Light-Induced Self-Assembled Polydiacetylene/Carbon Dot Functional "Honeycomb".

The design of functional supramolecular assemblies from individual molecular building blocks is a fundamental challenge in chemistry and material science. We report on the fabrication of "honeycomb" films by light-induced coassembly of diacetylene derivatives and carbon dots. Specifically, modulating noncovalent interactions between the carbon dots, macrocyclic diacetylene, and anthraquinone diacetylene facilitates formation of thin films exhibiting a long-range, uniform pore structure. We show that light irradiation at distinct wavelengths plays a key role in the assembly process and generation of unique macro-porous morphology, by both initiating interactions between the carbon dots and the anthraquinone moieties and giving rise to the topotactic polymerization of the polydiacetylene network. We further demonstrate utilization of the macro-porous film as a photocatalytic platform for water pollutant degradation and as potential supercapacitor electrodes, both applications taking advantage of the high surface area, hydrophobicity, and pore structure of the film.

Genistein carbon dots exhibit antioxidant and anti-inflammatory effects in vitro.

Genistein, an isoflavone from soybean, has attracted attention due to its health benefits, particularly antioxidant and anti-inflammatory activities. Clinical applications of genistein, however, have been limited due to the considerable hydrophobicity and lower bioavailability of the molecule. In this study, carbon dots (C-dots) synthesized from genistein as the carbonaceous precursor exhibit antioxidant properties in test-tube and cell experiments. Anti-inflammatory activity of the genistein-C-dots was also recorded in LPS stimulated macrophages, manifested in inhibition of pro-inflammatory cytokine levels and enhancement anti-inflammatory cytokine expression. The antioxidant and anti-inflammatory effects of the genistein-C-dots, particularly in comparison to the parent genistein molecules, likely account to the display of functional genistein residues on the C-dots' surfaces, and low band gap energy facilitating electron scavenging. Importantly, the genistein-C-dots featured biocompatibility and low cytotoxicity, underlining their potential as a therapeutic vehicle against inflammatory conditions.

Multispectral and Circular Polarization-Sensitive Carbon Dot-Polydiacetylene Capacitive Photodetector.

Multispectral photodetectors (MSPs) and circularly polarized light (CPL) sensors are important in opto-electronics, photonics, and imaging. A capacitive photodetector consisting of an interdigitated electrode coated with carbon dot/anthraquinone-polydiacetylene is constructed. Photoexcitation of the carbon dots induces transient electron transfer to the anthraquinone moieties, and concomitant change in the film dielectric constant and recorded capacitance. This unique photodetection mechanism furnishes wavelength selectivity that is solely determined by the absorbance of the carbon dots incorporated in the anthraquinone-polydiacetylene matrix. Accordingly, employing an array of polymerized-anthraquinone photodetector films comprising carbon dots (C-dots) exhibiting different excitation wavelengths yielded optical "capacitive fingerprints" in a broad spectral range (350-650 nm). Furthermore, circular light polarization selectivity is achieved through chiral polymerization of the polydiacetylene framework. The carbon dot/anthraquinone-polydiacetylene capacitive photodetector features rapid photo-response, high fidelity, and recyclability as the redox reactions of anthraquinone are fully reversible. The carbon dot/anthraquinone-polydiacetylene platform is inexpensive, easy to fabricate, and consists of environmentally friendly materials.

Size-Selective Detection of Nanoparticles in Solution and Air by Imprinting.

Monitoring of nanoparticles (NPs) in air and aquatic environments is an unmet challenge accentuated by the rising exposure to anthropogenic or engineered NPs. The inherent heterogeneity in size, shape, and the stabilizing shell of NPs makes their selective recognition a daunting task. Thus far, only a few technologies have shown promise in detecting NPs; however, they are cumbersome, costly, and insensitive to the NPs morphology or composition. Herein, we apply an approach termed nanoparticle-imprinted matrices (NAIM), which is based on creating voids in a thin layer by imprinting NPs followed by their removal. The NAIM was formed on an interdigitated electrode (IDE) and used for the size-selective detection of silica NPs. Three- and 5-fold increases in capacitance were observed for the reuptake of NPs with similar diameter, compared to smaller or larger NPs, in air and liquid phase, respectively. En masse, the proposed approach lays the foundation for the emergence of field-effective, inexpensive, real-life applicable sensors that will allow online monitoring of NPs in air and liquids.

Metal-catalyst-free gas-phase synthesis of long-chain hydrocarbons.

Development of sustainable processes for hydrocarbons synthesis is a fundamental challenge in chemistry since these are of unquestionable importance for the production of many essential synthetic chemicals, materials and carbon-based fuels. Current industrial processes rely on non-abundant metal catalysts, temperatures of hundreds of Celsius and pressures of tens of bars. We propose an alternative gas phase process under mild reaction conditions using only atomic carbon, molecular hydrogen and an inert carrier gas. We demonstrate that the presence of CH2 and H radicals leads to efficient C-C chain growth, producing micron-length fibres of unbranched alkanes with an average length distribution between C23-C33. Ab-initio calculations uncover a thermodynamically favourable methylene coupling process on the surface of carbonaceous nanoparticles, which is kinematically facilitated by a trap-and-release mechanism of the reactants and nanoparticles that is confirmed by a steady incompressible flow simulation. This work could lead to future alternative sustainable synthetic routes to critical alkane-based chemicals or fuels.

Sniffing Bacteria with a Carbon-Dot Artificial Nose.

HIGHLIGHTS: Novel artificial nose based upon electrode-deposited carbon dots (C-dots). Significant selectivity and sensitivity determined by "polarity matching" between the C-dots and gas molecules. The C-dot artificial nose facilitates, for the first time, real-time, continuous monitoring of bacterial proliferation and discrimination among bacterial species, both between Gram-positive and Gram-negative bacteria and between specific strains. Machine learning algorithm furnishes excellent predictability both in the case of individual gases and for complex gas mixtures. Continuous, real-time monitoring and identification of bacteria through detection of microbially emitted volatile molecules are highly sought albeit elusive goals. We introduce an artificial nose for sensing and distinguishing vapor molecules, based upon recording the capacitance of interdigitated electrodes (IDEs) coated with carbon dots (C-dots) exhibiting different polarities. Exposure of the C-dot-IDEs to volatile molecules induced rapid capacitance changes that were intimately dependent upon the polarities of both gas molecules and the electrode-deposited C-dots. We deciphered the mechanism of capacitance transformations, specifically substitution of electrode-adsorbed water by gas molecules, with concomitant changes in capacitance related to both the polarity and dielectric constants of the vapor molecules tested. The C-dot-IDE gas sensor exhibited excellent selectivity, aided by application of machine learning algorithms. The capacitive C-dot-IDE sensor was employed to continuously monitor microbial proliferation, discriminating among bacteria through detection of distinctive "volatile compound fingerprint" for each bacterial species. The C-dot-IDE platform is robust, reusable, readily assembled from inexpensive building blocks and constitutes a versatile and powerful vehicle for gas sensing in general, bacterial monitoring in particular.

Carbon dot-polymer nanoporous membrane for recyclable sunlight-sterilized facemasks.

Facemasks are considered the most effective means for preventing infection and spread of viral particles. In particular, the coronavirus (COVID-19) pandemic underscores the urgent need for developing recyclable facemasks due to the considerable environmental damage and health risks imposed by disposable masks and respirators. We demonstrate synthesis of nanoporous membranes comprising carbon dots (C-dots) and poly(vinylidene fluoride) (PVDF), and demonstrate their potential use for recyclable, self-sterilized facemasks. Notably, the composite C-dot-PVDF films exhibit hydrophobic surface which prevents moisture accumulation and a compact nanopore network which allows both breathability as well as effective filtration of particles above 100 nm in diameter. Particularly important, self-sterilization occurs upon short solar irradiation of the membrane, as the embedded C-dots efficiently absorb visible light, concurrently giving rise to elevated temperatures through heat dissipation.

The pro-apoptotic domain of BIM protein forms toxic amyloid fibrils.

BIM is a key apoptotic protein, participating in diverse cellular processes. Interestingly, recent studies have hypothesized that BIM is associated with the extensive neuronal cell death encountered in protein misfolding diseases, such as Alzheimer's disease. Here, we report that the core pro-apoptotic domain of BIM, the BIM-BH3 motif, forms ubiquitous amyloid fibrils. The BIM-BH3 fibrils exhibit cytotoxicity, disrupt mitochondrial functions, and modulate the structures and dynamics of mitochondrial membrane mimics. Interestingly, a slightly longer peptide in which BIM-BH3 was flanked by four additional residues, widely employed as a model of the pro-apoptotic core domain of BIM, did not form fibrils, nor exhibited cell disruptive properties. The experimental data suggest a new mechanistic role for the BIM-BH3 domain, and demonstrate, for the first time, that an apoptotic peptide forms toxic amyloid fibrils.

Porous Graphene Oxide-Metal Ion Composite for Selective Sensing of Organophosphate Gases.

Organophosphates are used as agricultural pesticides and also encountered as toxic nerve agents in chemical warfare. Accordingly, development of sensors for detecting and monitoring organophosphate vapors is highly sought after. We present a new capacitive gas sensor exhibiting remarkable specificity and sensitivity toward the organophosphate nerve gas simulants triethyl-phosphate (TEP) and dimethyl methyl phosphate and the pesticide dichlorvos. Specifically, the capacitive sensor comprises a composite porous graphene oxide matrix intercalating cobalt or nickel ions, prepared through a simple freeze-drying procedure. We demonstrate that the porous graphene oxide/metal ion electrode undergoes fast capacitance changes only upon exposure to organophosphate vapors. Moreover, the sensor exhibits extraordinary sensitivity upon interactions with TEP. Detailed mechanistic analyses, carried out in comparison to porous graphene oxide coupled to other transition metal ions, reveal that the remarkable sensing properties of the Co2+ or Ni2+/porous graphene oxide systems likely arise from the distinct mode of metal ion incorporation into the graphene oxide host matrix and substitution of metal-complexed water ligands with organophosphate molecules. The new metal ion/porous graphene oxide capacitive sensor may be employed for alerting and monitoring organophosphate gases in different environments.