Optical Asymmetry and Structural Complexity in Hierarchically Organized Chiral CuO Nanostructures: Insight into the Geometric and Crystallographic Effects on Cooperative Chirality.

Optical asymmetry and structural complexity across different length scales were realized in flower-shaped CuO nanostructures, prepared through refluxing an aqueous solution of copper acetate, sodium hydroxide, and D-tartaric acid, as well as in their toroid-like forms obtained on calcination at 600 °C. Atomic scale chirality in the flower morphology could be visualized as putative Boerdijk-Coexter-Bernal like tetrahelical fragments, while that in the toroid form could be identified as screw dislocation-driven helicity. The fraction of asymmetry in the nanostructures has been evaluated from their chiroptical responses based on Kuhn asymmetry factor (g) from circular dichroism (CD) spectroscopy in the entire UV-vis range. The origin of chirality in the two CuO nanostructures has been assigned to the helical arrangement of the Cu-O-Cu network in accordance with their microscopic and spectroscopic observations. Attempts have been made to interpret the crystallographic and geometric chiralities in the two CuO nanostructures based on the redshift and augmented intensity of the CD signal along with an increase in their corresponding anisotropic factor on calcination. Further, the diverse interaction of the toroid-shaped CuO nanostructures with enantiomeric tryptophan moieties has been illustrated from the measurement of their corresponding thermodynamic parameters.

Role of Surface Oxygen Vacancies and Oxygen Species on CuO Nanostructured Surfaces in Model Catalytic Oxidation and Reductions: Insight into the Structure-Activity Relationship Toward the Performance.

Defect engineering, such as modification of oxygen vacancy density, has been considered as an effective approach to tailor the catalytic performance on transition-metal oxide nanostructured surfaces. The role of oxygen vacancies (OV) on the surface of the as-prepared, zinnia-shaped morphology of CuO nanostructures and their marigold forms on calcination at 800 °C has been investigated through the study of model catalytic reactions of reduction of 4-nitrophenol and aerobic oxidation of benzyl alcohol. The OV on the surfaces of different morphologies of CuO have been identified and quantified through Rietveld analysis and HRTEM, EPR, and XPS studies. The structure-activity relationships between surface oxygen vacancies (OV) and catalytic performance have been systematically investigated. The enhanced catalytic performance of the cubic CuO nanostructures compared to their as-prepared forms has been attributed to the formation of surface oxygen species on the reactive and dominant (110) surface that has low oxygen vacancy formation energy. The mechanistic role of surface oxygen species in the studied reactions has been quantitatively correlated with the catalytic activity of the different morphological forms of the CuO nanostructures.

Biocompatible fluorescent carbon nanoparticles as nanocarriers for targeted delivery of tamoxifen for regression of Breast carcinoma.

Breast cancer (BC) is the most common malignancy among females worldwide, and its high metastasis rates are the leading cause of death just after lung cancer. Currently, tamoxifen (TAM) is a hydrophobic anticancer agent and a selective estrogen modulator (SERM), approved by the FDA that has shown potential anticancer activity against BC, but the non-targeted delivery has serious side effects that limit its ubiquitous utility. Therefore, releasing anti-cancer drugs precisely to the tumor site can improve efficacy and reduce the side effects on the body. Nanotechnology has emerged as one of the most important strategies to solve the issue of overdose TAM toxicity, owing to the ability of nano-enabled formulations to deliver desirable quantity of TAM to cancer cells over a longer period of time. In view of this, use of fluorescent carbon nanoparticles in targeted drug delivery holds novel promise for improving the efficacy, safety, and specificity of TAM therapy. Here, we synthesized biocompatible carbon nanoparticles (CNPs) using chitosan molecules without any toxic surface passivating agent. Synthesized CNPs exhibit good water dispersibility and emit intense blue fluorescence upon excitation (360 nm source). The surface of the CNPs has been functionalized with folate using click chemistry to improve the targeted drug uptake by the malignant cell. The pH difference between cancer and normal cells was successfully exploited to trigger TAM release at the target site. After six hours of incubation, CNPs released âˆ¼ 74 % of the TAM drug in acidic pH. In vitro, studies have also demonstrated that after treatment with the synthesized CNPs, significant inhibition of the tumor growth could be achieved.

Pyridinic-N-rich carbon dots in IFE-based Turn-off Fluorometric detection of nerve agent Mimic- Diethyl chlorophosphate and multicolor cell imaging.

Fluorometric sensors for the detection of nerve agent mimics have received a lot of interest nowadays due to their high sensitivity and selectivity, ease of operation, and real-time monitoring. Pyridinic-N-rich carbon dots (NCDs) prepared through microwave-assisted pyrolysis of l-Malic acid and urea have been explored first time in this work as a novel turn-off fluorescent probe for the sensitive and selective detection of diethyl chlorophosphate (DCP), a nerve agent mimic. The as-prepared carbon dots contained a large amount of pyridinic nitrogen on their surface, which can modulate the photoluminescence properties of the NCDs. The blue emissive NCDs possessed both excitation wavelength-dependent and independent emission behavior. The detection of DCP was premised on quenching of the fluorescence emission intensity of NCDs in the presence of similar chemical reagents (e.g., trimethyl phosphate, triethyl phosphate, triethyl phosphonoacetate, triphenyl phosphate, diphenyl phosphate, tributyl phosphate). Fluorescence quenching of the NCDs in the presence of DCP has been attributed to the inner filter effect (IFE). From the linear Stern-Volmer plot (R2 = 0.9992), the limit of detection (LOD) was found to be 84 µM for sensing DCP for the concentration ranging between 3 and 15 mM. The biocompatibility of NCDs was assessed through cytotoxicity assay on MDA-MB-231 breast cancer cells. Fluorescence imaging demonstrated that NCDs have low cytotoxicity and can be employed successfully in cell imaging.

White light emission from helically stacked humin-mimic based H-aggregates in heteroatom free carbon dots.

White light emission (WLE), particularly from heteroatom free carbon dots (CDs), is unusual. Besides, deciphering the origin of WLE from a H-aggregated molecular fluorophore in such kinds of CDs is a challenging task due to their non-fluorescent character resulting from a forbidden transition from a lower-energy excitonic state. Therefore, rigorous investigation on their elusive excited state photophysical properties along with their steady-state optical phenomena has to be carried out to shed light on the nature of distinct emissive states formed in the CDs. Herein, for the first time, we report WLE from imperfect H-aggregates of co-facially π-π stacked humin-like structures comprising furfural monomer units as a unique molecular fluorophore in CDs, as revealed from combined spectroscopic and microscopic studies, synthesized through hydrothermal treatment of the single precursor, dextrose. H-aggregates in CDs show a broad range of excitation-dependent emission spectra with color coordinates close to pure white light, i.e., CIE (0.35, 0.37) and a color temperature of 6000 K. Imperfect orientation between the transition dipole moments of adjacent monomer units in the H-aggregate's molecular arrangement is expected to cause ground state symmetry breaking, as confirmed by Circular Dichroism (CD) studies, which established helically stacked nature in molecular aggregates and produced significant oscillatory strength at lower energy excitonic states to enable fluorescence. TRES and TAS investigations have been performed to minimise the intricacies associated with excited state photophysics, which is regarded as an essential step in gaining a grasp on emissive states. Based on the observation of two isoemissive spots in the time-resolved area normalized emission spectra (TRANES), the existence of three oligomeric species in the excited state equilibrium of the pure/hybrid H-aggregates has been established. The exciton dynamics through electron relaxation from the higher to the lower excitonic states, charge transfer (CT) states, and surface trap mediated emission in excimer states of H-aggregates have also been endorsed as three distinct emissive states from femtosecond transient absorption spectroscopy (TAS) studies corroborating with their steady-state absorption and emission behavior. The results would demonstrate the usage of CDs as a cutting-edge fluorescent material for creating aggregate-induced white light emission.