Biodegradation Study of Styrene-Butadiene Composites with Incorporated Arthrospira platensis Biomass.

The preparation of polymer composites that incorporate material of a biogenic nature in the polymer matrices may lead to a reduction in fossil polymer consumption and a potentially higher biodegradability. Furthermore, microalgae biomass as biogenic filler has the advantage of fast growth and high tolerance to different types of culture media with higher production yields than those provided by the biomass of terrestrial crops. On the other hand, algal biomass can be a secondary product in wastewater treatment processes. For the present study, an SBS polymer composite (SBSC) containing 25% (w/w) copolymer SBS1 (linear copolymer: 30% styrene and 70% butadiene), 50% (w/w) copolymer SBS2 (linear copolymer: 40% styrene and 60% butadiene), and 25% (w/w) paraffin oil was prepared. Arthrospira platensis biomass (moisture content 6.0 ± 0.5%) was incorporated into the SBSC in 5, 10, 20, and 30% (w/w) ratios to obtain polymer composites with spirulina biomass. For the biodegradation studies, the ISO 14855-1:2012(E) standard was applied, with slight changes, as per the specificity of our experiments. The degradation of the studied materials was followed by quantitatively monitoring the CO2 resulting from the degradation process and captured by absorption in NaOH solution 0.5 mol/L. The structural and morphological changes induced by the industrial composting test on the materials were followed by physical-mechanical, FTIR, SEM, and DSC analysis. The obtained results were compared to create a picture of the material transformation during the composting period. Thus, the collected data indicate two biodegradation processes, of the polymer and the biomass, which take place at the same time at different rates, which influence each other. On the other hand, it is found that the material becomes less ordered, with a sponge-like morphology; the increase in the percentage of biomass leads to an advanced degree of degradation of the material. The FTIR analysis data suggest the possibility of the formation of peptide bonds between the aromatic nuclei in the styrene block and the molecular residues resulting from biomass biodegradation. It seems that in industrial composting conditions, the area of the polystyrene blocks from the SBS-based composite is preferentially transformed in the process.

Influence of Biogenic Material Content on the Biodegradability of Styrene-Butadiene Composites with Incorporated Chlorella vulgaris Biomass.

Bio-fillers are intensively studied for advanced polymer composite circular design and production. In this context, the algal biomass may be considered an important and relatively low-cost resource, when harvested as a by-product from wastewater treatment plants. The biomass of the algal species Chlorella vulgaris is frequently used in this type of environmental process, and its macro constituents' composition ranges from around 15-25% carbohydrates, 10-20% lipids, and 50-60% proteins. Poly (styrene-butadiene-styrene) (SBS) copolymers have a matrix composed of glassy polystyrene domains connected by flexible polybutadiene segments. Although the physical-mechanical properties of SBS copolymers recommend them for many industrial applications, they have the drawback of low biodegradability. This study aimed to assess the aerobic biodegradability of polymer composites by integrating biomass from Chlorella vulgaris at varying mass percentages of 5, 10, and 20% into SBS copolymer composites. Biodegradation tests were conducted under industrial composting conditions (58 °C and 50% relative humidity) for 180 days. The biodegradability of materials was evaluated by measuring the CO2 produced in each vessel during the study period. Potential correlations between the amount of carbon dioxide released and the percentage of biomass added to the polymer matrix were examined. Structural and morphological changes were assessed using Fourier Transform infrared spectroscopy (FTIR), thermal analysis (DSC), and scanning electron microscopy (SEM). Physical and chemical testing revealed a decrease in sample density after the industrial composting test, along with noticeable changes in melt flow index (MFI). The observed physical and chemical changes, coupled with FTIR, SEM, and DSC data, indicate increased cross-linking and higher porosity in biodegraded polymer structures with higher biomass content. This behavior is likely due to the formation of cross-linked connections between polymer chains and polypeptide chains resulting from protein degradation, enhancing connections between polystyrene units facilitated by peptide bonds with the benzene units of the styrene blocks within the polymer matrix.

Phytochemical Statistical Mapping of Red Grape Varieties Cultivated in Romanian Organic and Conventional Vineyards.

Red grapes are rich in phytochemicals such as phenolics and flavonoids, which are strongly correlated with their antioxidant activity. Thus, grapes as-harvested and grape extracts, especially those obtained from their seeds and pulp, have been reported to have health benefits, and accordingly, grapes and their derivatives are considered potential functional food ingredients. The total phenolic content, total flavonoid content, and the antioxidant activity of skin, pulp, and seeds of four grape varieties grown both in conventional and organic vineyards were examined in this study. Phytochemical characteristics of one native Romanian variety, Feteasca Neagra, were compared with data measured for three red grape varieties more commonly cultivated worldwide (Merlot, Pinot Noir, and Muscat Hamburg). It was found that the seeds of the Pinot Noir variety grown in an organic system contained the highest total phenolics of 169.53 ± 7.32 mg gallic acid equivalents/g and the highest total flavonoid content of 388.25 ± 10.72 mg quercetin equivalents/g, values corresponding to high antioxidant activity (312.84 ± 12.81 mg ascorbic acid equivalents/g). The total flavonoid content in the hydroalcoholic extracts obtained from seeds of Pinot Noir (organic vineyard) was around 24.5-fold higher than that of the skin of Pinot Noir (conventional vineyard). Experiments showed that seeds of all four tested grape varieties are good sources of total flavonoids, not only of total phenolics. When referring to the organic vineyard, the skin and pulp grapes showed good results for the total phenolic content. The antioxidant activities of the hydroalcoholic extracts were well-correlated with the total phenolic content and total flavonoid content. Lower values of these parameters were found for extracts obtained from skin and pulp than for those obtained from seeds of the same grape variety regardless of the culture management system (organic/conventional). Data mining techniques such as regression analysis, principal component analysis, and clustering analysis were applied to establish the potential correlation between the phytochemical content and the antioxidant activities of the red grapes on the one hand, and grape variety, anatomical parts, and vineyard type (organic/conventional) on the other hand.

Functional Enhancement and Characterization of an Electrophysiological Mapping Electrode Probe with Carbonic, Directional Macrocontacts.

Electrophysiological mapping (EM) using acute electrode probes is a common procedure performed during functional neurosurgery. Due to their constructive specificities, the EM probes are lagging in innovative enhancements. This work addressed complementing a clinically employed EM probe with carbonic and circumferentially segmented macrocontacts that are operable both for neurophysiological sensing ("recording") of local field potentials (LFP) and for test stimulation. This paper illustrates in-depth the development that is based on the direct writing of functional materials. The unconventional fabrication processes were optimized on planar geometry and then transferred to the cylindrically thin probe body. We report and discuss the constructive concept and architecture of the probe, characteristics of the electrochemical interface deduced from voltammetry and chronopotentiometry, and the results of in vitro and in vivo recording and pulse stimulation tests. Two- and three-directional macrocontacts were added on probes having shanks of 550 and 770 µm diameters and 10-23 cm lengths. The graphitic material presents a ~2.7 V wide, almost symmetric water electrolysis window, and an ultra-capacitive charge transfer. When tested with clinically relevant 150 µs biphasic current pulses, the interfacial polarization stayed safely away from the water window for pulse amplitudes up to 9 mA (135 µC/cm2). The in vivo experiments on adult rat models confirmed the high-quality sensing of LFPs. Additionally, the in vivo-prevailing increase in the electrode impedance and overpotential are discussed and modeled by an ionic mobility-reducing spongiform structure; this restricted diffusion model gives new applicative insight into the in vivo-uprisen stimulation overpotential.

Preparation and Characterization of Microalgae Styrene-Butadiene Composites Using Chlorella vulgaris and Arthrospira platensis Biomass.

The food industry is a high consumer of polymer packing materials, sealing materials, and engineering components used in production equipment. Biobased polymer composites used in the food industry are obtained by incorporating different biogenic materials into the structure of a base polymer matrix. Renewable resources such as microalgae, bacteria, and plants may be used as biogenic materials for this purpose. Photoautotrophic microalgae are valuable microorganisms that are able to harvest sunlight energy and capture CO2 into biomass. They are characterized by their metabolic adaptability to environmental conditions, higher photosynthetic efficiency than terrestrial plants, and natural macromolecules and pigments. The flexibility of microalgae to grow in either low-nutrient or nutrient-rich environments (including wastewater) has led to the attention for their use in various biotechnological applications. Carbohydrates, proteins, and lipids are the main three classes of macromolecular compounds contained in microalgal biomass. The content in each of these components depends on their growth conditions. In general, proteins represent 40-70% of microalgae dry biomass, followed by carbohydrates (10-30%) and lipids (5-20%). A distinctive feature of microalgae cells is the presence of light-harvesting compounds such as photosynthetic pigments carotenoids, chlorophylls, and phycobilins, which are also receiving growing interest for applications in various industrial fields. The study comparatively reports on polymer composites obtained with biomass made of two species of green microalgae: Chlorella vulgaris and filamentous, gram-negative cyanobacterium Arthrospira. Experiments were conducted to reach an incorporation ratio of the biogenic material into the matrix in the 5-30% range, and the resulting materials were characterized by their mechanical and physicochemical properties.

Laser Processed Hybrid Lead-Free Thin Films for SAW Sensors.

In this study we report the specific interaction of various gases on the modified surface of acoustic wave devices for gas sensor applications, using the piezoelectric ceramic material BaSrTiO3 (BST), with different concentrations of Sr. For enhancing the sensitivity of the sensor, the conductive polymer polyethylenimine (PEI) was deposited on top of BST thin films. Thin films of BST were deposited by pulsed laser deposition (PLD) technique and integrated into a test heterostructure with PEI thin films deposited by matrix assisted pulsed laser evaporation (MAPLE) and interdigital Au electrodes (IDT). Further on, the layered heterostructures were incorporated into surface acoustic wave (SAW) devices, in order to measure the frequency response to various gases (N2, CO2 and O2). The frequency responses of the sensors based on thin films of the piezoelectric material deposited at different pressures were compared with layered structures of PEI/BST, in order to observe differences in the frequency shifts between sensors. The SAW tests performed at room temperature revealed different results based on deposition condition (pressure of oxygen and the percent of strontium in BatiO3 structure). Frequency shift responses were obtained for all the tested sensors in the case of a concentration of Sr x = 0.75, for all the analysed gases. The best frequency shifts among all sensors studied was obtained in the case of BST50 polymer sensor for CO2 detection.

Ternary Nanocomposites Based on Oxidized Carbon Nanohorns as Sensing Layers for Room Temperature Resistive Humidity Sensing.

This paper presents the relative humidity (RH) sensing response of a resistive sensor employing sensing layers based on a ternary nanocomposite comprising graphene oxide-oxidized carbon nanohorns-polyvinylpyrrolidone (GO-CNHox-PVP), at 1/1/1, 1/2/1, and 1/3/1 w/w/w mass ratios. The sensing structure is composed of a silicon substrate, a SiO2 layer, and interdigitated transducers (IDT) electrodes, on which the sensing layer is deposited via the drop-casting method. The morphology and the composition of the sensing layers are investigated through scanning electron microscopy (SEM) and RAMAN spectroscopy. The RH sensing capability of each carbonaceous nanocomposite-based thin film was analyzed by applying a current between the two electrodes and by measuring the voltage difference when varying the RH from 0% to 100% in humid nitrogen. The sensors have a room temperature response comparable to that of a commercial humidity sensor and are characterized by a rapid response, excellent linearity, good sensitivity, and recovery time. The manufactured sensing devices' transfer functions were established, and we extracted the response and recovery times. While the structures with GO/CNHox/PVP at 1/1/1 ratio (w/w/w) had the best performance in terms of relative sensibility, response time, and recovery time, the sensors employing the GO/CNHox/PVP nanocomposite at the 1/2/1 ratio (w/w/w) had the best linearity. Moreover, the ternary mixture proved to have much better sensing properties compared to CNHox and CNHox-PVP-based sensing layers in terms of sensitivity and linearity. Each component of the ternary nanocomposites' functional role is explained based on their physical and chemical properties. We analyzed the potential mechanism associated with the sensors' response; among these, the effect of the p-type semiconductor behavior of CNHox and GO, correlated with swelling of the PVP, was dominant and led to increased resistance of the sensing layer.

Electrical Percolation Threshold and Size Effects in Polyvinylpyrrolidone-Oxidized Single-Wall Carbon Nanohorn Nanocomposite: The Impact for Relative Humidity Resistive Sensors Design.

This paper reports, for the first time, on the electrical percolation threshold in oxidized carbon nanohorns (CNHox)-polyvinylpyrrolidone (PVP) films. We demonstrate-starting from the design and synthesis of the layers-how these films can be used as sensing layers for resistive relative humidity sensors. The morphology and the composition of the sensing layers are investigated through Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), and RAMAN spectroscopy. For establishing the electrical percolation thresholds of CNHox in PVP, these nanocomposite thin films were deposited on interdigitated transducer (IDT) dual-comb structures. The IDTs were processed both on a rigid Si/SiO2 substrate with a spacing of 10 µm between metal digits, and a flexible substrate (polyimide) with a spacing of 100 µm. The percolation thresholds of CNHox in the PVP matrix were equal to (0.05-0.1) wt% and 3.5 wt% when performed on 10 µm-IDT and 100 µm-IDT, respectively. The latter value agreed well with the percolation threshold value of about 4 wt% predicted by the aspect ratio of CNHox. In contrast, the former value was more than an order of magnitude lower than expected. We explained the percolation threshold value of (0.05-0.1) wt% by the increased probability of forming continuous conductive paths at much lower CNHox concentrations when the gap between electrodes is below a specific limit. The change in the nanocomposite's longitudinal Young modulus, as a function of the concentration of oxidized carbon nanohorns in the polymer matrix, is also evaluated. Based on these results, we identified a new parameter (i.e., the inter-electrode spacing) affecting the electrical percolation threshold in micro-nano electronic devices. The electrical percolation threshold's critical role in the resistive relative-humidity sensors' design and functioning is clearly emphasized.

Organic-Inorganic Ternary Nanohybrids of Single-Walled Carbon Nanohorns for Room Temperature Chemiresistive Ethanol Detection.

Organic-inorganic ternary nanohybrids consisting of oxidized-single walled carbon nanohorns-SnO2-polyvinylpyrrolidone (ox-SWCNH/SnO2/PVP) with stoichiometry 1/1/1 and 2/1/1 and ox-SWCNH/ZnO/PVP = 5/2/1 and 5/3/2 (all mass ratios) were synthesized and characterized as sensing films of chemiresistive test structures for ethanol vapor detection in dry air, in the range from 0 up to 50 mg/L. All the sensing films had an ox-SWCNH concentration in the range of 33.3-62.5 wt%. A comparison between the transfer functions and the response and recovery times of these sensing devices has shown that the structures with ox-SWCNH/SnO2/PVP = 1/1/1 have the highest relative sensitivities of 0.0022 (mg/L)-1, while the devices with ox-SWCNH/SnO2/PVP = 2/1/1 have the lowest response time (15 s) and recovery time (50 s) for a room temperature operation, proving the key role of carbonic material in shaping the static and dynamic performance of the sensor. These response and recovery times are lower than those of "heated" commercial sensors. The sensing mechanism is explained in terms of the overall response of a p-type semiconductor, where ox-SWCNH percolated between electrodes of the sensor, shunting the heterojunctions made between n-type SnO2 or ZnO and p-type ox-SWCNH. The hard-soft acid-base (HSAB) principle supports this mechanism. The low power consumption of these devices, below 2 mW, and the sensing performances at room temperature may open new avenues towards ethanol sensors for passive samplers of environment monitoring, alcohol test portable instruments and wireless network sensors for Internet of Things applications.

Oxidized Carbon Nanohorns as Novel Sensing Layer for Resistive Humidity Sensor.

The paper reports the relative humidity (RH) sensing response of a resistive sensor employing oxidized carbon nanohorns - based sensing layer. The sensing layer is deposited on an interdigitated (IDT) structure, comprising a Si substrate, a SiO2 layer, and IDT electrodes. The structure exhibits good RH sensitivity when varying RH from 0% up to 90%, either in humid nitrogen or in a humid air environment. The conductivity of the sensing layer decreases, while the RH level increases. During the interaction with the water molecules (acting as electron donors), the number of holes will decrease and oxidized single-walled carbon nanohorns (SWCNHs), considered normally p-type semiconductor, will become more resistive. The sensing mechanism is explained in terms of the Hard Soft Acid Base (HSAB) paradigm, building on the fact that water molecules are hard bases, while oxidized carbon nanohorns can be virtually assimilated with hard acids.

Nanostructured semiconducting metal oxides for ammonia sensors. A novel HSAB sensing paradigm.

The paper demonstrates how the Hard-Soft Acid Base (HSAB) theory can be used as a valuable criterion in the selection process of semiconducting metal oxides (MOX) suitable as sensing layers for ammonia detection. Six different cases of ammonia detection performed by chemiresistive sensors employing MOX and related nanocomposites as sensing layers are identified and discussed. The role of HSAB as an efficient selection tool for appropriate sensing layer (any type of gas), is further reinforced by analyzing and discussing literature results on MOX-based trimethylamine sensing layers. By analyzing the operation of a fiber-optic ammonia sensor, we demonstrate that the HSAB principle can be also successfully applied to the selection of sensing layers for detectors employing other sensing principles, different than the chemiresistive one. Changing the sensing paradigm (i.e., the amino groups-based compounds are part of the sensing layer, rather than part of the analyte), the paper shows that these types of molecules (polymers, carbon nanotubes, ionic liquids) are appropriate constituents of a CO2 sensing layer, in full accordance to the HSAB criteria.

Low Power Resistive Oxygen Sensor Based on Sonochemical SrTi0.6Fe0.4O2.8 (STFO40).

The current paper reports on a sonochemical synthesis method for manufacturing nanostructured (typical grain size of 50 nm) SrTi0.6Fe0.4O2.8 (Sono-STFO40) powder. This powder is characterized using X ray-diffraction (XRD), Mössbauer spectroscopy and Scanning Electron Microscopy (SEM), and results are compared with commercially available SrTi0.4Fe0.6O2.8 (STFO60) powder. In order to manufacture resistive oxygen sensors, both Sono-STFO40 and STFO60 are deposited, by dip-pen nanolithography (DPN) method, on an SOI (Silicon-on-Insulator) micro-hotplate, employing a tungsten heater embedded within a dielectric membrane. Oxygen detection tests are performed in both dry (RH = 0%) and humid (RH = 60%) nitrogen atmosphere, varying oxygen concentrations between 1% and 16% (v/v), at a constant heater temperature of 650 °C. The oxygen sensor, based on the Sono-STFO40 sensing layer, shows good sensitivity, low power consumption (80 mW), and short response time (25 s). These performance are comparable to those exhibited by state-of-the-art O2 sensors based on STFO60, thus proving Sono-STFO40 to be a material suitable for oxygen detection in harsh environments.