Mechanical Tuning of Fluorescence Lifetime and Bandgap in an Elastically Flexible Molecular Semiconductor Crystal.

Despite having superior transport properties, lack of mechanical flexibility is a major drawback of crystalline molecular semiconductors as compared to their polymer analogues. Here single crystals of an organic semiconductor are reported that are not only flexible but exhibit systematic tuning of bandgaps, fluorescence lifetime, and emission wavelengths upon elastically bending. Spatially resolved fluorescence lifetime imaging and confocal fluorescence microscopy reveals systematic trends in the lifetime decay across the bent crystal region along with shifts in the emission wavelength. From the outer arc to the inner arc of the bent crystal, a significant decrease in the lifetime of ≈1.9 ns is observed, with a gradual bathochromic shift of ≈10 nm in the emission wavelength. For the crystal having a bandgap of 2.73 eV, the directional stress arising from bending leads to molecular reorientation effects and variations in the extent of intermolecular interactions- which are correlated to the lowering of bandgap and the evolution of the projected density of states. The systematic changes in the interactions quantified using electron density topological analysis in the compressed inner arc and elongated outer arc region are correlated to the non-radiative decay processes, thus rationalizing the tuning of fluorescence lifetime.

Superior Photophysical and Photosensitizing Properties of Nanoaggregates of Weakly Emissive Dyes for Use in Bioimaging and Photodynamic Therapy.

The development of luminescent dyes based on 1,1,4,4-tetracyanobuta-1,3-dienes (TCBDs) is an active research area, and a quantum yield (ΦF) of 7.8% has been achieved so far in cyclohexane by appending a fluorophore. Our novel method radically refines weakly emissive 2,3-disubstituted TCBD (phenyl-TCBD 1) (ΦF = 2.3% in CH3CN) into a water-soluble, biocompatible nanoformulation as highly emissive aggregates 1NPs ⊂ PF-127 with ΦF = 7.9% in H2O and without fluorophore conjugation. Characterization of 1NPs ⊂ PF-127 was carried out using various spectroscopic techniques, and its predominant size was found to be 80-100 nm according to transmission electron microscopy and dynamic light scattering techniques. Spectroscopic studies including Fourier transform infrared spectroscopy revealed that aggregated phenyl-TCBD particles were encapsulated in a nonluminescent triblock copolymer (PF-127)-based nanomicelles with the TCBD entrapment efficiency of 77%. With increasing water fraction, the phenyl-TCBD nanoaggregates exhibited a 3-fold higher quantum yield, a greater lifetime, and a red shift (155 nm). This remarkable enhancement in red emissivity enabled them to be used as a bioprobe for bioimaging applications and in photodynamic therapy to selectively target cancer cell lines with singlet oxygen generation capability (ΦΔ = 0.25). According to the MTT assay, compared to the native molecular form (1229 nM), the aggregated 1NPs ⊂ PF-127 (13.51 nM) exhibited dose-dependent cell death when exposed to light with 91-fold increased activity. The histoarchitectures of various vital organs (liver, kidneys, heart, lungs, and spleen) were intact when tested for in vivo biocompatibility. This study has significant implications for developing nonplanar push-pull chromophore-based dyes as biosensors and with potential applications beyond bioimaging.

A study of [2 + 2] cycloaddition-retroelectrocyclization in water: observation of substrate-driven transient-nanoreactor-induced new reactivity.

Organic solvents limit [2 + 2] cycloaddition-retroelectrocyclization (CA-RE) in biological fields. We examined the formation of 1,1,4,4-tetracyanobuta-1,3-dienes (TCBDs) through CA-RE reactions and their unusual reactivity to produce N-heterocyclic compounds when the nature of the surfactant and the concentrations were varied in the aqueous phase. An environment in which transient self-assemblies (vesicles) were induced by the substrate and surfactant molecules initiated new reactivity through H2O addition on the TCBD, generating the enol form of the intermediate, which results in the formation of the 6,6-dicyano-heteropentafulvene (amidofulvene) compound, while lamellar sheets at higher concentrations favored TCBD generation. Interestingly, the amidofulvene underwent a clean transformation to 6-membered heterocycles that resemble cardiotonic drugs (milrinone, amrinone) via keto-enol tautomerism mediated by a polar aprotic solvent, opening up a new avenue for drug discovery. Unlike organic-solvent-mediated CA-RE reactions, the present nanoreactor-mediated approach enabled the selective production of TCBDs as well as new heterocycles using H2O as a green solvent. In addition to the widely explored organic electronics/materials, we believe that this study will help to overcome the long-standing limitation of CA-RE reaction applicability in biological fields.

New Water-Soluble Magnetic Field-Induced Drug Delivery System Obtained Via Preferential Molecular Marriage over Narcissistic Self-Sorting.

Nanomaterials that respond to stimuli are of considerable interest for drug delivery applications. Drug delivery has been a leading challenge when it comes to the externally triggered controlled release of hydrophobic drugs. The present paper describes a unique arrangement of polymers in a competitive environment derived from the dynamic self-sorting behavior of the hydrophobic chains of amphiphilic mPEG-PLLA and poly-l-lactic acid (PLLA)-coated iron oxide nanoparticles IONP@PLLA to achieve a core-shell structure in which the hydrophobic PLLA part acts as a dense core and poly(ethylene glycol) (PEG) as an uncrowded shell. By using irreversible covalent interactions created by hydrophobic polymer-functionalized IONPs, it was possible to selectively form socially self-sorted nanocarriers (SS-NCs) with a higher hydrophobic core than the hydrophilic shell over narcissistic self-sorted nanocarriers (NS-NCs), that is, homo-micelles of amphiphilic polymers. The higher hydrophobic core of SS-NCs is indeed helpful in achieving higher drug [doxorubicin (DOX)] loading and encapsulation efficiencies of around 17 and 90%, respectively, over 10.3 and 65.6% for NS-NCs. Furthermore, due to the presence of IONPs and the densely packed hydrophobic compartments, the controlled release of DOX was facilitated by direct magnetism and temperature stimulation when an alternating magnetic field (AMF) was applied. An appreciably higher rate of drug release (∼50%) than that without AMF (∼18%) was achieved under ambient conditions in 24 h. The present study, therefore, proposes a new drug delivery system that exceeds homo-micelles and adds an extra feature of manipulating drug release through magnetism and temperature, that is, hyperthermia.

Nanotechnology-Assisted, Single-Chromophore-Based White-Light-Emitting Organic Materials with Bioimaging Properties.

White-light-emitting (WLE) organic materials, especially small molecules comprising a single chromophoric unit, have received much attention due to their tremendous use in modern-day electronic devices and biomaterials. They can increase the efficiency and lifetime of devices compared to the currently used combination approach. Herein, we explored a small symmetric push-pull organic molecule Hexyl-TCBD with a single 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) chromophoric unit containing urea as a key functional group on an acceptor-donor∼donor-acceptor (A-D∼D-A) backbone for its ability to show white-light emission in solution as well as in the solid state. The luminescence was absent in the solid state due to the H-bonding- and π-stacking-driven quenching processes, while emission behavior in solution was tunable with variable CIE chromaticity index values via hydrogen (H)-bonding-governed disaggregation phenomena. Translation of WLE from the Hexyl-TCBD solution to a solid state was demonstrated by utilizing nonemissive polystyrene (80 wt % with respect to the chromophore) as the matrix to obtain WLE nanofibers (made by the electrospun technique) via segregating the molecules. The optical microscopy study validated the WLE nanofibers. The presence of multicolor photoluminescence, including white light, could be fine-tuned through various excitation wavelengths, solvent polarities, and polystyrene matrices. Furthermore, the detailed photophysical studies, including lifetime measurements, indicated that the inherent intramolecular charge transfer (ICT) bands of Hexyl-TCBD exhibit better ICT state stabilization by space charge distribution through the modulation of H-bonding between urea groups. Finally, a cytotoxicity study was performed for Hexyl-TCBD on normal and cancer cell lines using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) assay to explore bioimaging applications in biosystems. MTT results revealed significant toxicity toward cancer cells, whereas normal cells exhibited good biocompatibility.

Reticular-Chemistry-Inspired Supramolecule Design as a Tool to Achieve Efficient Photocatalysts for CO2 Reduction.

Photocatalytic CO2 reduction into C1 products is one of the most trending research subjects of current times as sustainable energy generation is the utmost need of the hour. In this review, we have tried to comprehensively summarize the potential of supramolecule-based photocatalysts for CO2 reduction into C1 compounds. At the outset, we have thrown light on the inert nature of gaseous CO2 and the various challenges researchers are facing in its reduction. The evolution of photocatalysts used for CO2 reduction, from heterogeneous catalysis to supramolecule-based molecular catalysis, and subsequent semiconductor-supramolecule hybrid catalysis has been thoroughly discussed. Since CO2 is thermodynamically a very stable molecule, a huge reduction potential is required to undergo its one- or multielectron reduction. For this reason, various supramolecule photocatalysts were designed involving a photosensitizer unit and a catalyst unit connected by a linker. Later on, solid semiconductor support was also introduced in this supramolecule system to achieve enhanced durability, structural compactness, enhanced charge mobility, and extra overpotential for CO2 reduction. Reticular chemistry is seen to play a pivotal role as it allows bringing all of the positive features together from various components of this hybrid semiconductor-supramolecule photocatalyst system. Thus, here in this review, we have discussed the selection and role of various components, viz. the photosensitizer component, the catalyst component, the linker, the semiconductor support, the anchoring ligands, and the peripheral ligands for the design of highly performing CO2 reduction photocatalysts. The selection and role of various sacrificial electron donors have also been highlighted. This review is aimed to help researchers reach an understanding that may translate into the development of excellent CO2 reduction photocatalysts that are operational under visible light and possess superior activity, efficiency, and selectivity.

Synergistic Effects of Carbon Dots and Palladium Nanoparticles Enhance the Sonocatalytic Performance for Rhodamine B Degradation in the Absence of Light.

Carbon dot (CD) and palladium nanoparticle (Pd NP) composites are semiconducting materials having tremendous applications in catalysis with suitable band gaps. However, their combination with a suitable polymer matrix in sonophotocatalysis has not been explored. Herein, we have synthesized and characterized a new nanohybrid catalyst from a polyamide cross-linked CD-polymer and subsequent deposition of Pd NPs. A sonocatalytic activity of 99% rhodamine B dye degradation was achieved in mere 5 min in the dark. A model catalyst replacing CDs with benzene and other control studies revealed that the synergistic effects of CDs and Pd NPs enhance the sonocatalytic activity of the nanohybrid catalyst. Interestingly, visible light did not influence the activity significantly. Mechanistic investigations suggest that generation of reactive oxygen species on the surface of the CD-polymer initiated by ultrasound, which is further facilitated by Pd NPs, is the key for remarkable catalytic activity (a rate constant of 0.99 min-1). Recyclable heterogeneous catalysts under ambient conditions are promising for exploring sono-assisted dark catalysis for several avenues.

Tuning of cross-Glaser products mediated by substrate-catalyst polymeric backbone interactions.

Tuning of cross-Glaser products using different polymeric backbones supported by copper oxide nano-catalysts has been demonstrated by tweaking the substrate-catalyst interactions under greener conditions. Further, highly reactive magnetically separable and recyclable catalyst with scalability is demonstrated.

Designing of Push-Pull Chromophores with Tunable Electronic and Luminescent Properties Using Urea as the Electron Donor.

Urea-functionalized 4-ethynylbenzenes undergo facile formal [2 + 2] cycloaddition followed by retroelectrocyclization upon reaction with tetracyanoethylene, yielding 1,1,4,4-tetracyanobuta-1,3-dienes-based push-pull chromophores. Unlike the N,N'-dialkylamino group, urea functionalization provides easy access to further functionalization on these chromophores. The resulting chromophores exhibit unexpected white light emissions apart from various inherent properties like intramolecular charge-transfer band and redox behavior.