An Effective Approach for High‐Efficiency Photoelectrochemical Solar Cells by Using Bifunctional DNA Molecules Modified Photoanode

This paper firstly reports the effect of deoxyribonucleic acid (DNA) molecules extracted from chickpea and wheat plants on the injection/recombination of photogenerated electrons and sensitizing ability of dye‐sensitized solar cells (DSSCs). These high‐yield DNA molecules are applied as both linker bridging unit as well as thin tunneling barrier (TTB) at titanium dioxide (TiO₂ )/dye interface, to build up high‐efficient DSSCs. With its favorable energy levels, effective linker bridging role, and double helix structure, bifunctional DNA modifier shows an efficient electron injection, suppressed charge recombination, longer electron lifetime, and higher light harvesting efficiency, which leads to higher photovoltaic performance. In particular, a photoconversion efficiency (PCE) of 9.23% is achieved by the binary chickpea and wheat DNA‐modified TiO₂ (CW@TiO₂) photoanode. Furthermore, time‐resolved fluorescence spectroscopy measurements confirm a better electron transfer kinetics for DNA‐modified TiO₂ photoanodes, implying a higher electron transfer rate (k_ET). This work highlights a great contribution for the photoanodes that are linked with DNA molecule, which act as both bridging unit and TTB to control the charge recombination and injection dynamics, and hence, boost the photovoltaic performance in the DSSCs.     

The Effects of Heat Treatment on Some Mechanical Properties of Juvenile Wood and Mature Wood of Eucalyptus grandis

Heat treatment is a well-known method for modifying wood that is applied in different ways, and treatment schedules change from tree to tree. This treatment improves the physical properties of wood but, in general, it reduces the mechanical properties of wood. The effects of heat treatment on the mechanical properties of juvenile and mature wood of the same tree species have not been well-defined. Therefore, we focused our study on the differences in the mechanical properties of juvenile wood and mature wood of Eucalyptus grandis after both were subjected to heat treatment. Wood samples were treated at temperatures of 120, 150, and 180°C for 4, 6, and 8 h. The test results showed that decreases in the mechanical properties of juvenile wood (e.g., modulus of elasticity (MOE), modulus of rupture (MOR), compression strength (CS), and impact bending (IB)) were greater than the decreases that occurred in mature wood that was heat treated at the same conditions.     

ALKYLATION OF BENZENE USING BATCH AND CONTINUOUS FIXED-BED REACTORS

Alkylation reactions of benzene with propylene using heterogeneous catalysts H⁺-β zeolite, MCM-22, and ZSM-5 were studied for their affinity for cumene production. This work focused on the gas-phase reaction using different crystalline catalysts at several temperatures and amounts of reactants using both batch and continuous fixed-bed reactors. The properties of baseline commercial H⁺-β catalysts versus versions modified with Ga, La, and Pt were studied. Quantitative analysis of product mixture was performed by gas chromatography. For the batch reactor, β-zeolite produced the highest cumene yield and selectivity of 72% and 92%, respectively, at 225°C. At this temperature, a benzene:propylene dilution of 7:1 molar ratio was the optimum. For the continuous system, cumene production is favored at lower space velocities, higher benzene-to-propylene ratio, and temperatures close to 225°C. Ga modification of the H⁺-β zeolite significantly enhanced cumene yield in the continuous fixed-bed reactor at 225°C, from 27% of the unmodified β-zeolite to 36% for the Ga-modified one. The life span of modified β-catalysts was studied in the fixed-bed reactor for the first eight hours of reaction.     

Soft Matter Technology at KIT: Chemical Perspective from Nanoarchitectures to Microstructures

Bioinspiration has emerged as an important design principle in the rapidly growing field of materials science and especially its subarea, soft matter science. For example, biological cells form hierarchically organized tissues that not only are optimized and designed for durability, but also have to adapt to their external environment, undergo self‐repair, and perform many highly complex functions. Being able to create artificial soft materials that mimic those highly complex functions will enable future materials applications. Herein, soft matter technologies that are used to realize bioinspired material structures are described, and potential pathways to integrate these into a comprehensive soft matter research environment are addressed. Solutions become available because soft matter technologies are benefitting from the synergies between organic synthesis, polymer chemistry, and materials science.     

Comparison of a sMBR and a CASP system for wastewater reclamation and re-use

The performance of a submerged membrane bioreactor (sMBR) for municipal wastewater reclamation and re-use was compared with that of a current classic activated sludge process (CASP). The average chemical oxygen demand (COD) of CASP effluent was 75 mg/l, while the average COD of sMBR filtrate was 15 mg/l. In general, COD removal was above 98%. However, the best results were obtained at a sludge rentention time (SRT) of 50 days. The total phosphorus (TP) content of the filtrate decreased to a level <1 mg/l under aerobic conditions in which aeration occurred continuously. It was shown that the filtrate TP and orthoposphate (Orto-P) concentrations increased dramatically during the periods of intermittent aeration because phosphorus is released under anoxic conditions. In the CASP effluent, the average TP and Orto-P were 7.9 mg/l and 7.1 mg/l, respectively. The filtrate was free of suspended solids (SS) and total coliform bacteria. The effluent SS in the CASP was 40 mg/l. The turbidity removal in the sMBR reached almost 99%, i.e. generally less than 1 NTU, while the average turbidity of the CASP effluent was almost 15 NTU. The removal of ammonium nitrogen (NH₄⁺-N) in the sMBR was almost 99.8%. In addition, the nitrate concentration in the filtrate decreased to 2.4 mg/l under both aerobic & anoxic conditions. It was shown that both nitrification and denitrification could be successfully reduced through intermittent aeration. Average total Kjeldehl nitrogen (TKN) and NH₄⁺-N in the CASP effluent were 30.2 mg/l and 20 mg/l, respectively, i.e. the nitrification efficiency was 42.9%, and the denitrification value was not available. When these results are compared with those in the CASP, it indicated that the sMBR could be successfully used for reclamation and re-use of municipal wastewater.     

Determination of the quality and purity characteristics of olive oils obtained from different regions of Turkey,depending on climatic changes

Virgin olive oils (VOOs) obtained from olives grown in different regions of Turkey under changing climatic conditions sometimes show different sensory and chemical properties. This study was planned to determine whether these deviations are due to climatic changes or not. For this purpose, five different olive varieties (Ayvalık, Memecik, Gemlik, Nizip Yağlık, Kilis Yağlık) of commercial importance were harvested from the provinces/districts (four different region) where cultivation is intense during the 2017/2018–2020/2021 harvest years. Every year, olive samples were collected from 3 orchards from 13 provinces/districts. One hundred and fifty-six samples were subjected to the purity, quality and sensory analysis. Basic climatic values (average, minimum and maximum temperature, humidity and precipitation) were examined for four consecutive years. All of the examined olive oil samples were determined within the legal limits in terms of fatty acid composition and fatty acid ethyl ester values. However, delta-7-stigmastenol value from the sterol composition was found to be above 0.5% in some samples in all the years studied (total 21 samples). Delta-7-stigmastenol values of olive oil samples varied between 0.16% and 1.14%. Multiple linear regression analysis was applied using a genetic algorithm-based inverse least squares method to determine whether there is a relationship between climate data and delta-7-stigmastenol values. According to this result, it has been determined that the delta-7-stigmastenol value is high when the annual average relative humidity is low and the annual average temperature is high. There is an urgent need to make forward-looking plans due to climate change.     

Improvement of Interfacial Adhesion of Glass Fiber/Epoxy Composite by Using Plasma Polymerized Glass Fibers

This study intends to produce plasma polymer thin films of γ-glycidoxypropyltrimethoxysilane (γ-GPS) on glass fibers in order to improve interfacial adhesion of glass fiber-reinforced epoxy composites. A low frequency (LF) plasma generator was used for the plasma polymerization of γ-GPS on the surface of glass fibers at different plasma powers and exposure times. X-ray photoelectron spectroscopy (XPS) and SEM analyses of plasma polymerized glass fibers were conducted to obtain some information about surface properties of glass fibers. Interlaminar shear strength (ILSS) values and interfacial shear strength (IFSS) of composites reinforced with plasma polymerized glass fiber were evaluated. The ILSS and IFSS values of non-plasma polymerized glass fiber-reinforced epoxy composite were increased 110 and 53%, respectively, after plasma polymerization of γ-GPS at a plasma power of 60 W for 30 min. The improvement of interfacial adhesion was also confirmed by SEM observations of fractured surface of the composites.     

Preparation and Characterization of PVA/PVP Nanofibers as Promising Materials for Wound Dressing

The PVA/PVP, PVA/PVP with 5% and 10% chitosan and PVA/PVP-Iodine fibers were produced via electrospinning technique. Their morphological and chemical characteristics were examined with SEM, TGA, FT-IR, viscometer and four-point probe conductivity measurement apparatus. The addition of chitosan increased the viscosity and the electrical conductivity of the polymer. The increase chitosan contents resulted in the diameters of the fibers smaller than expected. This was attributed to the increase in the viscosity of the solution and the electrical conductivity of the resulting fibers. The DSC results show that iodine was efficiently cross-linked with the polymer, forming an amorphous structure.     

Effect of mechanical and air-particle cleansing protocols of provisional cement on immediate dentin sealing layer and subsequent adhesion of resin composite cement

Immediate dentin sealing (IDS) could avoid contamination of dentin from impression material and provisional cement but prior to final cementation of indirect restorations, removal of the provisional cement may damage the IDS. The objectives of this study were to investigate the effect of mechanical and air-particle cleansing protocols of provisional cement on IDS layer and subsequent adhesion of resin composite cement. The cuspal dentin surfaces of human third molars (N = 21, n_quadrant = 84) were exposed by a low-speed diamond saw under water cooling and conditioned with an adhesive system based on the three-step etch and rinse technique (OptiBond FL). Provisional cement (Freegenol) was applied on each specimen. They were then randomly divided into six subgroups where the provisional cement was removed either by (1) air-borne particle abrasion with 50-μm Al₂O₃ particles at 2 bar (AL2), (2) air-borne particle abrasion with 50-μm Al₂O₃ particles at 3.5 bar (AL3.5), (3) air-borne particle abrasion with 30-μm SiO₂ particles at 2 bar (SL2), (4) air-borne particle abrasion with 30-μm SiO₂ particles at 3.5 bar (SL3.5), (5) prophylaxy paste (Cleanic) (PP) or (6) pumice-water slurry (PW) at 1500 rpm for 15 s. The dentin surface on each tooth was assigned to four quadrants and each quadrant received the cleansing methods in a clockwise sequence. The non-contaminated and non-cleansed teeth acted as the control (C). Two separate teeth, contaminated and cleansed according to six cleansing protocols, were allocated for scanning electron microscopy (SEM) analysis (×2000). The dentin surfaces in each quadrant received resin composite luting cement (Variolink II, Ivoclar Vivadent) incrementally in a polyethylene mould (diameter: 1 mm²; height: 4 mm) and photopolymerized. The specimens were stored in distilled water for 24 h at 37 °C until the testing procedures and then shear force was applied to the adhesive interface until failure occurred in a universal testing machine (0.5 mm/min). Microshear bond (μSBS) was calculated by dividing the maximum load (N) by the bonding surface area of the resin cement. Failure types were analysed using optical microscope and SEM. Data (MPa) were analysed using one-way ANOVA (α = 0.05). Two-parameter Weibull distribution values including the Weibull modulus, scale (m) and shape (₀), values were calculated. Mean μSBS results (MPa) showed a significant difference between the experimental groups (p = 0.011) and were in a descending order as follows: C (8 ± 2.3)^a < AL2 (6.7 ± 2.4)^b < PP (6.9 ± 2)^b < PW (6.5 ± 2.1)^b < AL3.5 (5.8 ± 1.1)^b < SL2 (5.3 ± 1)^b < SL3.5 (5.2 ± 1)^b. Failure types were predominantly mixed failure type between the dentin and the adhesive resin which is a combination of adhesive and cohesive failures in the adhesive resin. Cohesive failure in the dentin was not observed in any of the groups. Weibull distribution presented lower shape (₀) for C (3.9), AL2 (3.2), PP (3.5) and PW (3.6). SEM analysis showed rough surfaces especially in the air-abraded groups whereas mechanical cleansing methods presented smoother surfaces and partially covered by particle remnants all of which occluded the dentin tubuli.     

Analysis of structural,morphological alterations,wettability characteristics and adhesion to enamel after various surface conditioning methods

Minimal invasive dental reconstructions and orthodontic appliances are bonded to enamel without removing the enamel with rotating instruments but the top layer of enamel may be partially aprismatic and impair adhesion. The objectives of this study were to investigate the effect of mechanical surface conditioning methods for removing enamel on its structural, morphological alterations, wettability characteristics, and adhesion of resin-based cement to the conditioned surfaces. Maxillary human incisors (N = 40, n_quadrant = 160) were obtained and coronal sections were embedded in acrylic with their labial surfaces exposed. The teeth were randomly divided into four groups and the enamel surface of each tooth was divided into four quadrants. The surfaces were conditioned in a clockwise manner by one of the following methods: (1) Non-conditioned enamel acted as the control group (C); (2) Silicone-coated disk (Sof-Lex disc, Black, 3 M ESPE) (SD); (3) Diamond bur at slow speed (DB) and (4) Airborne particle abrasion (50 μm Al₂O₃, 2 bar, 5 s) (AA). Surface roughness was measured at each quadrant using a non-contact digital profilometer and contact angle measurements were performed using a goniometer. Enamel surfaces were then etched with 37% H₃PO₄ for 60 s and roughness and wettability measurements were repeated. The enamel surfaces in each quadrant received resin composite luting cement (Variolink II, Ivoclar Vivadent) incrementally in a polyethylene mold (diameter: 1 mm²; height: 4 mm) and photopolymerized. The specimens were stored in distilled water for 24 h at 37 °C until the testing procedures and then shear force was applied to the adhesive interface until failure occurred in a Universal Testing Machine (0.5 mm/min). Microshear bond (μSBS) was calculated by dividing the maximum load (N) by the bonding surface area of the resin cement. Representative enamel surfaces were analyzed under the scanning electron microscope (SEM) (x5000) to assess the surface morphology. Failure types were analyzed using optical microscope and SEM. Data (MPa) were analyzed using one-way ANOVA and Tukey`s test for each parameter and Linear model for group comparisons (α = 0.05). Surface conditioning method significantly affected the adhesion results (p < 0.001), surface roughness (p = 0.017), and contact angle (p < 0.001). Interaction terms were significant (p > 0.05). AA (338 ± 182) created significantly higher surface roughness compared to SD (308 ± 180) and DB (242 ± 197) (p < 0.05). After etching with 37% H₃PO₄, DB (307 ± 223) resulted in significantly lower roughness than those of SD (385 ± 173) and AA (414 ± 193) (p < 0.05). AA (40 ± 11) delivered significantly lower contact angle compared to those of SD (61 ± 9) and DB (59 ± 10). After etching with 37% H₃PO₄, AA (42 ± 10) and DB (50 ± 10) presented the lowest contact angle (p < 0.05). Mean μSBS results (MPa) showed significant difference between the experimental groups (p = 0.011) and were in descending order as follows: DB (20 ± 8)^a?a b < C (12 ± 5)^b. Failure types were predominantly mixed failure type between the enamel and the resin cement with more than half of the resin remained on the enamel surface (32 to 33 out of 40) in all groups. Cohesive failure in the enamel was not observed in any of the groups. SEM analysis showed that AA group leaves abundant particles on the enamel surface and after DB and AA, etching could not remove the particles completely and expose the enamel prisms.