RSC Advances

Gao, Xianlong; Mo, Wenlong; Ma, Fengyun; Noritatsu, Tsubaki; Wu, Hongli; Fan, Xing

doi: 10.1039/c9ra10200kpmid: 35497417

Three commercial Ni–Al alloys formed by a vacuum atomization method (NAV), atmospheric atomization method (NAA) and high-temperature melting method (NAH) were leached by 10 wt% NaOH solution to prepare three RANEY®-Ni catalysts (RNAV, RNAA and RNAH, correspondingly). The effects of a forming process on the structure of Ni–Al alloys and the corresponding RANEY®-Ni catalysts were investigated via XRD, XPS, SEM, TEM, NH3-TPD, N2 adsorption–desorption and EDX-mapping studies. Also, the as-prepared RANEY®-Ni catalysts were evaluated via the hydrogenation of 1,4-butenediol (BED) to produce 1,4-butanediol (BDO). The results showed that the specific surface areas and surface morphologies of the Ni–Al alloys present significant differences. Meanwhile, the RNAA sample presented a comparatively regular morphology, similar to a small piece of sugar cane. The weak and medium acid peak areas of the RNAA catalyst were lower than those of the other samples. RNAV showed higher weak and medium acid peak areas, demonstrating the higher number of acid centers on the surface of the catalyst. The surface of the RNAA catalyst obtained from NAA contained more active component-Ni, about 90 wt% on the surface, and the specific surface area of the sample was 75 times that of its precursor Ni–Al alloy powder (NAA). The evaluation results present that the RNAA catalyst shows better hydrogenation performance, with BED conversion of 100%, both BDO selectivity and yield of 46.11%.

Wadhwa, Geetika; Krishna, Kowthavarapu Venkata; Taliyan, Rajeev; Tandon, Neeraj; Yadav, Satyapal Singh; Katiyar, Chandrakant; Dubey, Sunil Kumar

doi: 10.1039/c9ra08121fpmid: 35497432

A reliable and sensitive ultra-performance liquid chromatography-tandem mass spectrometry-based method has been developed for the estimation of 4-hydroxyisoleucine (4-HI), a potent insulinotropic and hypolipidemic agent. The extraction of 4-HI from plasma was accomplished by the protein precipitation technique using l-isoleucine as an internal standard. The separation of analytes was achieved with a mobile phase consisting of acetonitrile and 0.1% formic acid in an isocratic flow system on a BEH Shield RP-18 column (150 mm × 2.1 mm, 1.7 μm). 4-HI and l-isoleucine were detected using an electrospray ionization (ESI) ion source, using multiple reaction monitoring (MRM) in positive ion mode. The precursor to product ion transitions of 4-HI and l-isoleucine were found at m/z values of 148.19 > 74.02 and 132.17 > 69.04, respectively. As per the guidelines for bioanalytical methods, all validation parameter results were within the acceptable range. The method exhibited a robust and reproducible linearity range of 1–5000 ng mL−1 with a coefficient of regression of 0.9999. The method was successfully applied for the estimation of pharmacokinetic parameters after oral administration of 4-HI (10 mg kg−1) in Wistar rats, by using Thoth Pro (version: 4.3) software. Herein, the two-compartment model was statistically fitted based on AIC and SBC values for evaluation of the pharmacokinetic parameters of 4-HI. Pharmacodynamic studies were also performed by measuring the levels of triglyceride and total cholesterol, and showed that the pharmacokinetic and pharmacodynamic data of 4-HI correlated with each other.

Wu, Jiaxiang; Liu, Qiang; Feng, Bin; Wu, Shuangzhang; Zhang, Sheng; Gao, Zhenru; Yin, Qin; Li, Yuchun; Xiao, Liming; Huang, Junyi

doi: 10.1039/d0ra00044bpmid: 35497435

Thermite serves as a kind of representative energetic material, which is extensively applied in the civil and military fields. In this paper, PTFE/Al/Fe2O3, PTFE/Al/MnO2 and PTFE/Al/MoO3, solid fluorine-containing thermite with different PTFE content, were successfully fabricated by referring to the traditional thermite and adding PTFE as a binder or matrix. Quasi-static compression tests were performed to investigate the mechanical and reactive behavior of fluorine-containing thermite. SEM and XRD were employed to analyze and characterize the energetic composites and reaction residuals. The results show that all types of fluorine-containing thermite exhibited different mechanical behavior. PTFE/Al/MnO2 exhibited the lowest yield strength and strain hardening modulus, but the highest compressive strength and toughness. With the increase of PTFE content, the strength of fluorine-containing thermite improved. No reaction occurred when the PTFE content was 60 vol%, while fluorine-containing thermite with a PTFE content of 80 vol% experienced a severe exothermic reaction under quasi-static compression. The ignition of PTFE/Al/MoO3 and PTFE/Al/Fe2O3 actually attributed to the reaction of Al and PTFE, and the reaction between Al and Fe2O3 or MoO3 was not excited due to the insufficient input energy. The thermite reaction between Al and MnO2, as well as the reaction of MnO2 and PTFE, was induced because PTFE/Al/MnO2 possessed excellent ductility and absorbed the most energy during compression, accompanied with the production of Mn and MnF2.

Hricovíni, Michal; Asher, James; Hricovíni, Miloš

doi: 10.1039/c9ra10730dpmid: 35497446

EPR and NMR experiments on a quinazolinone-based Schiff's base in DMSO solution showed that irradiation with UV light (365 nm) leads to photochemically-induced isomerization from the anti- to the higher-energy syn-form around the –N–N linkage. The anti- to syn-isomerization was relatively fast, and the maximum amount of conversion detected (25%) was reached within 10 min; thermodynamic equilibrium re-established itself in about 15 min. DFT calculations were performed on the investigated compound and small model systems, and reproduced the experimental fact of the anti-conformer being lower in energy than the syn. Theoretical analysis of excited states, including visualisation of natural transition orbitals, identified possible pathways for syn–anti isomerisation, although the details vary with π-system size, making the use of small models of limited utility. The investigated compound probably isomerises through the third singlet excited state (S3), a π–π* excitation, relaxing through S2, also a π–π* state.

Benavides, Brenda S.; Valandro, Silvano; Kurtz, Donald M.

doi: 10.1039/d0ra00341gpmid: 35497424

The quest for efficient solar-to-fuel conversion has led to the development of numerous homogeneous and heterogeneous systems for photochemical stimulation of 2H+ + 2e− → H2. Many such systems consist of a photosensitizer, an H2-evolving catalyst (HEC), and sacrificial electron donor often with an electron relay between photosensitizer and HEC. Colloidal platinum remains a popular HEC. We report here a novel, simple, and high yield synthesis of Pt nanoparticles (Pt NPs) associated with human heavy chain ferritin (Hfn). The formation of the Pt NPs capitalizes on Hfn's native catalysis of autoxidation of Fe(ii)(aq) (ferroxidase activity). Fe(ii) reduces Pt(ii) to Pt(0) and the rapid ferroxidase reaction produces FeO(OH), which associates with and stabilizes the incipient Pt NPs. This Pt/Fe-Hfn efficiently catalyzes photosensitized H2 production when combined with Eosin Y (EY) as photosensitizer and triethanolamine (TEOA) as sacrificial electron donor. With white light irradiation turnover numbers of 300H2 per Pt, 250H2 per EY were achieved. A quantum yield of 18% for H2 production was obtained with 550 nm irradiation. The fluorescence emission of EY is quenched by TEOA but not by Pt/Fe-Hfn. We propose that the photosensitized H2 production from aqueous TEOA, EY, Pt/Fe-Hfn solution occurs via a reductive quenching pathway in which both the singlet and triplet excited states of EY are reduced by TEOA to the anion radical, EY−˙, which in turn transfers electrons to the Pt/Fe-Hfn HEC. Hfn is known to be a remarkably versatile scaffold for incorporation and stabilization of noble metal and semiconductor nanoparticles. Since both EY and Hfn are amenable to scale-up, we envision further refinements to and applications of this photosensitized H2-generating system.

Qin, Wu; Zhang, Yi; Wu, Jianqing

doi: 10.1039/c9ra09805dpmid: 35497463

A pore-sealing method for preparation of high-permeance alumina microfiltration (MF) membranes free of any intermediate layers is presented. It involves sequential coating of a polyvinyl butyral (PVB) layer and an alumina membrane precursor on the surface of the macroporous alumina support. An alumina MF membrane with no intermediate layers can be obtained on the support after pyrolysis of the PVB interlayer. The interlayer-free membrane prepared by this method has an average pore diameter of 0.26 μm and a water permeance of 1468 ± 81 L m−2 h−1 bar−1 which is prominently higher than that of the ceramic membranes prepared with other techniques. The conspicuous increase of water permeance is speculated mainly due to the filtration resistance decrease of the interlayer-free ceramic membrane.

Huo, Gengyang; Chen, Wenyong; Wang, Jianhua; Chu, Xinxing; Xu, Wei; Li, Bin; Zhang, Yi; Xu, Binqian; Zhou, Xingfei

doi: 10.1039/c9ra09943cpmid: 35497413

Copper ions play a critical role in human islet amyloid polypeptide (hIAPP) aggregation, which has been found in more than 90% of patients with type-2 diabetes (T2D). The role of Cu(ii) in the cell cytotoxicity with hIAPP has been explored in two aspects: inhibiting the formation of fibrillar structures and stimulating the generation of reactive oxygen species (ROS). In this work, we carried out spectroscopic studies of Cu(ii) interacting with several hIAPP fragments and their variants as well. Electron paramagnetic resonance (EPR) measurements and Amplex Red analysis showed that the amount of H2O2 generated in hIAPP(11-28) solution co-incubated with Cu(ii) was remarkably more than hIAPP(1-11) and hIAPP(28-37). Furthermore, the H2O2 level was seriously reduced when His18 of hIAPP(11-28) was replaced by Arg(R) or Ser(S), indicating that His18 is the key residue of Cu(ii) binding to hIAPP(11-28) to promote H2O2 generation. This is likely because the donation of electrons from the peptide to Cu(ii) ions would result in the formation of the redox-active complexes, which could stimulate the formation of H2O2. Overall, this study provides further insight into the molecular mechanism of Cu(ii) induced ROS generation.

Liu, Jian; Li, Tao; Wang, Shun; Qi, Qingrong; Song, Hang; Li, Zicheng; Yang, Li; Huang, Wencai

doi: 10.1039/c9ra10882cpmid: 35497447

To achieve sensitive, selective and facile detection of hydrazine in environmental and biological systems, a fluorescent probe (Che-Dcv) with a unique nonaromatic fluorophore was developed. Upon hydrazine addition in 20% DMSO–PBS buffer (pH = 7.4, 10 mM, v/v) at room temperature, the probe displayed a strong emission at 496 nm along with a color change from brown-red to yellow. The response was attributed to the reaction of dicyanovinyl groups with hydrazine to afford hydrazone, which was supported by 1H NMR and HRMS. The detection limit of Che-Dcv for hydrazine was estimated to be as low as 1.08 ppb and good selectivity over amines including hydroxylamine was observed. Then, the potential of probe-coated test papers to detect hydrazine in solution and vapor phase was demonstrated. Moreover, the bioimaging of hydrazine in living H1975 cells was performed successfully.

Chen, Chih-Yao; Yang, Jyun-Hao; Lin, Tzu-Yu; Ma, Hao-Yuan; Chen, I-Chen

doi: 10.1039/c9ra10457gpmid: 35497457

A local contact patterning process based on dewetting of 50 nm-thick polystyrene (PS) films has been developed for fabrication of silicon PERC (Passivated Emitter and Rear Cell) solar cells. Holey PS films with a random pattern of holes were prepared on dielectric passivated silicon wafers through the dewetting process, and then served as etch masks for selective plasma etching of dielectric passivation layers, in doing so metal contact patterns could be generated. The impact of local back contact formation on cell performance was studied as a function of the metallization fraction. This chemical-based patterning process, which broadens the applications of dewetting of polymer films, offers an interesting alternative to laser-based approaches as it may avoid silicon surface damage and lower the manufacturing costs. The application of this patterning technique to PERC fabrication could result in a preliminary efficiency of 13.5% with a Voc = 655 mV and a Jsc = 38.4 mA cm−2. An apparent gain in conversion efficiency of 0.6% could be achieved compared to the full-area aluminum back surface field reference cell.

Zhang, Liping; Gonçalves, Alexandre A. S.; Jaroniec, Mietek

doi: 10.1039/d0ra00769bpmid: 35497459

Crystals with exposed facets are popular materials in many catalytic applications due to their high reactivity. Facet identification is often conducted by transmission electron microscopy (TEM). In this work, we analyze the effects of doping, vacancy creation, anisotropic broadening, and preferred orientation on the intensity of X-ray diffraction (XRD) peaks by using tetragonal bismuth oxyhalides (BiOX, X = Cl, Br, and I) as examples. The differences in these effects were successfully used to identify the preferentially exposed (001) facets of BiOX nanoplates synthesized by a polymer-assisted precipitation method. In comparison to TEM, the XRD analysis is not only cheaper and easier to perform, but also it gives results representative for the sample. This work aims to provide further justification for the use of XRD as a powerful and handy characterization technique in the field of crystal facet engineering.