 1 (C1), to estimate intersystem crossing rates, understand the mechanisms of fluorescence and phosphorescence, and evaluate TC1's potential as a solvation dynamics probe. Enclosing TC1 within an organic capsule indicates its potential applications, even in aqueous environments. Ultrafast studies reveal a dominant subpicosecond intersystem crossing process, indicating the importance of upper excited singlet and triplet states in the molecule's photochemistry. The distinct fluorescence and phosphorescence origins, along with the presence of closely spaced singlet excited states, support the observed efficient intersystem crossing. The sulfur atom alters the excited-state behavior, shedding light on reactive triplet states and paving the way for further investigations.

Vibration-Assisted Intersystem Crossing in the Ultrafast Excited-State Relaxation Dynamics of Halocoumarins.

Due to its numerous applications, triplet formation and resulting phosphorescence remain a frontier area of research for over eight decades. Facile intersystem crossing (ISC) is the primary requirement for triplet formation and observation of phosphorescence. The incorporation of a heavy atom in molecules is one of the common approaches employed to facilitate ISC. A detailed study of the excited state dynamics that governs ISC is necessary to understand the mechanism of heavy atom effect (HAE). Incorporation of iodine at the 3 position of coumarin-1 reduces fluorescence quantum yield (ϕf) drastically as expected, whereas bromine substitution at the same position increased the ϕf. Such a contrasting effect of the two heavy atoms suggests that there are other features yet to be discovered to fully understand the HAE. Detailed steady state and femtosecond transient absorption studies along with theoretical calculations suggest that the C3-X (X = Br, I) bond vibration plays an important role in the ISC process. The study reveals that while in the case of the iodo-derivative there is no energy barrier in the singlet triplet crossing path, there is a barrier in the case of the bromo-derivative, which slows the ISC process. Such an unexpected phenomenon is not limited to halocoumarins as this rationalizes the photobehavior of 1-bromo-/iodo-substituted naphthalenes as well.

Unusual higher-order nonlinear optical properties in Au-coated triangular Ag-Au nanostructures.

Here, we report hitherto unobserved local field (LF)-assisted pump wavelength-dependent nonlinear optical (NLO) effects of three-photon (3PA)-induced four-photon absorption (4PA) at 532 nm and two-photon-induced 3PA at 730 nm in triangular-shaped core-shell Ag-Au nanoparticles (TrAg@Au) by femtosecond Z-scan. The shell thickness-dependent enhancement in the LF is observed by a COMSOL simulation. The intensity-dependent interplay between saturable and reverse-saturable absorptions along with switching of nonlinear (NL) phase is reported at 730 nm, showing the superiority of TrAg@Au in optical switching (OS). The optical limiting (OL) threshold (Fth) of 5.9(6.5)mJ/cm2 at 730 (532) nm boost their potential over benchmarked materials.

Synthesis and Characterization of Acid-Responsive Luminescent Fe(II) Metallopolymers of Rigid and Flexible Backbone N-Donor Multidentate Conjugated Ligands.

In this report we have disclosed the syntheses and properties of two new conjugated organic moieties bearing the same coordination sites but possessing different backbone rigidities and rotational flexibilities. Two new metallopolymers have been synthesized from the corresponding ligands under identical reaction conditions, and they have been thoroughly characterized through different techniques to understand the effect of backbone rigidity on the evolution of different properties in these metallopolymers. A FESEM micrograph of the rigid metallopolymer confirms the formation of a rigid nanorod type structure, while long agglomerated nanofiber strands are visible on the substrate in the case of the flexible analogue. All of the newly synthesized materials are fluorescence active. An Fe(II) metallopolymer of the flexible ligand showed huge changes in emission properties in the presence of different acids and showed a possibility of it being used as a thin film acid vapor sensor. All of the materials showed reversible electrochemical activity, and both of these polymers have shown electroluminescence when an appropriate potential is applied.

Switching of Trp-214 intrinsic rotamer population in human serum albumin: An insight into the aftermath of embracing therapeutic bioorganic luminophore azapodophyllotoxin into sudlow site I.

Human serum albumin is perceived to be the most abundant protein in human blood plasma and functions as a major carrier of different enzymes and drugs inside human body. The present article puts in an effort to demonstrate the attitude adopted by human serum albumin towards a potential therapeutic luminophore 4-(2-Hydroxyethyl)-10-phenyl-3,4,6,7,8,10-hexahydro-1H-cyclopenta[g]furo[3,4-b]quinoline-1-one (HPFQ). HPFQ is a prodigy from azapodophyllotoxin class of compounds, which have been synthesized from the perspective of improved bioactivity than its prologue podophyllotoxins. While, HPFQ has proved to be highly bioactive against most cancer cell lines with best GI50 values of <0.1 µM for a major number of cell lines; it also showed terrific fluorescent properties throughout the polarity scale, worthy of a promising imaging agent. The binding mechanism of HPFQ with HSA has been established by combining in vitro spectroscopic techniques, in silico molecular docking and induced fit docking (IFD). The competitive site-binding studies demonstrated that the otherwise anion-receptor sudlow site I of HSA nurtures neutral HPFQ with prudent affinity (Binding constant, Kb = 0.74 × 105 M-1). The time-resolve fluorescence studies reveal an appreciable reduction in HSA average radiative lifetime against an increase in HPFQ concentration and provided evidence for Forster's resonance energy transfer (FRET) being responsible for the dominant quenching mechanism, escorted by minor structural deformations in the backbone of protein structure. HPFQ institutes itself near Trp-214 within protein matrix, and subsequently the "hydrophobic amino acids" dominated cybotactic environment of Trp-214 experiences a reduction in the micropolarity. The allosteric modulation triggered by the stronger association of HPFQ with HSA leads towards minor deformation in secondary structure of protein. Sudlow site I of HSA proficiently embraces a favourable conformation like malleable dough to furnish space for arriving bioactive HPFQ molecule. HPFQ is also believed to administer the conformational regulation in HSA domain by affecting inter-conversion of HSA rotamers, which may prove to be an enlightening area to decode the preferable interaction between them. The juxtaposed spectroscopic research described herein is expected to embolden design of azapodophyllotoxin based anti-proliferative clinical agents for efficient in vivo bio-distribution employing HSA-centred drug delivery and administration systems.

A novel quinoline-appended chalcone derivative as potential Plasmodium falciparum gametocytocide.

BACKGROUND & OBJECTIVES: Malaria has remained a global health problem despite the effective control and treatment measures. In the backdrop of drug resistance, developing novel hybrid molecules targeting the sexual stages (gametocytes) of the human malaria parasite Plasmodium falciparum is of great significance. Recently, chalcone- based polyphenols have generated a great interest in the malaria research community worldwide due to their ease of synthesis and significant biological activity. The primary objective of this study was to investigate the interaction of a newly synthesized quinoline-appended chalcone derivative (ADMQ) with gametocyte specific proteins, Pfg 27 and Pfs 25 and explore its in vitro gametocytocidal potential. METHODS: The characterization of ligand-protein interactions at the atomistic level was done by a simulation strategy that combines molecular docking and molecular dynamics (MD) simulation in a coherent workflow. The X-ray crystal structure of Pfg 27 was retrieved from protein data bank and Pfs 25 was built using the Iterative Threading ASSembly Refinement (I-TASSER) server. The detailed interaction of both ADMQ and a known gametocytocidal agent, methylene blue (MB) (used as a positive control) with gametocyte proteins Pfg 27 and Pfs 25 was studied with a 50 ns explicit MD simulation. The ligand binding pose in terms of glide score, molecular mechanics-generalized born surface area (MM-GBSA) binding energies, protein-ligand root-mean-square-deviation (RMSD) and secondary structure elements (SSE) changes were analyzed accordingly. The direct effect of ADMQ on structural integrity of P. falciparum gametocytes was also examined using in vitro microscopy. RESULTS: The analogous Glide score and MM-GBSA free energy of binding indicated stable interactions for both ADMQ and MB harboured in the active site of targeted gametocyte proteins, Pfg 27 and Pfs 25, separately. Explicit MD simulation by Desmond software package indicated similar distinguishable conformational changes in the active site of target polypeptide chain due to the specific accommodation of ADMQ molecule. The simulation also manifested comparable mechanistic profile in terms of protein-ligand RMSD and changes in secondary structure elements (SSE). Further, ADMQ treatment was found to adversely affect the structural integrity of gametocytes, which resulted in appearance of vesicles protruding from the gametocytes. INTERPRETATION & CONCLUSION: The consolidated in silico molecular modeling and in vitro study described herein may give an insight into the interaction patterns of quinoline-chalcone hybrids with critical gametocyte proteins in the mosquito. This study will possibly pave the way for further exploration of similar heterocyclic quinoline-chalcone hybrids to open up new avenues in drug candidate development against P. falciparum gametocytes.

Development of multifunctional heterocyclic Schiff base as a potential metal chelator: a comprehensive spectroscopic approach towards drug discovery.

Amyloid-ß peptides and their metal-associated aggregated states have been implicated in the pathogenesis of Alzheimer's disease. The present paper epitomises the design and synthesis of a small, neutral, lipophilic benzothiazole Schiff base (E)-2-((6-chlorobenzo[d]thiazol-2-ylimino)methyl)-5-diethylamino)phenol (CBMDP), and explores its multifunctionalty as a potential metal chelator/fluorophore using UV-visible absorption, steady-state fluorescence, single molecule fluorescence correlation spectroscopic (FCS) techniques which is further corroborated by in silico studies. Some pharmaceutically relevant properties of the synthesized compound have also been calculated theoretically. Steady-state fluorescence and single molecule FCS reveal that the synthesized CBMDP not only recognizes oligomeric Aß40, but could also be used as an amyloid-specific extrinsic fluorophore as it shows tremendous increase in its emission intensity in the presence of Aß40. Molecular docking exercise and MD simulation reveal that CBMDP localizes itself in the crucial amyloidogenic and copper-binding region of Aß40 and undergoes a strong binding interaction via H-bonding and π-π stacking. It stabilizes the solitary α-helical Aß40 monomer by retaining the initial conformation of the Aß central helix and mostly interacts with the hydrophilic N-terminus and the α-helical region spanning from Ala-2 to Val-24. CBMDP exhibits strong copper as well as zinc chelation ability and retards the rapid copper-induced aggregation of amyloid peptide. In addition, CBMDP shows radical scavenging activity which enriches its functionality. Overall, the consolidated in vitro and in silico results obtained for the synthesized molecule could provide a rational template for developing new multifunctional agents.

Is the Sudlow site I of human serum albumin more generous to adopt prospective anti-cancer bioorganic compound than that of bovine: A combined spectroscopic and docking simulation approach.

A comparative biophysical study on the individual conformational adaptation embraced by two homologous serum albumins (SA) (bovine and human) towards a potential anticancer bioorganic compound 2-(6-chlorobenzo[d] thiazol-2-yl)-1H-benzo[de] isoquinoline-1,3(2H)- dione (CBIQD) is apparent from the discrimination in binding behavior and the ensuing consequences accomplished by combined in vitro optical spectroscopy, in silico molecular docking and molecular dynamics (MD) simulation. The Sudlow site I of HSA although anion receptive, harbors neutral CBIQD in Sudlow site I (subdomain IIA, close to Trp) of HSA, while in BSA its prefers to snugly fit into Sudlow site II (subdomain IIIA, close to Tyr). Based on discernable diminution of HSA mean fluorescence lifetime as a function of biluminophore concentration, facile occurrence of fluorescence resonance energy transfer (FRET) is substantiated as the probable quenching mechanism accompanied by structural deformations in the protein ensemble. CBIQD establishes itself within HSA close to Trp214, and consequently reduces the micropolarity of the cybotactic environment that is predominantly constituted by hydrophobic amino acid residues. The stronger association of CBIQD with HSA encourages an allosteric modulation leading to slight deformation in its secondary structure whereas for BSA the association is comparatively weaker. Sudlow site I of HSA is capable to embrace a favorable conformation like malleable gold to provide room for incoming CBIQD, whereas for BSA it behaves more like rigid cast-iron which does not admit any change thus forcing CBIQD to occupy an altogether different binding location i.e. the Sudlow site II. The anticancer CBIQD is found to be stable within the HSA scaffold as vindicated by root mean square deviation (RMSD) and root mean square fluctuation (RMSF) obtained by MD simulation. A competitively inhibited esterase-like activity of HSA upon CBIQD binding to Lys199 and Arg257 residues, plausibly envisions that similar naphthalimide based prodrugs, bearing ester functionality, can be particularly activated by Sudlow site I of HSA. The consolidated spectroscopic research described herein may encourage design of naphthalimide based pro-drugs for effective in vivo biodistribution using HSA-based drug delivery systems.

Conformation controlled turn on-turn off phosphorescence in a metal-free biluminophore: thriving the paradox that exists for organic compounds.

The legacy of phosphorescence from expensive organometallic compounds has inspired researchers to develop efficient metal-free organic phosphors. Although organic phosphors offer a cheaper alternative, the long-lived triplets of organic phosphors that are primarily consumed by vibrational dissipation need to be adequately suppressed, and this provides an opportunity to design new organic entities, at par with the organometallic compounds, based on conformational control and incorporation of useful functional groups to alter their emissive properties, especially phosphorescence. Here, we have achieved a proficient dual state emission, underlining the key design rule of conformational control in an organic molecular platform for 2-(6-chlorobenzo[d]thiazol-2-yl)-1H-benzo[de]isoquinoline-1,3(2H)-dione (CBIQD). In contrast to other known naphthalimides, the system limiting access to non-radiative triplet states is achieved by steric encumbrance which exhibits strong phosphorescence. Here, in addition to strong fluorescence (from planar conformer), phosphorescence is unlocked by suppression of non-radiative channels from the non-planar conformer in glassy solvents (77 K) and when embedded in a polymer matrix of poly(methyl methacrylate) (PMMA) at RT. The spectroscopic delineation of adopted geometry and optical property relationship is sought by a steric approach, extent of intramolecular charge transfer (ICT), presence of carbonyl groups, directed heavy atom effect and the spin-orbit coupling (SOC) invoked by -S- and -Cl atoms. Time dependent density functional theory (TD-DFT) is used to explain the favourable mechanistic path for the decay of excited states (ESs) leading to phosphorescence from a non-planar conformer and fluorescence from a planar conformer. The spectacular access to the radiative singlet and triplet states suggests that there is less scope for loss channels. The phosphorescence of the CBIQD-PMMA system may find use in other biomedical applications due to the biocompatibility of each component.

Design, Synthesis, and Proticity Inclined Conformational Modulation in a Highly Fluorescent Bichromophoric Naphthalimide Derivative: Hint Directed from RICT Perspective.

The present study embodies design, in silico DNA interaction, synthesis of benzothiazole containing naphthalimide derivative, 2-(6-chlorobenzo[d]thiazol-2-yl)-1H-benzo[de] isoquinoline-1,3(2H)-dione (CBIQD) along with its systematic photophysics, solvatochromic behavior, and solvation dynamics using an experimental and theoretical spectroscopic approach. Steady-state dual emission and biexponential fluorescence decay reveals the formation of two different excited species. Ground- and excited-state optimized geometry and the potential-energy curve obtained from DFT and TD-DFT calculation ascertained the existence of nonplanar and planar conformation. When the solvent polarity is changed from nonpolar to protic polar, the feebly emissive emission band highly intensifies probably due to the reversal of n, π*-π, π* emissive state along with consequent modulation of their energy gap that is induced by H-bonding. Excluding nonpolar solvents, in all other solvents, the Stokes shift correlates linearly with orientation polarizability, whereas in water, the story remains intriguing. With photoexcitation, intermolecular H-bonding stimulates the pyramidalization tendency of imide "N" with subsequent conformational change of GS nonplanar geometry to a coplanar one through acceptor rehybridization generating a rehybridized intramolecular charge transfer (RICT) state that caused a dramatic fluorescence upsurge. This allosteric modulation is promoted by excited-state H-bonding dynamics especially in strong H-bond donor water. A close interplay between preferential solvation and the proximity effect is evident in the emission behavior in a benzene (Bn)-ethanol (EtOH) binary mixture. Molecular docking analysis delineates considerable noncovalent sandwiched π-π stacking interactions of CBIQD with the pyrimidine rings as well as with imidazole rings of dG 6 and dG 2 base pairs of B-DNA double helix, which probably suffices the design strategy adopted. Overall, a strategic design to synthesize a highly fluorescent and potential bioactive agent is executed to revolutionize the fluorophore field due its enormous progressive importance in biochemical applications.

Composite-walled magnetic microcapsules at the water-toluene interface by ligand polymerization.

The liquid-liquid interface has been exploited as a platform for devising gold and iron oxide nanoparticle (NP)-decorated composite microcapsules (MCs) by cross-linking between -OH groups of poly(ethylene glycol) (PEG) attached to the iron oxide (Fe3O4) nanoparticle surface and starch attached to the gold (Au) nanoparticle surface in the presence of terephthaloyl chloride as a cross-linker. These nanoparticle-decorated capsules form a shell of both types of nanoparticles with water as the minor phase and toluene as the major phase. The morphology of these capsules has been characterized by optical, transmission, and scanning electron microscopy images, and the polymerization reaction has been established by UV-vis and FTIR spectroscopic studies. The magnetic behavior of the capsules has been illustrated by using an external magnetic field to tailor the magnetic control of the capsules. The encapsulated phase was impregnated with dye molecules of three different sizes, viz., fluorescein isothiocyanate and its dextran conjugates, to investigate the permeability of the capsule wall by fluorescence spectroscopy. Interestingly, the microcapsules exhibit size-selective permeability across the capsule wall that points to their plausible applications in controlled encapsulation and release.

Interfacial assembly of ZnO quantum dots into giant supramolecular architectures.

Para-aminobenzoic acid (PABA) stabilised zinc oxide (ZnO) quantum dots (QDs) have been synthesised by refluxing zinc acetate dihydrate in methanol under alkaline condition and re-dispersed into water by centrifugation. Aqueous dispersion of PABA-stabilised ZnO QDs was taken with seven different organic solvents in test tubes and subjected to diazo reaction under specified conditions. It was seen that the quantum dots assembled into diverse superstructures depending on the nature of the immiscible solvent at the aqueous-organic interface. The assemblies so obtained have been characterised by energy dispersive X-ray (EDX) analysis, Fourier transform infrared (FTIR), fluorescence and Raman spectroscopy, X-ray diffraction (XRD) and thermogravimetric analysis (TGA), optical, fluorescence and scanning electron microscopic (SEM) images. It has been observed that the ensuing supramolecular assemblies exhibit significant electrical conductivity and photoluminescence properties.

Angle-resolved plasmonic photocapacitance of gold nanorod dimers.

The assembly of nanostructures with plausible statistical orientations has provided the opportunity to correlate physical observables to develop a diverse range of niche applications. The dimeric configurations of gold nanorods have been chosen as atypical model systems to correlate optoelectronic with mechanical properties at a number of combinations of angular orientations. Metals are considered as conductors in electronics and reflectors in optics - therefore, metallic particles at the nanoscale exhibit unique optoelectronic characteristics that enable the design of materials to meet the demand of the modern world. Gold nanorods have often been adopted as prototypical anisotropic nanostructures owing to their excellent shape-selective plasmonic tunability in the vis-NIR region. When a pair of metallic nanostructures is sufficiently close to exhibit electromagnetic interaction, the evolution of collective plasmon modes, substantial enhancement of the near-field and strong squeezing of the electromagnetic energy at the interparticle spatial region of the dimeric nanostructures occur. The localised surface plasmon resonance energies of the nanostructured dimers strongly depend on the geometry as well as the relative configurations of the neighbouring particle pairs. Recent advances in the 'tips and tricks' guide have even made it possible to assemble anisotropic nanostructures in a colloidal dispersion. The optoelectronic characteristics of gold nanorod homodimers at different mutual orientations with statistical variation of the angle between 0 and 90° at particular interparticle distances have been elucidated from both theoretical and experimental perspectives. It has been observed that the optoelectronic properties are governed by mechanical aspects of the nanorods at different angular orientations of the dimers. Therefore, we have approached the design of an optoelectronic landscape through the correlation of the plasmonics and photocapacitance through the optical torque of gold nanorod dimers.

Switching of the Polarity-Sensitive Aggregation Pattern of a Thiosemicarbazone-Based Anticancer Luminophore and Its Involvement in Cellular Apoptosis of the Human Lung Cancer Cell Line.

Elucidation of the photophysical and biochemical properties of small molecules can facilitate their applications as prospective therapeutic imaging (theragnostic) agents. Herein, we demonstrate the luminescence behavior of a strategically designed potential therapeutic thiosemicarbazone derivative, (E)-1-(4-(diethylamino)-2-hydroxybenzylidene)-4,4-dimethylthiosemicarbazide (DAHTS), accompanied by the illustration of its solvation and solvation dynamics using spectroscopic techniques and exploring its promising antitumor activities by adopting the necessary biochemical assays. Solvent-dependent photophysical properties, namely UV-vis absorption, fluorescence emission, and excitation profiles, concentration-dependent studies, and time-resolved fluorescence decays, serve as footprints to explain the existence of DAHTS monomers, its excited-state intramolecular proton transfer (ESIPT) product, and dimeric and aggregated forms. The emission intensity progressively intensifies with increasing polarity and proticity of the solvents up to MeOH, but in water, a sudden dip is seen. Solvent polarity and H-bonding modulate the fluorescence behavior of the primary emission peak and significantly influence the formation of the dimer and DAHTS aggregates. The designed luminophore (DAHTS) exhibits significant antiproliferative activity against the human lung cancer (A549) cell lines with inhibitory concentrations (IC50) of 16.88 and 11.92 µM for 24 and 48 h, respectively. DAHTS effectively reduces the cell viability and induces cytotoxicity with extensive morphological changes in A549 cells in the form of spikes when compared to the normal HEK cell lines. More importantly, it increases the p53 expression at the mRNA level that consolidates its potential therapeutic activity. The effect of DAHTS on apoptotic pathways against the A549 cell line has been investigated to determine its probable mechanism of cell death. Thus, the all-inclusive understanding of the photophysical properties and the necessary biochemical assays put forward important steps toward tailoring the thiosemicarbazone core structure for favorable cancer theragnostic applications in academic and pharmaceutical research.

Effect of artificial sweetener saccharin on lysozyme aggregation: A combined spectroscopic and in silico approach.

The use of saccharin in food products attracts much attention as it involves the risk of lethal allergies and many protein aggregation diseases. However, its role in protein aggregation has not been explored to date. This study embodies the effect of artificial sweeteners on HEWL in the absence and presence of commonly available natural products such as curcumin and EGCG. Various techniques have been used to characterize the protein interaction, such as steady-state emission and time-resolved fluorescence, FTIR, gel electrophoresis, TEM, and molecular docking. Steady-state and time-resolved studies revealed the binding strength and concomitant effect of saccharin on HEWL protein. Kinetic measurements revealed that saccharin causes significant enhancement of HEWL aggregation with a considerable reduction in lag phase time i.e. from 37 hr to 08 hr. Whereas in the presence of natural products, the effect of saccharin on HEWL aggregation was significantly reduced specifically in the case of curcumin. The result obtained in the fluorescence experiment were also supported by the gel electrophoresis technique and morphological images taken by TEM. The rapid change in the secondary structure of the protein in the presence of saccharin was confirmed by the FTIR spectroscopy technique. This study is instrumental in understanding the effect of saccharin on protein aggregation and the role of commonly available natural products in curbing its effect.

Photothermal Reshaping of One-Dimensional Plasmonic Polymers: From Colloidal Dispersion to Living Cells.

Cellular internalization of plasmonic metal nanostructured materials has recently become a requisite for biomedical engineering of several intracellular processes that could foster an extensive paradigm to perform desired functions in the living cells. While numerous anisotropic metal nanostructures can be employed to pursue the specific functions, their incorporation becomes restricted due to morphological specificity to be engulfed in the cells. Due to recent advent in the self-assembly strategies, individual gold nanospheres could be interdigitated to one-dimensional plasmonic polymers and undergo subsequent laser-induced photothermal reshaping to rod-like nanostructures. The salient feature of biological significance is merely the variation of particle size within the polymers that engenders a dramatic impact on the radiative and nonradiative properties expressed in the scale of Faraday number (F a) and Joule number (J 0), respectively, as a function of the aspect ratio (α) of the nanorods. The effect on the nonradiative properties augments designing of nanoscale thermometry essential for photothermal applications in living cells. The conception of the colloidal dispersion has been extended to the cellular environment in a mice model; the selective accumulation of the nanostructures in the cells could provide an invading relationship between plasmonic characteristics, temperature distribution, and the biological issues. The critical correlation between optical and thermal characteristics toward biomedical manipulation from both theoretical and experimental perspectives could augment a milestone toward the progress of modern medical sciences.

A Catalogue of Indian Hydraenidae (Insecta: Coleoptera).

This catalogue lists 46 valid species included in 7 genera and two subfamilies of the family Hydraenidae (Coleoptera), recorded from India. The subfamily Hydraeninae accommodates 24 species (5 genera), and Ochthebiinae 22 species (2 genera). We include synonyms, type localities, type depositories, and distribution of the species. The Himalayan region supports the maximum diversity (31 species), followed by Deccan Peninsula (5 species), Western-Ghats (5 species), Northeast (4 species), Gangetic Plains (4 species), Semi-Arid (2 species), and Islands (one species).

Stabilization of a potential anticancer thiosemicarbazone derivative in Sudlow site I of human serum albumin: In vitro spectroscopy coupled with molecular dynamics simulation.

Human Serum Albumin (HSA) is the most important protein in human blood plasma and can acts as a major transporting agent for various drug molecules with flexible binding interaction. To elucidate the interaction of a newly designed potential anticancer thiosemicarbazone based luminophore (E)-1-(4-(diethylamino)-2-hydroxybenzylidene)-4,4-dimethyl-thiosemicarbazide (DAHTS) with HSA under physiological condition, in vitro optical spectroscopic experiments viz UV-Vis absorption, steady state fluorescence, fluroscence anisotropy, time resolved fluorscence (TRF) and cicular dichroism (CD) spectroscopy have been scrutinised. The experimental findings have been corroborated with in silico molecular docking analysis and Molecular Dynamics (MD) simulation. The spectroscopic results demonstrated that the conventionally anion-favouring Sudlow site I of HSA copiously adapt neutral DAHTS molecule with moderate binding affinity. The mean fluorescence lifetime of the sole tryptophan (Trp-214) present in the macromolecule experiences an appreciable diminution with an increase in concentration of the synthesized molecule. DAHTS localize itself close to Trp-214 within subdomain IIA (Sudlow site I) and surrounded by multiple hydrophobic amino acid residues (Val-235, Val-231, Ala-229, Phe-228, Val-325, Phe-326, Leu-327, Met-329, Phe-330, Leu-331, Tyr-332, Leu-346, Leu-347, Val-482, Leu-349, Ala-350, Ala-210, Trp-214, Ala- 213 and Val-216) in HSA. The distinct fluorescence lifetime, diverse pathways and changing rate of population indicates that the rotamerisation of Trp-214 residue is controlled by the guest molecule. Sudlow site I of HSA behaves flexibly and induces an allosteric modulation in the macromolecule resulting a minor deformation in the protein secondary structure as observed in CD (observed 11% change of α-helix content) as well as in MD simulation. The integrated multi-spectroscopic research described herein provides several important information about the binding interaction of a thiosemicarbazone Schiff base with HSA, which can be very significant for thiosemicarbazone based drug designing for academia as well as industry.

Plasmonic Sensing: Connecting the Dots.

Plasmonic sensitivity of noble metals has often been attributed to the morphology of the nanostructures and dielectric effects of both the materials and the surrounding medium. The measurable plasmonic shift with respect to the change in local dielectric as a function of analyte concentrations within nanoscale volume forms the basis of plasmonic sensing. However, the situation of the surrounding medium in the presence of multicomponent systems and, moreover, inhomogeneous adsorption around the anisotropic nanostructures become seemingly complicated as the precise description of several individual components becomes nearly impossible. Therefore, we have designed a retrospective formalism through a critical condensation of the electromagnetic scattering theories, macroscopic mixing rules, and micromechanics at the metal-analyte interface that can be adopted as generalized model irrespective of morphology of the nanostructures and the nature of analytes to account for the response of all the individual (microscopic) components to the observed (macroscopic) plasmonic sensing.

Diversity in the Family of Manganese Oxides at the Nanoscale: From Fundamentals to Applications.

The interesting chemistry of manganese is due to its various oxidation states. The possibility of several oxidation states has offered the element a special position among the transition metal elements in the periodic table. Amidst the possible oxidation states of manganese (in the range of -3 to +7), the +2, +3, and +4 oxidation states are the most prevalent in nature. Manganese possesses the ability to form multiple bonds with oxygen through spontaneous oxidation to a variety of stoichiometric oxides/hydroxides/oxyhydroxides that are collectively coined as "manganese oxides". However, using the recent advances in the synthetic strategies and characterization techniques over the past couple of decades, the investigation of the physicochemical properties of manganese oxides has been extended up to the nanoscale dimensions beyond the molecular. Moreover, the family of the manganese oxides also includes a series of porous architectures that are, often, stabilized at the nanoscale dimensions. Exquisite synthetic control over the size, shape, organization, and mass production of a variety of oxides at the nanoscale dimensions renders outstanding structural, optical, catalytic, magnetic, and transport properties. The tunable properties along with the chemical and biological accessibility open up new opportunities in a diverse range of niche applications critical to global society. Therefore, beyond the multivariance, polymorphism, thermodynamics, phase transition, crystallinity, magnetism, semiconducting behavior, and biogenecity may serve as the key factors to describe the compelling applications in health and other fields and to further understand the manganese oxides at the nanoscale.