A possible approach for enhancement of Poly(vinyl alcohol) (PVA) humidity-sensing performance using hydrophobically modified PVA copolymers is studied. Series of poly(vinylalcohol-co-vinylacetal)s (PVA–Ac) of acetal content in the range 18%–28% are synthesized by partial acetalization of hydroxyl groups of PVA with acetaldehyde and thin films are deposited by spin-coating using silicon substrates and glass substrates covered with Au–Pd thin film with thickness of 30 nm. Sensing properties are probed through reflectance measurements at relative humidity (RH) in the range 5%–95% RH. The influence of film thickness, post-deposition annealing temperature, and substrate type/configuration on hysteresis, sensitivity, and accuracy/resolution of humidity sensing is studied for partially acetalized PVA copolymer films, and comparison with neat PVA is made. Enhancement of sensing behavior through preparation of polymer–silica hybrids is demonstrated. The possibility of color sensing is discussed.
The influence of the macromolecular architecture of block copolymers containing poly(N,N-dimethyl acrylamide) (PDMA) on the optical characteristics and sensing properties of corresponding thin films is discussed. Series of hydrophilic PDMA-based copolymers of different chemical composition and chain architecture such as triblock, star-shaped, and branched were synthesized. The copolymers were characterized using conventional spectroscopic techniques as well as methods for characterization of copolymer macromolecular characteristics in solution, namely size-exclusion chromatography and static light scattering. Thin films of the copolymers of nanometer scale thickness were deposited on silicon substrates by the spin-coating method. The refractive index and extinction coefficient of the copolymer films were calculated from the reflectance spectra by using non-linear curve fitting methods and the composition-structure-optical properties relationships were evaluated. Humidity-sensing properties of the films were studied by measuring reflectance spectra of the films at a relative humidity range from 5 to 95%RH. The implementation of the copolymer films as optical sensors of humidity is justified and discussed.
Mechanically and thermally stable novel gel polymer electrolytes (GPEs) have been prepared and applied in supercapacitor cells. Quasi-solid and flexible films were prepared by solution casting technique and formulated by immobilization of ionic liquids (ILs) differing in their aggregate state. A crosslinking agent and a radical initiator were added to further stabilize them. The physicochemical characteristics of the obtained crosslinked films show that the realized cross-linked structure contributes to their improved mechanical and thermal stability, as well as an order of magnitude higher conductivity than that of the non-crosslinked ones. The obtained GPEs were electrochemically tested as separator in symmetric and hybrid supercapacitor cells and showed good and stable performance in the investigated systems. The crosslinked film is suitable for use as both separator and electrolyte and is promising for the development of high-temperature solid-state supercapacitors with improved capacitance characteristics.
Two new asymmetric monomethine cyanine dyes, featuring dimethoxy quinolinium or methyl quinolinium end groups and benzothiazole or methyl benzothiazole end groups were synthesized. The chemical structures of the two dyes—(E)-6,7-dimethoxy-1-methyl-4-((3-methylbenzo[d]thiazol-2(3H)-ylidene)methyl)quinolin-1-ium iodide (3a) and (E)-4-((3,5-dimethylbenzo[d]thiazol-2(3H)-ylidene)methyl)-1,2-dimethylquinolin-1-ium iodide (3b)—were confirmed through NMR spectroscopy and MALDI-TOF mass spectrometry. A new methodology was developed to study monocationic dyes in the absence of a matrix and cationizing compounds in MALDI-TOF mass experiments. The newly synthesized dyes contain hydrophobic functional groups attached to the chromophore, enhancing their affinity for the hydrophobic regions of nucleic acids within the biological matrix. The dyes’ photophysical properties were investigated in aqueous solutions and DMSO, as well as in the presence of nucleic acids. The dyes exhibit notable aggregachromism in both pure aqueous and buffered solutions. The observed aggregation phenomena were further elucidated using computational methods. Fluorescence titration experiments revealed that upon contact with nucleic acids, the dyes exhibit bioaggregachromism–aggregachromism on the surfaces of the respective biomolecular matrix (RNA or DNA). This bioaggregachromism was further confirmed by CD spectroscopy. Given the pronounced aggregachromism detected, we conclude that the dyes investigated in this study are highly suitable for use as fluorogenic probes in biomolecular recognition techniques. The unique absorption and fluorescence spectra of these dyes make them promising fluorogenic markers for various bioanalytical methods related to biomolecular recognition.
In recent years, deep eutectic solvents (DESs) have attracted a lot of attention as a substitute for the current toxic organic solvents and can be applied in many chemical processes such as extraction and synthesis. The development of new deep eutectic solvents for use in the isolation of valuable biologically active substances with significant benefits for health, the environment, and others is being investigated with increasing scientific interest. Deep eutectic solvents were prepared using menthol as a hydrogen bond donor and different tertiary amines as hydrogen bond acceptors by varying the ratio of the two constituents. The DESs obtained were analyzed using densitometry, viscosimetry, IR, TGA, and DSC. The potential of the DESs for extraction and re-extraction was evaluated with a water solution of lactic acid. All the DESs obtained are suitable for the extraction of lactic acid. Deep eutectic solvents based on menthol and dioctyl amine (M/DOA 2:1), trioctyl amine (M/TOA 2:1), tridodecyl amine (M/TDDA 1:2), and trihexyl amine (M/THA 2:1) show highest results.
In this study, the possibilities of a new “in situ” LED UV illumination NMR spectroscopic technique for performing an initiator-free thiol–ene “click” coupling reaction of an allyl-functionalized poly(allyl glycidyl ether) (PAGE) prepolymer with a number of mono- and di-oligo polyethylene glycol (PEG) thiols is demonstrated. The state-of-the-art setup constructed with LEDs as UV light sources that illuminate through optical fibers directly into an NMR testing tube at a fixed wavelength of 365 nm is appropriate for various polymeric materials and biologically active substances. The selected experimental protocol uses a series of periods of irradiation and dark periods, thus providing opportunities to conduct an effective thiol–ene “click” reaction and simultaneously study the kinetics of the photochemical reaction with the exposure time, as well as macromolecular association directly in a solution applying the whole types of NMR methods: from conventional 1H or 13C NMR to diffusion NMR spectroscopy (DOSY). In addition, the molecular mass characteristics of the prepared copolymers were studied by gel-permeation chromatography (GPC). The observed differences in the reaction rates as well as in the size of species formed (the corresponding hydrodynamic radiuses Rh of aggregates) as a result of the coupling process of parent PAGE prepolymers and model PEG thiols were thoroughly discussed and the reaction pathway proposed.