Aptamer and Electrochemical Aptasensor towards Selenate Ions (SeO42-).

Selenium is an essential inorganic compound in human and animal nutrition, involved in the proper functioning of the body. As a micronutrient, it actively contributes to the regulation of various metabolic activities, i.e., thyroid hormone, and protection against oxidative stress. However, Se exhibits a narrow concentration window between having a positive effect and exerting a toxic effect. In higher doses, it negatively affects living organisms and causes DNA damage through the formation of free radicals. Increased reactivity of Se anions can also disrupt the integrity and function of DNA-repairing proteins. As the permissible concentration of Se in drinking water is 10 µg/L, it is vital to develop sensitive and robust methods of Se detection in aqueous samples. In this study, for the first time, we proposed a selective aptamer for selenate ion detection, chosen following the SELEX process, and its application in the construction of an electrochemical aptasensor towards SeO42- ions. Measurement conditions such as the used redox marker and pH value of the measurement solution were chosen. The proposed aptasensor is characterized by good selectivity and an LOD of 1 nM. Conditions for biosensor regeneration and storage were also investigated in this research.

Development of a novel LED-IoT photoreactor for enhanced removal of carbamazepine waste driven by solar energy.

This study introduces an innovative LED-IoT photoreactor, representing a significant advancement in response to the demand for sustainable water purification. The integration of LED-IoT installations addresses the challenge of intermittent sunlight availability, employing LEDs with a spectrum mimicking natural sunlight. Passive Infra-Red (PIR) sensors and Internet of things (IoT) technology ensure consistent radiation intensity, with the LED deactivating in ample sunlight and activating in its absence. Utilizing a visible light-absorbing photocatalyst developed through sol-gel synthesis and mild-temperature calcination, this research demonstrates a remarkable carbamazepine removal efficiency exceeding 95% under LED-IoT system illumination, compared to less than 90% efficiency with sunlight alone, within a 6-h exposure period. Moreover, the designed photocatalytic system achieves over 60% mineralization of carbamazepine after 12 h. Notably, the photocatalyst demonstrated excellent stability with no performance loss during five further cycles. Furthermore, integration with renewable energy sources facilitated continuous operation beyond daylight hours, enhancing the system's applicability in real-world water treatment scenarios. A notable application of the LED-IoT system at an operating sewage treatment plant showed nearly 80% efficiency in carbamazepine removal from sewage in the secondary settling tank after 6 h of irradiation, coupled with nearly 40% mineralization efficiency. Additionally, physicochemical analyses such as XPS and STA-FTIR confirm that the carbamazepine photooxidation process does not affect the surface of the photocatalyst, showing no adsorption for degradation products.

Study of the Crystal Structure and Hydrogen Bonding during Cold Crystallization of Poly(trimethylene 2,5-furandicarboxylate).

Here, we present a detailed description of the in situ isothermal crystallization of poly(trimethylene 2,5-furandicarboxylate)(PTF) as revealed by real-time Fourier transform infrared spectroscopy (FTIR) and grazing incidence wide-angle X-ray scattering (GIWAXS). From FTIR experiments, the evolution of hydrogen bonding with crystallization time can be monitored in real time, while from GIWAXS, crystal formation can be followed. Density functional theory (DFT) calculations have been used to simulate FTIR spectra for different theoretical structures, enabling a precise band assignment. In addition, based on DFT ab initio calculations, the influence of hydrogen bonding on the evolution with crystallization time can be understood. Moreover, from DFT calculations and comparison with both FTIR and GIWAXS experiments, a crystalline structure of poly(trimethylene 2,5-furandicarboxylate) is proposed. Our results demonstrate that hydrogen bonding is present in both the crystalline and the amorphous phases and its rearrangement can be considered as a significant driving force for crystallization of poly(alkylene 2,5-furanoate)s.

Identification of medium- and mechanism-related pitfalls towards improved performance and applicability of electrochemical mercury(II) aptasensors.

The importance of understanding the mercury (II) ion interactions with thymine-rich DNA sequences is the reason for multiple comparative investigations carried out with the use of optical detection techniques directly in the depth of solution. However, the results of such investigations have limited applicability in the interpretation of the Hg2+ binding phenomenon by DNA sequences in thin, interfacial (electrode/solution), self-organized monolayers immobilized on polarizable surfaces, often used for sensing purposes in electrochemical biosensors. Overlooking the careful optimization of the measurement conditions is the source of discrepancies in the interpretation of the registered electrochemical signal. In this study, the chosen effects accompanying the efficiency of surface related recognition of Hg2+ by polyThymine DNA sequences labelled with methylene blue were investigated by voltammetry, QCM and spectro-electrochemical techniques. As was shown, the composition of the biosensing layer and buffers or the analytical procedures have a significant impact on the registered electrochemical readout which translates into signal stability, the biosensor's working parameters or even the mechanism of detection. After elucidation of the above factors, the complete and ready-to-use biosensor-based analytical solution was proposed offering subpicomolar mercury ion determination with high selectivity (also in aqueous real samples), reusability, and high signal stability even after long-term storage. The developed procedures were successfully used during the miniaturization process with self-prepared (PVD) elastic transducers. The obtained sensor, together with the simplicity of its use, low manufacturing cost, and attractive analytical parameters (i.e., LOD < < Hg2+ WHO limit) can present an interesting alternative for on-site mercury ion detection in environmental samples.

Hytrel-like Copolymers Based on Furan Polyester: The Effect of Poly(Butylene Furanoate) Segment on Microstructure and Mechanical/Elastic Performance.

This paper aims to compare the performance of two Hytrel-like segmented copolymers: "classic" PBT-b-PTMG and fully bio-based PBF-b-PTMG, containing poly(butylene furanoate) as the rigid segment. The idea behind this research is to assess whether the sustainable copolymers can successfully replace those "classic" once at the thermoplastic elastomers' market. Two series of copolymers were synthesized under the same process parameters, had the same compositions, but differed in aromatic ring structure in terephthalate/furanoate unit. Furthermore, the materials were processed by injection moulding as typical Hytrel products. Then, the samples were subjected to extensive characterisation including NMR, GPC, FTIR, DSC, WAXS, DMTA, TGA techniques and mechanical tests with particular interest in the microstructure formed during processing and its effect on the copolymers' mechanical and elastic behaviour. The detailed analysis proved that PBF-b-PTMG and PBT-b-PTMG copolymers represent two kinds of materials with similar chemical structure, some features of thermoplastic elastomers, but evident differences in their physical properties.

Modern Electrochemical Biosensing Based on Nucleic Acids and Carbon Nanomaterials.

To meet the requirements of novel therapies, effective treatments should be supported by diagnostic tools characterized by appropriate analytical and working parameters. These are, in particular, fast and reliable responses that are proportional to analyte concentration, with low detection limits, high selectivity, cost-efficient construction, and portability, allowing for the development of point-of-care devices. Biosensors using nucleic acids as receptors has turned out to be an effective approach for meeting the abovementioned requirements. Careful design of the receptor layers will allow them to obtain DNA biosensors that are dedicated to almost any analyte, including ions, low and high molecular weight compounds, nucleic acids, proteins, and even whole cells. The impulse for the application of carbon nanomaterials in electrochemical DNA biosensors is rooted in the possibility to further influence their analytical parameters and adjust them to the chosen analysis. Such nanomaterials enable the lowering of the detection limit, the extension of the biosensor linear response, or the increase in selectivity. This is possible thanks to their high conductivity, large surface-to-area ratio, ease of chemical modification, and introduction of other nanomaterials, such as nanoparticles, into the carbon structures. This review discusses the recent advances on the design and application of carbon nanomaterials in electrochemical DNA biosensors that are dedicated especially to modern medical diagnostics.

Recent Achievements in Electrochemical and Optical Nucleic Acids Based Detection of Metal Ions.

Recently nucleic acids gained considerable attention as selective receptors of metal ions. This is because of the possibility of adjusting their sequences in new aptamers selection, as well as the convenience of elaborating new detection mechanisms. Such a flexibility allows for easy utilization of newly emerging nanomaterials for the development of detection devices. This, in turn, can significantly increase, e.g., analytical signal intensity, both optical and electrochemical, and the same can allow for obtaining exceptionally low detection limits and fast biosensor responses. All these properties, together with low power consumption, make nucleic acids biosensors perfect candidates as detection elements of fully automatic portable microfluidic devices. This review provides current progress in nucleic acids application in monitoring environmentally and clinically important metal ions in the electrochemical or optical manner. In addition, several examples of such biosensor applications in portable microfluidic devices are shown.

Comparative Evaluation of Different Surface Coatings of Fe3O4-Based Magnetic Nano Sorbent for Applications in the Nucleic Acids Extraction.

Nucleic acid extraction and purification are crucial steps in sample preparation for multiple diagnostic procedures. Routine methodologies of DNA isolation require benchtop equipment (e.g., centrifuges) and labor-intensive steps. Magnetic nanoparticles (MNPs) as solid-phase sorbents could simplify this procedure. A wide range of surface coatings employs various molecular interactions between dsDNA and magnetic nano-sorbents. However, a reliable, comparative evaluation of their performance is complex. In this work, selected Fe3O4 modifications, i.e., polyethyleneimine, gold, silica, and graphene derivatives, were comprehensively evaluated for applications in dsDNA extraction. A family of single batch nanoparticles was compared in terms of morphology (STEM), composition (ICP-MS/MS and elemental analysis), surface coating (UV-Vis, TGA, FTIR), and MNP charge (ζ-potential). ICP-MS/MS was also used to unify MNPs concentration allowing a reliable assessment of individual coatings on DNA extraction. Moreover, studies on adsorption medium (monovalent vs. divalent ions) and extraction buffer composition were carried out. As a result, essential relationships between nanoparticle coatings and DNA adsorption efficiencies have been noticed. Fe3O4@PEI MNPs turned out to be the most efficient nano sorbents. The optimized composition of the extraction buffer (medium containing 0.1 mM EDTA) helped avoid problems with Fe3+ stripping, which improved the validity of the spectroscopic determination of DNA recovery.

Relaxation Dynamics of Biomass-Derived Copolymers With Promising Gas-Barrier Properties.

This article presents an experimental study on the relaxation dynamics of a series of random copolymers based on bio-friendly comonomers with interesting gas barrier properties. We analyze the relaxation response in the glassy and ultraviscous regime of poly (trimethylene furanoate/sebacate) random copolymers via dielectric spectroscopy. We report lower values of dynamic fragility [a dimensionless index introduced in 1985 (Angell, Relaxations in Complex Systems, 1985)] in comparison to popular polyesters widely used in industry, such as poly (ethylene terephthalate), suggesting that the amorphous phase of these furanoate-based polyesters adopt an efficient chain packing. This is consistent with their low permeability to gases. We also discuss on different equations (phenomenological and theory-based approaches) for fitting the temperature-evolution of the alpha relaxation time.

Biobased Thermoplastic Elastomers: Structure-Property Relationship of Poly(hexamethylene 2,5-furanodicarboxylate)-Block-Poly(tetrahydrofuran) Copolymers Prepared by Melt Polycondensation.

A series of poly(hexamethylene 2,5-furanodicarboxylate)-block-poly(tetrahydrofuran) (PHF-b-F-pTHF) copolymers were synthesized using a two-stage procedure, employing transesterification and polycondensation. The content of pTHF flexible segments varied from 25 to 75 wt.%. 1H nuclear magnetic resonance (NMR) and Fourier transformed infrared spectroscopy (FTIR) analyses were applied to confirm the molecular structure of the materials. Differential scanning calorimetry (DSC), dynamic mechanical measurements (DMTA), and X-ray diffraction (XRD) allowed characterizing the supramolecular structure of the synthesized copolymers. SEM analysis was applied to show the differences in the block copolymers' morphologies concerning their chemical structure. The influence of the number of flexible segments in the copolymers on the phase transition temperatures, thermal properties, as well as the thermo-oxidative and thermal stability was analyzed. TGA analysis, along with tensile tests (static and cyclic), confirmed the utilitarian performance of the synthesized bio-based materials. It was found that an increase in the amount of pTHF caused the increase of both number-average and weight-average molecular weights and intrinsic viscosities, and at the same time causing the shift of the values of phase transition temperatures toward lower ones. Besides, PHF-b-F-pTHF containing 75 wt.% of F-pTHF units was proved to be a promising thermoplastic shape memory polymer (SMP) with a switching temperature of 20 °C.

Comparing Multi-Walled Carbon Nanotubes and Halloysite Nanotubes as Reinforcements in EVA Nanocomposites.

The influence of carbon multi-walled nanotubes (MWCNTs) and halloysite nanotubes (HNTs) on the physical, thermal, mechanical, and electrical properties of EVA (ethylene vinyl acetate) copolymer was investigated. EVA-based nanocomposites containing MWCNTs or HNTs, as well as hybrid nanocomposites containing both nanofillers were prepared by melt blending. Scanning electron microcopy (SEM) images revealed the presence of good dispersion of both kinds of nanotubes throughout the EVA matrix. The incorporation of nanotubes into the EVA copolymer matrix did not significantly affect the crystallization behavior of the polymer. The tensile strength of EVA-based nanocomposites increased along with the increasing CNTs (carbon nanotubes) content (increased up to approximately 40% at the loading of 8 wt.%). In turn, HNTs increased to a great extent the strain at break. Mechanical cyclic tensile tests demonstrated that nanocomposites with hybrid reinforcement exhibit interesting strengthening behavior. The synergistic effect of hybrid nanofillers on the modulus at 100% and 200% elongation was visible. Moreover, along with the increase of MWCNTs content in EVA/CNTs nanocomposites, an enhancement in electrical conductivity was observed.

Enhanced Functional Properties of Low-Density Polyethylene Nanocomposites Containing Hybrid Fillers of Multi-Walled Carbon Nanotubes and Nano Carbon Black.

In this work, hybrid filler systems consisting of multi-walled carbon nanotubes (MWCNTs) and nano carbon black (nCB) were incorporated by melt mixing in low-density polyethylene (LDPE). To hybrid systems a mixture of MWCNTs and nCB a mass ratio of 1:1 and 3:1 were used. The purpose was to study if the synergistic effects can be achieved on tensile strength and electrical and thermal conductivity. The dispersion state of carbon nanofillers in the LDPE matrix has been evaluated with scanning electron microscopy. The melting and crystallization behavior of all nanocomposites was not significantly influenced by the nanofillers. It was found that the embedding of both types of carbon nanofillers into the LDPE matrix caused an increase in the value of Young's modulus. The results of electrical and thermal conductivity were compared to LDPE nanocomposites containing only nCB or only MWCNTs presented in earlier work LDPE/MWCNTs. It was no synergistic effects of nCB in multi-walled CNTs and nCB hybrid nanocomposites regarding mechanical properties, electrical and thermal conductivity, and MWCNTs dispersion. Since LDPE/MWCNTs nanocomposites exhibit higher electrical conductivity than LDPE/MWCNTs + nCB or LDPE/nCB nanocomposites at the same nanofiller loading (wt.%), it confirms our earlier study that MWCNTs are a more efficient conductive nanofiller. The presence of MWCNTs and their concentration in hybrid nanocomposites was mainly responsible for the improvement of their thermal conductivity.

Laser-Induced Periodic Surface Structuring of Poly(trimethylene terephthalate) Films Containing Tungsten Disulfide Nanotubes.

We report the study of the formation of Laser Induced Periodic Surface Structures (LIPSS), with UV femtosecond laser pulses (λ = 265 nm), in free-standing films of both Poly(trimethylene terephthalate) (PTT) and the composite PTT/tungsten disulfide inorganic nanotubes (PTT-WS2). We characterized the range of fluences and number of pulses necessary to induce LIPSS formation and measured the topography of the samples by Atomic Force Microscopy, the change in surface energy and contact angle using the sessile drop technique, and the modification in both Young's modulus and adhesion force values with Peak Force-Quantitative Nanomechanical Mapping. LIPSS appeared parallel to the laser polarization with a period close to its wavelength in a narrow fluence and number of pulses regime, with PTT-WS2 needing slightly larger fluence than raw PTT due to its higher crystallinity and heat diffusion. Little change was found in the total surface energy of the samples, but there was a radical increase in the negative polar component (γ-). Besides, we measured small variations in the samples Young's modulus after LIPSS formation whereas adhesion is reduced by a factor of four. This reduction, as well as the increase in γ-, is a result of the modification of the surface chemistry, in particular a slight oxidation, during irradiation.

Functional Properties of Poly(Trimethylene Terephthalate)-Block-Poly(Caprolactone) Based Nanocomposites Containing Graphene Oxide (GO) and Reduced Graphene Oxide (rGO).

This work reports a study on the influence of graphene oxide (GO) and reduced graphene oxide (rGO) on the functional properties of poly(trimethylene terephthalate)-block-poly(caprolactone) (PTT-block-PCL-T) (75/25 wt.%/wt.%) copolymer, obtained from dimethyl terephthalate (DMT), 1,3-biopropanediol and polycaprolactone diol (PCL) via in situ polymerization. The article presents, if and how the reduction of graphene oxide, in comparison to the non-reduced one, can affect morphological, thermal, electrical and mechanical properties. SEM examination confirms/reveals the homogeneous distribution of GO/rGO nanoplatelets in the PTT-block-PCL-T copolymer matrix. More than threefold increase in the value of the tensile modulus is achieved by the addition of 1.0 wt.% of GO and rGO. Moreover, the thermal conductivity and thermal stability of the GO and rGO-based nanocomposites are also improved. The differential scanning calorimetry (DSC) measurement indicates that the incorporation of GO and rGO has a remarkable impact on the crystallinity of the nanocomposites (an increase of crystallization temperature up to 58 °C for nanocomposite containing 1.0 wt.% of GO is observed). Therefore, the high performances of the PTT-block-PCL-T-based nanocomposites are mainly attributed to the uniform dispersion of nanoplatelets in the polymer matrix and strong interfacial interactions between components.

Electrically and Thermally Conductive Low Density Polyethylene-Based Nanocomposites Reinforced by MWCNT or Hybrid MWCNT/Graphene Nanoplatelets with Improved Thermo-Oxidative Stability.

In this paper, the electrical and thermal conductivity and morphological behavior of low density polyethylene (LDPE)/multi-walled carbon nanotubes (MWCNTs) + graphene nanoplatelets (GNPs) hybrid nanocomposites (HNCs) have been studied. The distribution of MWCNTs and the hybrid of MWCNTs/GNPs within the polymer matrix has been investigated with scanning electron microscopy (SEM). The results showed that the thermal and electrical conductivity of the LDPE-based nanocomposites increased along with the increasing content of carbon nanofillers. However, one could observe greater improvement in the thermal and electrical conductivity when only MWCNTs have been incorporated. Moreover, the improvement in tensile properties and thermal stability has been observed when carbon nanofillers have been mixed with LDPE. At the same time, the increasing content of MWCNTs and MWCNTs/GNPs caused an increase in the melt viscosity with only little effect on phase transition temperatures.

Phase Separation and Elastic Properties of Poly(Trimethylene Terephthalate)-block-poly(Ethylene Oxide) Copolymers.

A series of poly(trimethylene terephthalate)-block-poly(ethylene oxide) (PTT-b-PEOT) copolymers with different compositions of rigid PTT and flexible PEOT segments were synthesized via condensation in the melt. The influence of the block length and the block ratio on the micro-separated phase structure and elastic properties of the synthesized multiblock copolymers was studied. The PEOT segments in these copolymers were kept constant at 1130, 2130 or 3130 g/mol, whereas the PTT content varied from 30 up to 50 wt %. The phase separation was assessed using differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). The crystal structure of the synthesised block copolymers and their microstructure on the manometer scale was evaluated by using WAXS and SAXS analysis. Depending on the PTT/PEOT ratio, but also on the rigid and flexible segment length in PTT-b-PEO copolymers, four different domains were observed i.e.,: a crystalline PTT phase, a crystalline PEO phase (which exists for the whole series based on three types of PEOT segments), an amorphous PTT phase (only at 50 wt % content of PTT rigid segments) and an amorphous PEO phase. Moreover, the elastic deformability and reversibility of PTT-b-PEOT block copolymers were studied during a cyclic tensile test. Determined values of permanent set resultant from maximum attained stain (100% and 200%) for copolymers were used to evaluate their elastic properties.

Nematic-to-isotropic photo-induced phase transition in azobenzene-doped low-molar liquid crystals.

The photo-induced phase transition generated by several 4,4'-disubstituted azobenzenes in host nematic low-molar mass liquid crystals was quantified by means of the efficiency, DeltaT(N-I), using polarized optical microscopy (POM) at variable temperature. Non-covalent interactions established between mesogen and azobenzene were the main determinants of the photo-induced phase transition behaviour. The correct design of the chemical structure of the system components allows controlling the temperature range in which the photo-induced mesophase transition occurs. Therefore, more efficient systems were obtained when azobenzenes with an extended aromatic core were used.