Carbon-based dots (CDs) are a novel class of luminescent carbon nanomaterials that have attracted much attention as promising alternatives for cadmium-based quantum dots and fluorescent organic dyes. Although different strategies have been proposed to produce CDs with intense and tuneable one-photon excited fluorescence (OPEF), the case of analogous two-photon excited fluorescence (TPEF) has not been fully explored yet. By varying the synthesis conditions, we produced three types of phloroglucinol-based carbon nanodots (PG CNDs). Their remarkable OPEF and TPEF properties can be tuned by (Ia) the conjugated aromatic domains and (Ib) the content of oxygenous moieties. In addition, the emission colour of the PG CNDs is strongly responsive to (II) the hydrogen-bonding network, enabling colour-switching while maintaining excellent fluorescence yields (both OPEF and TPEF). These three factors were evaluated for their suitability for the tuning of the emission colour. Our studies point out the advantages of the tuneable PG CNDs to be used in optoelectronics and biological application domains.

The need for efficient probing, sensing, and control of the bioactivity of biomolecules (e.g., albumins) has led to the engineering of new fluorescent albumins' markers fulfilling very specific chemical, physical, and biological requirements. Here, we explore acetone-derived polymer dots (PDs) as promising candidates for albumin probes, with special attention paid to their cytocompatibility, two-photon absorption properties, and strong ability to non-destructively interact with serum albumins. The PDs show no cytotoxicity and exhibit high photostability. Their pronounced green fluorescence is observed upon both onephoton excitation (OPE) and two-photon excitation (TPE). Our studies show that both OPE and TPE emission responses of PDs are proteinaceous environment-sensitive. The proteins appear to constitute a matrix for the dispersion of fluorescent PDs, limiting both their aggregation and interactions with the aqueous environment. It results in a large enhancement of PD fluorescence. Meanwhile, the PDs do not interfere with the secondary protein structures of albumins, nor do they induce their aggregation, enabling the PD candidates to be good nanomarkers for non-destructive probing and sensing of albumins.

Nanoporous carbons remain the most promising candidates for effective hydrogen storage by physisorption in currently foreseen hydrogen-based scenarios of the world’s energy future. An optimal sorbent meeting the current technological requirement has not been developed yet. Here we first review the storage limitations of currently available nanoporous carbons, then we discuss possible ways to improve their storage performance. We focus on two fundamental parameters determining the storage (the surface accessible for adsorption and hydrogen adsorption energy). We define numerically the values nanoporous carbons have to show to satisfy mobile application requirements at pressures lower than 120 bar. Possible necessary modifications of the topology and chemical compositions of carbon nanostructures are proposed and discussed. We indicate that pore wall fragmentation (nano-size graphene scaffolds) is a partial solution only, and chemical modifications of the carbon pore walls are required. The positive effects (and their limits) of the carbon substitutions by B and Be atoms are described. The experimental ‘proof of concept’ of the proposed strategies is also presented. We show that boron substituted nanoporous carbons prepared by a simple arc-discharge technique show a hydrogen adsorption energy twice as high as their pure carbon analogs. These preliminary results justify the continuation of the joint experimental and numerical research effort in this field.

We report a microscopic model of the phonon-adsorption correlations in flexible metal−organic framework materials. We analyze the mechanism of the gate opening deformation using the notion of coupled phonon- and adsorption-induced structural transformation. Using the ZIF-8 structure as an example, we perform an analysis of transformation-related, low-frequency phonon modes of the framework.On the basis of structure-related quantities such as pore limiting diameter, void fraction, and adsorption uptake, we determine the conditions which lead to the gate opening transformation in ZIF-8. Energetic landscape of the deformation process is analyzed using grand thermodynamic potential of adsorption. We generalize our conclusions to other flexible ZIF structures with the same topology.

Competitive adsorption of water is an important issue in the adsorption-based industrial processes of bio- and flue gases separation. The dehumidification of gases prior to separation would increase process complexity and lower its economic interest. In this work, large-scale computational screening was applied to identify Metal-Organic Frameworks (MOFs) structures which exhibit high CO2/CH4 selectivity and total loading higher than 0.5 mol/kg (in the presence of water). High-throughput Grand Canonical Monte Carlo (GCMC) screening of nearly 3000 existing MOF materials was carried out. Initial selection assumed fixed values of pore limiting diameter (PLD) and Henry's constant for water and allowed one to preselect 764 structures. After GCMC simulations carried for 50/50 CO2/CH4 mixture, at ambient conditions (p = 1 bar, T = 298 K), and variable gas humidity (0%, 5%, 30% and 40%) the final selection revealed 13 most promising MOFs structures. We focused on analysis of the correlations between the properties of the selected MOFs and the separation selectivity. We show that the selectivity is a complex function of the porous materials characteristics and finding selective sorbent, performing well in dry and wet conditions requires careful analysis of available MOFs.

Carbon-based dots have been attracting much attention as potentially superior alternatives to more conventional semiconductor (e.g. cadmium-based) nanoparticles, due to their fascinating optical properties, chemical and photochemical stability, a unique environment-friendliness, and the versatility of fabrication routes. So far, different commercial materials and organic compounds were considered as carbon precursors for the syntheses but in many cases there are issues with their homogeneity or the fabrication that may require high-temperature conditions. We report on a simple low-cost procedure to produce hydrophilic and hydrophobic fractions of non-conjugated carbon-rich polymer dots (PDs) with the average diameter of 2-4 nm (hydrophilic PDs) and ca. 6 nm (hydrophobic PDs), involving acetone as carbon precursor. The as-obtained PDs reveal the greenish-blue photoluminescence (PL) that is characterized by high PL quantum yields (∼5-7%) and complex kinetics of the PL decays with the average lifetimes estimated to be 3.5 ns. Such luminescent acetone-based PDs may have potential in several application fields, including sensing and bioimaging.