RSC Advances

Liu, ChangSheng; Xue, ShaoLin

doi: 10.1039/d2ra08309dpmid: 36926296

Herein, a CuSe(Cu2Se) yolk–shell structure (CC) was synthesized when room temperature was 25 degree Celsius using Cu2O as a soft template, and the g-C3N4/CuSe(Cu2Se) heterojunction (CC-G) was formed by coupling appropriate amounts of g-C3N4 in the selenization process to provide a novel, green, economical, and efficient photo-Fenton catalytic material. Photo-Fenton degradation experiments proved that in the presence of hydrogen peroxide (H2O2), a small amount of g-C3N4 hybridization on Cu-based Fenton catalysts significantly improved methylene blue (MB) degradation. The suitable amount of g-C3N4 hybridization was selected according to the degradation efficiency. The mass of g-C3N4 constituted 20% of the mass of the Cu2O soft template. The composite material prepared using this combination (CC-G-20) exhibited the best MB degradation performance. The MB degradation efficiency in the CC-G-20/H2O2/visible light system was almost 98.3% after 60 min, which is higher than those of the parent materials (g-C3N4, 12.7%; CC, 58.6%) and had cyclic stability. The catalytic system can also stably degrade MB under dark conditions, where the MB degradation was almost 82% after 60 min. The heterojunction prevented excessive electrons and holes (e− and h+) recombination, stabilizing the reactive active substance of hydroxyl in the photo-Fenton-like catalytic system. Electron paramagnetic resonance and photoluminescence experiments confirmed this inference.

Luo, Liang; Zhou, Bao; Liu, Zhenzhen; Zhao, Qirong; Wang, Chao; Duan, Zhuoqi; Xie, Zaixin; Yang, Xiaobo; Hu, Yongmao

doi: 10.1039/d2ra04659hpmid: 36926303

Theoretically, cuprous oxide (Cu2O) is a particularly excellent potential material, for the hole transport layer (HTL) of perovskite solar cells (PSCs). However, the photoelectric conversion efficiency (PCE) of its experimental samples is still not ideal. The main reasons for this include the material, and inherent and interface defects of Cu2O, but this can be improved by doping. In this research, Te- and Se/Te-doped Cu2O were experimentally and numerically studied to check the improvement of the material and interface properties. It was found that, for both the electrical and optical properties, the Se/Te-doped Cu2O performed considerably better than that which had been Te-doped and the pure Cu2O. Compared with the pure Cu2O thin film, the carrier mobility of the Se/Te-doped Cu2O thin film is improved from 60 cm2 V−1 s−1 to 1297 cm2 V−1 s−1, and the bandgap changed from 2.05 eV to 1.88 eV. According to the results calculated using solar cell simulation software SCAPS, the cell efficiency of the Se/Te-doped Cu2O is improved by 22% when compared to that of pure Cu2O. This efficiency can be further improved to 34% by optimizing the thickness of the Se/Te-doped Cu2O thin film and the defect density of states between the material interfaces.

Saladin, Siriel; D'Aronco, Sara; Ingram, Gwyneth; Giorio, Chiara

doi: 10.1039/d2ra07166epmid: 36926302

The plant cuticle covers the plant's entire aerial surface and acts as the outermost protective layer. Despite being crucial for the survival of plants, surprisingly little is known about its biosynthesis. Conventional analytical techniques are limited to the isolation and depolymerization of the polyester cutin, which forms the cuticular scaffold. Although this approach allows the elucidation of incorporated cutin monomers, it neglects unincorporated metabolites participating in cutin polymerization. The feasibility of a novel approach is tested for in situ analysis of unpolymerized cuticular metabolites to enhance the understanding of cuticle biology. Intact cotyledons of Brassica napus and Arabidopsis thaliana seedlings are immersed in organic solvents for 60 seconds. Extracts are analyzed using high-resolution direct infusion mass spectrometry. A variety of different diffusion routes of plant metabolites across the cuticle are discussed. The results reveal different feasibilities depending on the research question and cuticle permeabilities in combination with the analyte's polarity. Especially hydrophilic analytes are expected to be co-located in the cell wall beneath the cuticle causing systematic interferences when comparing plants with different cuticle permeabilities. These interferences limit data interpretation to qualitative rather than quantitative comparison. In contrast, quantitative data evaluation is facilitated when analyzing cuticle-specific metabolites or plants with similar cuticle permeabilities.

Switzer, Hannah J.; Howard, Christina A.; Halonski, John F.; Peairs, Emily M.; Smith, Nolan; Zamecnik, Maddy P.; Verma, Sanjana; Young, Douglas D.

doi: 10.1039/d3ra00392bpmid: 36926306

A carboxylesterase derived from Sulfolobus solfataricus P1 was immobilized onto an epoxy-activated Sepharose resin via non-canonical amino acids. The immobilized enzyme exhibited heightened performance in organic solvents, recyclability, and stability at room temperature for over two years. The incorporation of a non-canonical amino acid afforded a high degree of control over the bioorthogonal immobilization reaction. These results indicate that the specificity conferred by genetic code expansion produces advantages in protein immobilization and broadens the utility of such proteins to non-biological settings.

Nie, Lei; Wei, Qianqian; Li, Jingyu; Deng, Yaling; He, Xiaorui; Gao, Xinyue; Ma, Xiao; Liu, Shuang; Sun, Yanfang; Jiang, Guohua; Okoro, Oseweuba Valentine; Shavandi, Amin; Jing, Shengli

doi: 10.1039/d2ra07195apmid: 36926300

Conductive hydrogels are platforms recognized as constituting promising materials for tissue engineering applications. This is because such conductive hydrogels are characterized by the inherent conductivity properties while retaining favorable biocompatibility and mechanical properties. These conductive hydrogels can be particularly useful in enhancing wound healing since their favorable conductivity can promote the transport of essential ions for wound healing via the imposition of a so-called transepithelial potential. Other valuable properties of these conductive hydrogels, such as wound monitoring, stimuli-response etc., are also discussed in this study. Crucially, the properties of conductive hydrogels, such as 3D printability and monitoring properties, suggest the possibility of its use as an alternative wound dressing to traditional dressings such as bandages. This review, therefore, seeks to comprehensively explore the functionality of conductive hydrogels in wound healing, types of conductive hydrogels and their preparation strategies and crucial properties of hydrogels. This review will also assess the limitations of conductive hydrogels and future perspectives, with an emphasis on the development trend for conductive hydrogel uses in wound dressing fabrication for subsequent clinical applications.

Dung, Tran Phuong; Chihaia, Viorel; Son, Do Ngoc

doi: 10.1039/d2ra08007apmid: 36926297

The activity of the oxygen reduction reaction (ORR) on the cathode is one of the dominant factors in the performance of proton exchange membrane fuel cells. Iron porphyrin has low cost, environmental benignity, and maximum efficiency of metal usage. Therefore, this material can be a promising single-atomic metal dispersion catalyst for fuel cell cathodes. The variation of functional groups was proven to effectively modify the activity of the ORR on the iron porphyrin. However, the influences of functional groups on the mechanisms of the ORR remain ambiguous. This work paid attention to the substitution of carboxyl (–COOH), methyl (–CH3), and amino (–NH2) functional groups at the meso positions of the porphyrin ring. By using van der Waals density functional theory (vdW-DF) calculations, we found that the ORR mechanisms can follow the associative and dissociative pathways, respectively. The Gibbs free energy diagrams revealed that the rate-limiting step occurs at the second hydrogenation step for the first pathway and the O2 dissociation step for the second pathway for all considered functional groups. The thermodynamic energy barrier at the rate-limiting step was found to be in the following order: porphyrin–(CH3)4 < porphyrin–(NH2)4 < original porphyrin < porphyrin–(COOH)4 for the associative mechanism and porphyrin–(NH2)4 < porphyrin–(CH3)4 < porphyrin–(COOH)4 < original porphyrin for the dissociative pathway. The findings suggested that porphyrin–(CH3)4 and porphyrin–(NH2)4 should be the best choices among the considered substrates for the oxygen reduction reaction. Furthermore, the interaction between the ORR intermediates and the substrates was attributed to the resonance of the dz2, dxz, and dyz components of the Fe d orbital and the C and N p orbitals of the substrates with the p orbitals of the oxygen atoms in the intermediates. Finally, the nature of the interaction between the adsorbent and adsorbate was charge transfer.

Xie, Xiaoyu; Wang, Wang; Chen, Haoran; Yang, Run; Wu, Han; Gan, Dechao; Li, Bin; Kong, Xianggui; Li, Qiqing; Chang, Yulei

doi: 10.1039/d3ra00716bpmid: 36926301

Lanthanide-doped upconversion nanoparticles (UCNPs) have attracted great attention in temperature sensing because of their widespread thermal quenching effect (TQE), a phenomenon in which luminescence intensity decreases as the temperature increases. However, enhancing the TQE of activated ions without changing the dopants or the host is still challenging. Herein, Yb3+ and Er3+ codoped UCNPs in a cubic CaGdF5 host were synthesized by a coprecipitation method for optical temperature sensing. Compared with the homogeneous shell (CaGdF5), those heterogeneous (CaF2) shelled UCNPs exhibited stronger upconversion luminescence (UCL) due to the significantly reduced multiphonon nonradiative relaxation. Further, we investigated the effects of homogeneous and heterogeneous shells on TQE. The relationship between the intensity ratio of the green emission bands of Er3+ ions (2H11/2 → 4I15/2 and 4S3/2 → 4I15/2) and temperature are obtained for these two core@shell UCNPs. The results demonstrated that the UCNPs with CaF2 shells are more sensitive to temperature in the 200–300 K. The maximum thermal sensitivity of CaGdF5:Yb,Er@CaF2 could reach 2.2% K−1 at 200 K. These results indicate that the heterogeneous core@shell UCNPs are promising for use as optical temperature sensors.

Eivazzadeh-Keihan, Reza; Pajoum, Zeinab; Aliabadi, Hooman Aghamirza Moghim; Mohammadi, Adibeh; Kashtiaray, Amir; Bani, Milad Salimi; Pishva, Banafshe; Maleki, Ali; Heravi, Majid M.; Mahdavi, Mohammad; Ziabari, Elaheh Ziaei

doi: 10.1039/d3ra00612cpmid: 36926298

Herein, a multifunctional nanobiocomposite was designed for biological application, amongst which hyperthermia cancer therapy application was specifically investigated. This nanobiocomposite was fabricated based on chitosan hydrogel (CS), silk fibroin (SF), water-soluble polymer polyvinyl alcohol (PVA) and iron oxide magnetic nanoparticles (Fe3O4 MNPs). CS and SF as natural compounds were used to improve the biocompatibility, biodegradability, adhesion and cell growth properties of the nanobiocomposite that can prepare this nanocomposite for the other biological applications such as wound healing and tissue engineering. Since the mechanical properties are very important in biological applications, PVA polymer was used to increase the mechanical properties of the prepared nanobiocomposite. All components of this nanobiocomposite have good dispersion in water due to the presence of hydrophilic groups such as NH2, OH, and COOH, which is one of the effective factors in increasing the efficiency of hyperthermia cancer therapy. The structural analyzes of the hybrid nanobiocomposite were determined by FT-IR, XRD, EDX, FE-SEM, TGA and VSM. Biological studies such as MTT and hemolysis testing proved that it is hemocompatible and non-toxic for healthy cells. Furthermore, it can cause the death of cancer cells to some extent (20.23%). The ability of the nanobiocomposites in hyperthermia cancer therapy was evaluated. Also, the results showed that it can be introduced as an excellent candidate for hyperthermia cancer therapy.

Guo, J.; Sarikhani, A.; Ghosh, P.; Heitmann, T.; Hor, Y. S.; Singh, D. K.

doi: 10.1039/d2ra08105apmid: 36936828

Magnetic semiconductors are at the core of recent spintronics research endeavors. Chemically doped II–VI diluted magnetic semiconductors, such as (Zn1−xCrx)Te, provide a promising platform in this quest. However, a detailed knowledge of the microscopic nature of magnetic ground state is necessary for any practical application. Here, we report on the synergistic study of (Zn1−xCrx)Te single crystals using elastic neutron scattering measurements and density functional calculations. For the first time, our research unveils the intrinsic properties of ferromagnetic state in a macroscopic specimen of (Zn0.8Cr0.2)Te. The ferromagnetism is onset at TC ∼ 290 K and remains somewhat independent to modest change in the substitution coefficient x. We show that magnetic moments on Zn/Cr sites develop ferromagnetic correlation in the a–c plane with a large ordered moment of μ = 3.08 μB. Magnetic moment across the lattice is induced via the mediation of Te sites, uncoupled to the number of dopant carriers as inferred from the density functional calculation. Additionally, the ab initio calculations also reveal half-metallicity in x = 0.2 composition. These properties are highly desirable for future spintronic applications.

Shcherbakov, Viacheslav; Denisov, Sergey A.; Mostafavi, Mehran

doi: 10.1039/d3ra00443kpmid: 36936851

In this work, the mechanism of dioxygen reduction catalysed by gold nanoparticles (AuNPs) by two electron donors was investigated, i.e., by sodium ascorbate and hydroethidine, focusing on potential ROS (reactive oxygen species) formation, such as O2˙− and H2O2. According to our results, when AuNPs catalyse the reduction of O2, ROS are formed only as intermediates on the surface of nanoparticles, and they are unavoidably reduced to water, catalysed by the AuNPs. Thus, the statement on ROS production in the presence of AuNPs often reported in the literature is excessive. The AuNPs can catalyze the oxidation of electron donors in the cell, e.g., antioxidants causing oxidative stress. Therefore we propose that when explaining damage in the living cells observed in the presence of AuNP, the catalysis of redox reactions by AuNPs must be considered.