Micro-Ring Morphology of Ag7NCs and Light-Induced Reversible Interconversion of FCC Ag14NCs via Cu2+ ions-Mediated Particle-Assisted Reversible Interconversion.

Despite the remarkable progress made on intercluster conversion in atomically precise metal nanoclusters (MNCs) and their self-organization to develop microscopic molecular architecture with well-defined size and shape, achieving light-induced reversible structural transformation and the development of micro-ring self-assembly in MNCs have, so far, remained elusive. The present investigation touches on these two long-standing quests by showcasing a new route, light-induced Particle-Assisted Reversible Interconversion (PARI) for the reversible transformation from Face Centered Cubic (FCC) Ag14NCs to Ag7NCs. Our studies reveal that the lack of plasmonic silver nanoparticles (AgNPs) in the system results in the formation of Ag7NCs with centrosymmetric metallic kernels having hexagonal crystal packing. The molecular self-organization of Ag7NCs through various non-covalent interactions such as C-H•••O, C-H•••H-C, and C-H•••ᴨ leads to the formation of micro-ring morphology, a unique molecular architecture in MNCs. The in-situ generated AgNPs due to the acceleration of the reaction kinetics by Cu2+ ions facilitate the growth of Ag14NCs with FCC metallic kernel. These two structural units of AgNCs show light-induced reversible structural transformation which is also associated with the reversible tuning of their spectroscopic and morphological signatures. This PARI-guided interconversion strategy put forward a most appropriate example of a structure-property relationship in MNCs.

A Bis-Porphyrin Cavitand Breathing-In to Constrict Bucky Balls.

Bis-porphyrin cages have long been exploited to bind fullerenes selectively for various applications. The major consideration for an effective binding here had been the cavity size. Herein, we structurally demonstrate that a bis-Ni-porphyrin cavitand having even a smaller cavity can host a larger fullerene by a breathing and ruffling mechanism. It has also been shown that both the electronic and steric influence at the meso- positions of the porphyrin in fact dictate the binding character. The smaller cavity of 2NiD exhibits preferential binding for C70 over C60; however, surprisingly, the larger cavities in 2HD and 2NiTD display stronger affinities for C60 over the larger fullerene. We show here that the structural elasticity infused both by the metalloporphyrins and the connecting bridges play a major role in directing the binding. These conclusions have adequately been supported by structural and spectroscopic investigations. Additionally, the suitability of one of the conjugates for photoinduced charge-separation has been investigated using ultrafast transient absorption measurements. 2NiD⊃C60 has a charge separation timescale of ~0.8 ps, while charge recombination occurs at a longer timescale of ~920 ps.

Assemble-Disassemble-Reassemble Dynamics in Copper Nanocluster-Based Superstructures.

Assembling metal nanoclusters (MNCs) to form superstructures generates exciting photophysical properties distinct from those of their discrete precursors. Controlling the assembly process of MNCs and understanding the assembly-disassembly dynamics can have implications in achieving the reversible self-assembly of MNCs. The formation of self-assembled copper nanoclusters (CuNCs) as homogeneous superstructures and the underlying mechanisms governing such a process remain unexplored. Smart molecular imprinting of surface ligands can establish the forces necessary for the formation of such superstructures. Herein, we report highly luminescent, ordered superstructures of 4-phenylimidazole-2-thiol (4-PIT)-protected CuNCs with the help of l-ascorbic acid as a secondary ligand. Through a comprehensive spectroscopic analysis, we deciphered the mechanism of the self-assembly process, where the role of interligand H-bonding and C-H-π interactions was established. Notably, efficient reversibility of assembly-disassembly was demonstrated by re-establishing the interligand interactions and regenerating their photophysical and morphological signatures.

In Situ Crystallization, Differential Growth, and Multicolor Emission of Silver Nanoclusters.

The real-time monitoring of the stepwise growth process of the molecular crystal reveals a conclusive understanding of the morphological evolution, which otherwise remains elusive during the conventional crystallization processes. Herein, we report the in situ crystallization of silver nanoclusters (AgNCs) with special emphasis on their differential growth and multicolor emissive properties. A subtle variation of the methanol (MeOH) proportion in the reaction mixture induces the differential growth of these AgNCs, and thereby, a dramatic modulation in their optical properties was observed. Additionally, by increasing the temperature of the reaction (from a low temperature ice bath to 25 °C), an uncontrolled formation of AgNCs along with metallic silver nanoparticles (AgNPs) was observed, which was primarily induced by accelerating the reaction kinetics. We hope that this investigation comprehensively uncovers the serious bottlenecks of the conventional crystallization processes by showcasing systematic monitoring of structural evolution to the higher-ordered crystalline state.

Mechanistic elucidation of the catalytic activity of silver nanoclusters: exploring the predominant role of electrostatic surface.

The core and the ligand shell of metal nanoclusters (MNCs) have an influential role in modulating their spectroscopic signatures and catalytic properties. The aspect of electrostatic interactions to regulate the catalytic properties of MNCs has not been comprehensively addressed to date. Our present work conclusively delineates the role of the metal core and the electrostatic surface of MNCs involved in the reduction of nitroarenes. A facile surface modification of mercaptosuccinic acid (MSA)-templated AgNCs has been selectively achieved through Mg2+ ions (Mg-AgNCs). Microscopic studies suggest that the size of Mg-AgNCs is ∼3.3 nm, which is considerably higher than that of MSA-templated AgNCs (∼1.75 nm), confirming the formation of a nano-assembled structure. Our spectroscopic and microscopic experiments revealed that the negatively charged AgNCs efficiently catalyze the reduction of 4-nitrophenol (4-NP) with a rate constant of 0.23 ± 0.01 min-1. However, upon surface modification, the catalytic efficiency almost doubles due to the formation of Mg-AgNCs. Catalysis through AgNCs and Mg-AgNCs collectively portrays the role of the core and electrostatic surfaces. Furthermore, the role of electrostatic interaction has been substantiated by varying the ionic strength of the medium, as well as employing different molecular systems. A quantitative assessment of the Debye screening length asserts the correlation between the ionic strength of the medium and the role of electrostatic interactions involved herein. This highly enhanced catalytic aspect has been utilized for the real sample analysis, wherein AgNCs unexpectedly outperform Mg-AgNCs. This approach of real sample analysis also emanates the role of electrostatics involved. This comprehensive investigation represents the influential role of the core and ligand shell of MNCs as well as the role of electrostatics on its catalytic activities, which is relevant for the rational design of highly efficient catalysts.

pH-Switchable phenylalanine-templated copper nanoclusters: CO2 probing and efficient peroxidase mimicking activity.

Inter-cluster conversion through the strategic tuning of external stimuli and thereby modulation of the optical properties of metal nanoclusters (MNCs) is an emerging domain for exploration. Herein, we report the preparation of blue-emitting CuNCs using phenylalanine (Phe) as a template under acidic conditions (pH ∼ 4). The as-prepared CuNCs exhibit a sequential tuning of the photophysical properties upon varying the pH of the solution from pH ∼4 to pH ∼12. Blue-emitting CuNCs (B-CuNCs, λem = 410 nm) are systematically converted to cyan-emitting CuNCs (C-CuNCs, λem = 490 nm) with a large red-shifted emission maximum by 80 nm as a function of pH. Our present investigation delineates an unprecedented switchability of the photoluminescence (PL) properties of the CuNCs with the variations of the pH from pH ∼4 to pH ∼12. Both the Phe-templated CuNCs (B-CuNCs and C-CuNCs) were broadly characterized by various spectroscopic and morphological techniques. The X-ray photoelectron spectroscopy (XPS) studies reveal the presence of different oxidation states in the metallic core of B-CuNCs and C-CuNCs. These results in turn substantiate the pH-induced intercluster conversion of CuNCs through the substantial change in their core composition as well as valence states. Owing to the pH sensitivity, the CuNCs act as an efficient and highly sensitive probe for CO2, and quantitative estimation of the dissolved CO2 in the form of bicarbonate ions has been achieved through the enhancement of the PL intensity, wherein a very low value of the limit of detection (LOD) of ∼60 µM was obtained. Furthermore, we demonstrated that the CuNCs act as an efficient bio-catalyst with peroxidase mimicking enzymatic activity which has been investigated using OPD as a substrate under physiological conditions (pH ∼7.4 and temperature ∼37 °C). The mechanistic investigations confirmed that the oxidation of OPD mainly proceeds through the generation of hydroxyl radicals (˙OH). We hope the present investigations shed light on a multidimensional aspect of MNCs and uncover an upsurging recent interest in MNCs to act as an artificial enzyme.

Solvent-Induced Modulation in the Optical Properties of Copper Nanoclusters and Revealing the Isomeric Effect of Templates.

The solvent plays an influential role in controlling the nucleation process of metal nanoclusters (MNCs) and thereby significantly modulates their optical signatures. Herein, we have demonstrated the solvent-induced modulation in the optical properties of copper nanoclusters (CuNCs), primarily governed by the solvent polarity. During the preparation of para-mercaptobenzoic acid (p-MBA)-templated CuNCs, the simultaneous formation of blue-emitting CuNCs (B-CuNCs) and red-emitting CuNCs (R-CuNCs) were observed up to 7 h of reaction time, reflected from the systematic increment in the photoluminescence (PL) intensity at 420 nm and 615 nm, respectively. However, after 7 h of reaction time, the exclusive formation of B-CuNCs was observed. Such simultaneous growth and depletion dynamics of CuNCs result in a significant modulation in their optical properties. The variation of the solvent from water to less polar solvents such as DMSO and DMF restricts this inter-cluster dynamics by stabilizing both the CuNCs (B-CuNCs and R-CuNCs). Thereby, a single-component White Light Emission (WLE) was realized in DMSO with CIE coordinates (0.37, 0.36). The isomeric effect of the templates has also been investigated which extensively controls the optical and catalytic properties of the CuNCs.

Macrocyclic Cavitand ß-Cyclodextrin Inhibits the Alcohol-Induced Trypsin Aggregation.

Trypsin, the most abundant pancreatic protein, aids in protein digestion by hydrolysis and exhibits aggregation propensity in presence of alcohol, which can further lead to pancreatitis and eventually pancreatic cancer. Herein, by several experimental and theoretical approaches, we unearth the inhibition of alcohol-induced aggregation of Trypsin by macrocyclic cavitand, ß-cyclodextrin (ß-CD). ß-CD interacts with the native protein and shows inhibitory effect in a dose dependent manner. Moreover, the secondary structures and morphologies of Trypsin in presence of ß-CD also clearly emphasize the inhibition of fibril formation. From Fluorescence Correlation Spectroscopy, we observed an enhancement in diffusion time of Nile Red with ∼2.5 times increase in hydrodynamic radius, substantiating the presence of fibrillar structure. Trypsin also shows reduction in its functional activity due to alcohol-induced aggregation. Our simulation data reports the probable residues responsible for fibril formation, which was validated by molecular docking studies.

Rh(III)-Catalyzed C(7)-H Alkylation of Quinolines in the Synthesis of Angular π-Extended Pyrroloquinolines for Single-Component White-Light Emission.

Reported herein is a sustainable approach for a regioselective, Rh(III)-catalyzed C(7)-H alkylation of 8-aminoquinolines via metal carbene migratory insertion. This transformation displays a high functional group tolerance and exquisite site selectivity to afford the C-7 alkylated products. These products are derivatized to afford π-extended angular pyrroloquinolines, one of which (4h) shows white-light emission (WLE) with CIE coordinates (0.26, 0.34). An excellent cell viability and in vivo cellular imaging substantiate the nontoxic nature of these compounds.

DNA-Templated Modulation in the Photophysical Properties of a Fluorescent Molecular Rotor Auramine O by Varying the DNA Composition.

This work delineates an integrative approach combining spectroscopic and computational studies to decipher the association-induced fluorescence properties of a fluorescent molecular rotor, viz., auramine O (AuO), after interacting with 20-mer duplex DNA having diverse well-matched base pairs. While exploring the scarcely explored sequence-dependent interaction mechanism of AuO and DNA, we observed that DNA could act as a conducive scaffold to the formation of AuO dimer through noncovalent interactions at lower molecular density. The photophysical properties of AuO depend on the nucleotide compositions as described from sequence-dependent shifting in the emission and absorption maxima. Furthermore, we explored such DNA base pair-dependent fluorescence spectral characteristics of AuO toward discriminating the thermodynamically most stable single nucleotide mismatch in a 20-mer sequence. Our results are interesting and could be useful in developing analogues with further enhanced emission properties toward mismatched DNA sequences.

Preferential Binding of Epirubicin Hydrochloride with Single Nucleotide Mismatched DNA and Subsequent Sequestration by a Mixed Micelle.

Targeting mismatched base pairs containing DNA using small molecules and exploring the underlying mechanism involved during the binding interactions is one of the fundamental aspects of drug design. These molecules in turn are used in nucleic acid targeted therapeutics and cancer diagnosis. In this work, we systematically delineate the binding of the anticancer drug, epirubicin hydrochloride (EPR) with 20-mer duplex DNA, having both natural nucleobase pairing and thermodynamically least stable non-Watson-Crick base pairing. From the thermal denaturation studies, we observed that EPR can remarkably enhance the thermal stability of cytosine-cytosine (CC) and cytosine-thymine (CT) mismatched (MM) DNA over other 20-mer duplex DNA. From steady-state fluorescence spectroscopy and isothermal titration calorimetry studies, we concluded that EPR binds strongly with the mismatched duplex DNA through the intercalation binding mode. The interaction of EPR and duplex DNA has also been monitored at a single molecular resolution using fluorescence correlation spectroscopy (FCS). Dynamic quantitates such as diffusion coefficients and hydrodynamic radii obtained from an FCS study along with association and dissociation rate constants estimated from intensity time trace analyses further substantiate the stronger binding affinity of EPR to the thermally less stable mismatched DNA, formed by the most discriminating nucleobase (viz. cytosine). Additionally, we have shown that EPR can be sequestered from nucleic acids using a mixed micellar system of an anionic surfactant and a triblock copolymer. From thermal denaturation studies and circular dichroism spectroscopy, we found that the extent of drug sequestration depends on the binding affinity of EPR to the duplex DNA, and this mixed micellar system can be employed for the removal of excess drug in the case of a drug overdose.

Contrasting Thermodynamics Governs the Interaction of 3-Hydroxyflavone with the N-Isoform and B-Isoform of Human Serum Albumin.

Herein we report the interaction of 3-hydroxyflavone (3HF) with various isomeric forms of Human Serum Albumin (HSA), namely, the N-isoform (or native HSA at pH 7.4) and the B-isoform (at pH 9.2). Spectroscopic signatures of 3HF reveal that the interaction of 3HF with the N-isoform of HSA results in significant lowering of absorbance of the neutral species (λabs ∼ 345 nm) with concomitant increase of the anionic species (λabs ∼ 416 nm) whereas interaction with the B-isoform of HSA leads to selective enhancement of absorbance of the anionic species. The fluorescence profile of 3HF displays marked increase of intensity of the proton transferred tautomer (λem ∼ 538 nm) as well as the anionic species (λem ∼ 501 nm) for both the forms of the protein. However, analyses of the associated thermodynamics through temperature-dependent isothermal titration calorimetric (ITC) indicate that the interaction of 3HF with the N-isoform of HSA is more enthalpic in the lower temperature limit while the entropy contribution predominates in the higher temperature limit. Consequently, the 3HF-HSA (N-isoform at pH 7.4) interaction reveals an unusual thermodynamic signature of a positive heat capacity change (ΔCp = 3.84 kJ mol-1K-1) suggesting the instrumental role of hydrophobic hydration. On the contrary, the 3HF-HSA (B-isoform at pH 9.2) interaction shows qualitatively reverse effect. Consequently, the interaction is found to be characterized by an enthalpy-dominated hydrophobic effect (negative heat capacity change, ΔCp = -1.15 kJ mol-1K-1) which is rationalized on the basis of the nonclassical hydrophobic effect.