Biocidal polymer derived near white light-emitting polymeric carbon particles for antibacterial and bioimaging applications.

A growing antimicrobial crisis has increased demand for antimicrobial materials. It has become increasingly popular to convert polymeric macromolecules into polymeric carbon particles (PCP) in order to achieve highly biocompatible materials with unique properties as a result of the ability to synthesize nanomaterials of the right size and add value to existing stable polymers. This work presents the tuning of PCP for antibacterial application by combining a biocidal polymer with one-pot solvothermal synthesis. PCP displayed broad-spectrum antibacterial activity via various mechanisms, including inhibition of bacterial cell walls, ROS generation, and antibiotic resistance. Furthermore, these biocidal PCP were observed to show excitation-independent near-white light emission which on the other hand is generally possible due to mixed sizes, doping, and surface effects. As opposed to the parent biocidal polymer, PCP added ROS-mediated bactericidal activity, increased cytocompatibility, and nanofibers with anti-adhesive effects and potential of imaging bacterial cells.

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.

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.