Insights on Antioxidant Assays for Biological Samples Based on the Reduction of Copper Complexes—The Importance of Analytical Conditions

Total antioxidant capacity assays are recognized as instrumental to establish antioxidant status of biological samples, however the varying experimental conditions result in conclusions that may not be transposable to other settings. After selection of the complexing agent, reagent addition order, buffer type and concentration, copper reducing assays were adapted to a high-throughput scheme and validated using model biological antioxidant compounds of ascorbic acid, Trolox (a soluble analogue of vitamin E), uric acid and glutathione. A critical comparison was made based on real samples including NIST-909c human serum certified sample, and five study samples. The validated method provided linear range up to 100 µM Trolox, (limit of detection 2.3 µM; limit of quantification 7.7 µM) with recovery results above 85% and precision <5%. The validated developed method with an increased sensitivity is a sound choice for assessment of TAC in serum samples.     

Strong Hydrogen Bonds in Acetylenedicarboxylic Acid Dihydrate

Acetylenedicarboxylic acid dihydrate (ADAD) represents a complex with strong hydrogen bonding between the carboxylic OH and the water molecule. An X-ray re-examination of the ADAD crystal structure confirms the O^…O distance of the short hydrogen bonds, and clearly shows different bond lengths between the two oxygen atoms with respect to the carbon atom in the carboxyl group, indicating a neutral structure for the complex. The neutral structure was also confirmed by vibrational spectroscopy, as no proton transfer was observed. The diffraction studies also revealed two polymorph modifications: room temperature (α) and low temperature (β), with a phase transition at approximately 4.9 °C. The calculated vibrational spectra are in satisfactory agreement with the experimental spectra. A comparison of the structure and the vibrational spectra between the ADAD and the oxalic acid dihydrate reveals some interesting details. The crystal structures of both crystal hydrates are almost identical; only the O^…O distances of the strongest hydrogen bonds differ by 0.08 Å. Although it was expected that a larger O^…O spacing in the ADAD crystal may significantly change the infrared and Raman spectra, especially for the frequency and the shape of the acidic OH stretching vibration, both the shape and frequency are almost identical, with all subpeaks topped on the broad OH stretching vibration. The O^…O distance dependent are only in- and out-of-plane OH deformations modes. The presence of polarons due to the ionized defects was not observed in the vibrational spectra of ADAD. Therefore, the origin of the broad OH band shape was explained in a similar way to the acid dimers. The anharmonicity of a potential enhances the coupling of the OH stretching with the low-frequency hydrogen bond stretching, which, in addition to the Fermi resonance, structures the band shape of the OH stretching. The fine structure found as a superposition of a broad OH stretching is attributed to Davydov coupling.     

Supramolecular Hydrogen Bonding Assembly from Non-Coplanar Aromatic Tetra-1H-Pyrazoles with Crystallization-Induced Emission (CIE)

Here, we report a design strategy for constructing supramolecular organic frameworks by introducing ¹H-pyrazole groups to aromatic cores as non-coplanar molecules to form diverse supramolecular assemblies through multiple ¹H-pyrazole [N−H···N] hydrogen bonds as well as other weak interactions. The new supramolecular organic frameworks displayed interesting crystallization-induced emission (CIE) behavior.     

Hydrogen isotope dissolution and release behavior in Y-doped BaCeO3

Oxides having a perovskite structure are known to exhibit good proton conductivity in a high-temperature region, which makes them potential candidates in the tritium recovery and purification system of the electrochemical devices of fusion reactors such as hydrogen pumps, hydrogen sensors, and tritium monitoring systems. But the dissolution of hydrogen into the proton conductor and its release behavior is not well known yet. In this study, the dissolution and release behavior of hydrogen was investigated in BaCe_0.9Y_0.1O_3−α proton conductor by exposing deuterium gas (D₂) and heavy water vapor (D₂O) at 600 or 700°C for 5 h. The dissolved deuterium amount in the sample was measured using a temperature-programmed desorption analysis (TDS) method. The relationship between the amount of deuterium dissolved in the sample with the exposure pressure was also investigated. At room temperature (RT), the diffusivity of hydrogen (e.g., deuterium) was calculated from the change of the amount of residual hydrogen in the exposed sample due to the change of storage time. The Tritium Migration Analysis Program, Version 4 (TMAP4) simulation code was used to simulate and compare the experimental value of the obtained diffusivity. Although diffusivity at RT has not been reported in the past, the diffusivity is close to the extrapolation value of the literature data. From the comparison of this research results with literature, it may consider that the dominant diffusion mechanism does not change regardless of the temperature range.     

Resistive Switching Characteristic Improvement in a Single-Walled Carbon Nanotube Random Network Embedded Hydrogen Silsesquioxane Thin Films for Flexible Memristors

In this study, we evaluated the improved memristive switching characteristics of hydrogen silsesquioxane (HSQ) nanocomposites embedded with a single-walled carbon nanotube (SWCNT) random network. A low-temperature solution process was implemented using a flexible memristor device on a polyethylene naphthalate (PEN) substrate. The difference in the resistive switching (RS) behavior due to the presence of the SWCNT random network was analyzed by the current transport mechanism. Such a random network not only improves the RS operation but also facilitates a stable multilevel RS performance. The multiple-resistance states exhibited highly reliable nonvolatile retention properties over 10⁴ s at room temperature (25 °C) and at a high temperature (85 °C), showing the possibility of an analog synaptic weight modulation. Consequently, the gradual weight potentiation/depression was realized through 3 × 10² synaptic stimulation pulses. These findings suggest that the embedded SWCNT random network can improve the synaptic weight modulation characteristics with high stability for an artificial synapse and hence can be used in future neuromorphic circuits.     

Hydrogen Bonds,Topologies, Energy Frameworks and Solubilities of Five Sorafenib Salts

Sorafenib (Sor) is an oral multi-kinase inhibitor, but its water solubility is very low. To improve its solubility, sorafenib hydrochloride hydrate, sorafenib hydrobromide and sorafenib hydrobromide hydrate were prepared in the mixed solvent of the corresponding acid solution, and tetrahydrofuran (THF). The crystal structures of sorafenib hydrochloride trihydrate (Sor·HCl.3H₂O), 4-(4-{3-[4-chloro-3-(trifluoro-methyl)phenyl]ureido}phenoxy)-2-(N-methylcarbamoyl) pyridinium hydrochloride trihydrate, C₂₁H₁₇ClF₃N₄O₃⁺·Cl⁻.3H₂O (I), sorafenib hydrochloride monohydrate (Sor·HCl.H₂O), C₂₁H₁₇ClF₃N₄O₃⁺·Cl⁻.H₂O (II), its solvated form (sorafenib hydrochloride monohydrate monotetrahydrofuran (Sor·HCl.H₂O.THF), C₂₁H₁₇ClF₃N₄O₃⁺·Cl⁻.H₂O.C₄H₈O (III)), sorafenib hydrobromide (Sor·HBr), 4-(4-{3-[4-chloro-3-(trifluoro-methyl)phenyl]ureido}phenoxy)-2-(N-methylcarbamoyl) pyridinium hydrobromide, C₂₁H₁₇ClF₃N₄O₃⁺·Br⁻ (IV) and sorafenib hydrobromide monohydrate (Sor·HBr.H₂O), C₂₁H₁₇ClF₃N₄O₃⁺·Br⁻.H₂O (V) were analysed. Their hydrogen bond systems and topologies were investigated. The results showed the distinct roles of water molecules in stabilizing their crystal structures. Moreover, (II) and (V) were isomorphous crystal structures with the same space group P2₁/n, and similar unit cell dimensions. The predicted morphologies of these forms based on the BFDH model matched well with experimental morphologies. The energy frameworks showed that (I), and (IV) might have better tabletability than (II) and (V). Moreover, the solubility and dissolution rate data exhibited an improvement in the solubility of these salts compared with the free drug.     

Enrichment of Secondary Wastewater Sludge for Production of Hydrogen from Crude Glycerol and Comparative Evaluation of Mono-, Co- and Mixed-Culture Systems

Anaerobic digestion using mixed-culture with broader choice of pretreatments for hydrogen (H₂) production was investigated. Pretreatment of wastewater sludge by five methods, such as heat, acid, base, microwave and chloroform was conducted using crude glycerol (CG) as substrate. Results for heat treatment (100 °C for 15 min) showed the highest H₂ production across the pretreatment methods with 15.18 ± 0.26 mmol/L of medium at 30 °C in absence of complex media and nutrient solution. The heat-pretreated inoculum eliminated H₂ consuming bacteria and produced twice as much as H₂ as compared to other pretreatment methods. The fermentation conditions, such as CG concentration (1.23 to 24 g/L), percentage of inoculum size (InS) (1.23% to 24% v/v) along with initial pH (2.98 to 8.02) was tested using central composite design (CCD) with H₂ production as response parameter. The maximum H₂ production of 29.43 ± 0.71 mmol/L obtained at optimum conditions of 20 g/L CG, 20% InS and pH 7. Symbiotic correlation of pH over CG and InS had a significant (p-value: 0.0011) contribution to H₂ production. The mixed-culture possessed better natural acclimatization activity for degrading CG, at substrate inhibition concentration and provided efficient inoculum conditions in comparison to mono- and co-culture systems. The heat pretreatment step used across mixed-culture system is simple, cheap and industrially applicable in comparison to mono-/co-culture systems for H₂ production.     

CdS/TiO2复合纳米粒子的制备及其产氢性能研究

采用化学沉淀法制备了CdS包覆TiO2（CdS/TiO2）复合纳米粒子,利用XRD、TEM、SEM、UV-vis吸收光谱等对其进行了表征分析,并以可见光分解水制氢为探针反应考察了复合纳米粒子的活性。结果表明,CdS/TiO2 复合纳米粒子的颗粒大小约为40nm,TiO2 以锐钛矿型存在,CdS以六方相存在;复合纳米粒子的吸收光谱较TiO2 发生“红移”,大幅拓宽了对可见光区的吸收范围。光解水制氢实验表明,CdS/TiO2 复合纳米粒子具有良好的可见光释氢活性和光学稳定性。     

Influence of Hydrogenation on Morphology,Chemical Structure and Photocatalytic Efficiency of Graphitic Carbon Nitride

In this contribution, the effect of hydrogenation conditions atmosphere (temperature and time) on physicochemical properties and photocatalytic efficiency of graphitic carbon nitride (g-C₃N₄, gCN) was studied in great details. The changes in the morphology, chemical structure, optical and electrochemical properties were carefully investigated. Interestingly, the as-modified samples exhibited boosted photocatalytic degradation of Rhodamine B (RhB) with the assistance of visible light irradiation. Among modified gCN, the sample annealed at 500 °C for 4 h (500-4) in H₂ atmosphere exhibited the highest photocatalytic activity—1.76 times higher compared to pristine gCN. Additionally, this sample presented high stability and durability after four cycles. It was noticed that treating gCN with hydrogen at elevated temperatures caused the creation of nitrogen vacancies on gCN surfaces acting as highly active sites enhancing the specific surface area and improving the mobility of photogenerated charge carriers leading to accelerating the photocatalytic activity. Therefore, it is believed that detailed optimization of thermal treatment in a hydrogen atmosphere is a facile approach to boost the photoactivity of gCN.     

Prototype Development of a Temperature-Sensitive High-Adhesion Medical Tape to Reduce Medical-Adhesive-Related Skin Injury and Improve Quality of Care

Medical adhesives are used to secure wound care dressings and other critical devices to the skin. Without means of safe removal, these stronger adhesives are difficult to painlessly remove from the skin and may cause medical-adhesive-related skin injuries (MARSI), including skin tears and an increased risk of infection. Lower-adhesion medical tapes may be applied to avoid MARSI, leading to device dislodgement and further medical complications. This paper outlines the development of a high-adhesion medical tape designed for low skin trauma upon release. By warming the skin-attached tape for 10–30 s, a significant loss in adhesion was achieved. A C14/C18 copolymer was developed and combined with a selected pressure-sensitive adhesive (PSA) material. The addition of 1% C14/C18 copolymer yielded the largest temperature-responsive drop in surface adhesion. The adhesive film was characterized using AFM, and distinct nanodomains were identified on the exterior surface of the PSA. Our optimized formulation yielded 67% drop in adhesion when warmed to 45 °C, perhaps due to melting nanodomains weakening the adhesive–substrate boundary layer. Pilot clinical testing resulted in a significant decrease in pain when a heat pack was used for removal, giving an average pain reduction of 66%.     

Evaluating the Effects of Subnormothermic Perfusion with AP39 in a Novel Blood-Free Model of Ex Vivo Kidney Preservation and Reperfusion

The use of blood for normothermic and subnormothermic kidney preservation hinders the translation of these approaches and promising therapeutics. This study evaluates whether adding hydrogen sulfide donor AP39 to Hemopure, a blood substitute, during subnormothermic perfusion improves kidney outcomes. After 30 min of renal pedicle clamping, porcine kidneys were treated to 4 h of static cold storage (SCS-4 °C) or subnormothermic perfusion at 21 °C with Hemopure (H-21 °C), Hemopure + 200 nM AP39 (H200nM-21 °C) or Hemopure + 1 µM AP39 (H1µM-21 °C). Then, kidneys were reperfused with Hemopure at 37 °C for 4 h with metabolic support. Perfusate composition, tissue oxygenation, urinalysis and histopathology were analyzed. During preservation, the H200nM-21 °C group exhibited significantly higher urine output than the other groups and significantly higher tissue oxygenation than the H1µM-21 °C group at 1 h and 2h. During reperfusion, the H200nM-21 °C group exhibited significantly higher urine output and lower urine protein than the other groups. Additionally, the H200nM-21 °C group exhibited higher perfusate pO₂ levels than the other groups and significantly lower apoptotic injury than the H-21 °C and the H1µM-21 °C groups. Thus, subnormothermic perfusion at 21 °C with Hemopure + 200 nM AP39 improves renal outcomes. Additionally, our novel blood-free model of ex vivo kidney preservation and reperfusion could be useful for studying other therapeutics.     

Hydrogen concentration in water from an Alkali–Ion–Water electrolyzer having a platinum-electroplated titanium electrode

The supersaturated concentration of hydrogen in electrolyzed water obtained from a flow-type electrolytic cell was studied under various electrolysis conditions. The degree of supersaturation was found to decrease as the solution supply rate to the cell increased. The ratio of observed hydrogen concentration to the theoretical hydrogen concentration obtained from the electrochemical equivalent, as calculated from the transfer of charge in the cell, was found to increase with the solution supply rate. The concentration of hydrogen in solution has a maximum at a current density of approximately 0.3 A dm^–2. This maximum was found to be independent of the flow rate, indicating that the hydrogen concentration is related to both the diffusion of dissolved hydrogen from the electrode surface to the bulk solution and hydrogen bubble growth.     

Sorption and Magnetic Properties of Oxalato-Based Trimetallic Open Framework Stabilized by Charge-Assisted Hydrogen Bonds

We report a new structure of {[Co(bpy)₂(ox)][{Cu₂(bpy)₂(ox)}Fe(ox)₃]}_n·8.5nH₂O NCU-1 presenting a rare ladder topology among oxalate-based coordination polymers with anionic chains composed of alternately arranged [Cu₂(bpy)₂(ox)]²⁺ and [Fe(ox)₃]³⁻ moieties. Along the a axis, they are separated by Co(III) units to give porous material with voids of 963.7 ų (16.9% of cell volume). The stability of this structure is assured by a network of stacking interactions and charge-assisted C-H…O hydrogen bonds formed between adjacent chains, adjacent cobalt(III) units, and alternately arranged cobalt(III) and chain motifs. The soaking experiment with acetonitrile and bromobenzene showed that water molecules (8.5 water molecules dispersed over 15 positions) are bonded tightly, despite partial occupancy. Water adsorption experiments are described by a D’arcy and Watt model being the sum of Langmuir and Dubinin–Serpinski isotherms. The amount of primary adsorption sites calculated from this model is equal 8.2 mol H₂O/mol, being very close to the value obtained from the XRD experiments and indicates that water was adsorbed mainly on the primary sites. The antiferromagnetic properties could be only approximately described with the simple Cu^II-ox-Cu^II dimer using H = −J·S₁·S₂, thus, considering non-trivial topology of the whole Cu-Fe chain, we developed our own general approach, based on the semiclassical model (SC) and molecular field (MF) model, to describe precisely the magnetic superexchange interactions in NCU-1. We established that Cu(II)-Cu(II) coupling dominates over multiple Cu(II)-Fe(III) interactions, with J_CuCu = −275(29) and J_CuFe = −3.8(1.6) cm⁻¹ and discussed the obtained values against the literature data.     

Gas-Transport Characteristics of PdCu–Nb–PdCu Membranes Modified with Nanostructured Palladium Coating

A method for obtaining composite gas-diffusion PdCu–Nb–PdCu membranes modified with a nanostructured crystalline coating was developed to increase the performance of Nb-based membranes. A modifying functional layer with a controlled size and composition was synthesized by electrochemical deposition, which made it possible to determine a certain geometric shape for palladium nanocrystallites. Developed PdCu–Nb–PdCu membranes have demonstrated flux values up to 0.232 mmol s⁻¹ m⁻² in the processes of diffusion purification of hydrogen at 400 °C. A very significant difference in the hydrogen fluxes through the modified and non-modified composite PdCu–Nb–PdCu membranes reached 1.73 times at the lower threshold temperature of 300 °C. Cu doping of protective layer did not affect the selective properties of the membranes, which was confirmed by the obtained high selectivity values up to 1323, and made it possible to reduce the noble metal content. The research data indicate that the modification of the membrane surface significantly accelerates the hydrogen transfer process at sufficiently low temperatures due to the acceleration of dissociative–associative processes on the surface. The reported approach demonstrates new possibilities for creating productive and cost-efficient membranes based on niobium.     

制氢技术研究进展及在燃料电池中的应用前景

分析了当前能源现状和形势,并对氢的特点、制氢技术的新近研究进展进行了阐述。氢能作为一种很有应用前景的载能体,已得到越来越广泛的研究和应用。在化学制氢、电解水制氢、生物制氢这3种制氢模式中,化学制氢仍是近期主要的制氢方式,其中催化重整制氢仍然是大规模制氢的主流,随着燃料电池这一环境友好的发电方式在技术上的不断突破,许多其他的制氢技术也得到了迅速的发展,并将伴随着燃料电池、氢燃料发动机等技术的发展和应用,一同步入氢能时代。     

镍纳米管的制备及电化学储氢性能

本文以多孔氧化铝(AAO)为模板,采用电化学沉积法制备了镍纳米管,通过透射电镜(TEM),能谱仪(EDX),选区电子衍射图(SAED)对镍纳米管的形貌、微观结构及组成进行了表征。并将所制备的镍纳米管制成微电极,用循环伏安法测试了其电化学储氢性能。结果表明,所制备的镍纳米管管径约20nm,管长可达微米级,且相比于镍粉,镍纳米管的电化学储氢性能更好。     

Flavonoid and Phenolic Acids Content and In Vitro Study of the Potential Anti-Aging Properties of Eutrema japonicum (Miq.) Koidz Cultivated in Wasabi Farm Poland

Skin aging is a natural, unavoidable, and complex process caused by oxidative stress. As a consequence, it leads to an increase in the activation of extracellular matrix disruption enzymes and DNA damage. The search for natural sources that inhibit these mechanisms can be a good approach to prevent skin aging. The purpose of our study was to evaluate the composition of flavonoids and phenolic acids in the extracts obtained from the flowers, roots, and leaves of Eutrema japonicum cultivated in Poland. Then, the resultant extracts were subjected to an assessment of antioxidant, anti-collagenase, anti-elastase, anti-hyaluronidase, antibacterial, and cytotoxic properties. It was demonstrated that the extract from the flowers had the highest content of flavonoid glycosides (17.15 mg/g DE). This extract showed the greatest antioxidant, anti-collagenase, anti-elastase, and anti-hyaluronidase activities compared to the other samples. Importantly, the collagenase inhibitory activity of this extract (93.34% ± 0.77%) was better than that of positive control epigallocatechin gallate (88.49% ± 0.45%). An undeniable advantage of this extract was also to possess moderate antibacterial properties and no cytotoxicity towards normal human skin fibroblasts. Our results suggest that extracts from E. japonicum flowers may be considered as a promising antiaging compound for applications in cosmetic formulations.     

Ferromagnetism and optical properties of La1???x Al x FeO3 nanopowders

La_{1 − x} Al _x FeO₃ (x = 0.0, 0.05, 0.1, 0.2, 0.3, 0.4, and 0.5) nanopowders were prepared by polymerization complex method. All prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), and UV-vis spectrophotometry (UV-vis). The magnetic properties were investigated using a vibrating sample magnetometer (VSM). The X-ray results of all samples show the formation of an orthorhombic phase with the second phase of α-Fe₂O₃ in doped samples. The crystallite sizes of nanoparticles decreased with increasing Al content, and they are found to be in the range of 58.45 ± 5.90 to 15.58 ± 4.64 nm. SEM and TEM images show the agglomeration of nanoparticles with average particle size in the range of 60 to 75 nm. The FT-IR spectra confirm the presence of metal oxygen bonds of O-Fe-O and Fe-O in the FeO₆ octahedra. The UV-vis spectra show strong absorption peaks at approximately 285 nm, and the calculated optical band gaps are found to be in the range of 2.05 to 2.09 eV with increasing Al content. The M-H loop of the pure sample is antiferromagnetic, whereas those of the doped samples tend to be ferromagnetic with increasing Al content. The magnetization, remanent magnetization, and coercive field of the Al-doped sample with x = 0.5 are enhanced to 1.665 emu/g, 0.623 emu/g, and 4,087.0 Oe, respectively.