RSC Advances

Popa, Marcel Mirel; Shova, Sergiu; Hrubaru, Madalina; Barbu, Loredana; Draghici, Constantin; Dumitrascu, Florea; Dumitrescu, Denisa E.

doi: 10.1039/d0ra02368jpmid: 35493656

New 1-arylpyrazoles substituted with halogen atoms (Br, I) were synthesized from the corresponding sydnones by 1,3-dipolar cycloaddition. By introduction of a prochiral group such as isopropyl, in the ortho position of the benzene ring, in the starting phenylglycine 1 the rotamers caused by the hindered rotation between the phenyl and the heterocyclic ring were detected by NMR spectroscopy for 1-arylpyrazoles and for the first time for 3-arylsydnones. The N-nitrosophenylglycines present E–Z stereoisomerism due to the partial C–N double bond character. All the new compounds were structurally characterized by NMR spectroscopy and confirmed by X-ray crystallography. The crystal structures of N-nitrosophenylglycine 2c and of the sydnone 3c present similar Br⋯Br type II halogen contacts.

Oda, Shinya; Kohara, Shinji; Tsutsui, Ryo; Kasasaku, Mamoru; Kozuka, Hiromitsu

doi: 10.1039/d0ra01047bpmid: 35493678

Titanium-n-butoxide was hydrolyzed in the presence of benzoylacetone, and the resulting solution was concentrated and dried at 120 or 140 °C to obtain transparent amorphous materials. High-energy X-ray diffraction measurement was conducted at the SPring-8 facility, and the reduced pair distribution function, G(r) was calculated by Fourier transform of the total structure factor, S(Q). The G(r) value suggested that the materials are composed of TiO6 octahedra linked by corner- and edge-sharing. Low temperature thermomechanical analysis (TMA) and differential scanning calorimetry (DSC) were conduced on the materials, where a deflection was detected both in the TMA and DSC curves, revealing the glass transition of the materials. Combined with the previous work based on infrared absorption spectroscopy and gel permeation chromatography, the materials are demonstrated to be a new class of glassy materials composed of linked metal-oxygen polyhedra chelated with organic molecules. The materials are innovative due to the high refractive indices that originate in the metal-oxo oligomers and to the shapability given by their thermoplastic properties.

Obodo, K. O.; Gebreyesus, G.; Ouma, C. N. M.; Obodo, J. T.; Ezeonu, S. O.; Rai, D. P.; Bouhafs, B.

doi: 10.1039/d0ra02464cpmid: 35493683

Two dimensional HfS2 is a material with potential applications in the field of photo-catalysis and advanced solid state devices. Density functional theory with the Hubbard U parameter (DFT+U) calculations were carried out to investigate the structural, electronic and optical properties of lanthanide dopant atoms (LN = La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu) in the HfS2 mono-layer. The calculated electronic band gap for a pristine HfS2 mono-layer is 1.30 eV with a non-magnetic ground state. The dopant substitutional energies under both Hf-rich and S-rich conditions were evaluated, with the S-rich condition for the dopant atoms being negative. This implies that the incorporation of these LN dopant atoms in the HfS2 is feasible and experimental realization possible. The introduction of LN dopant atoms in the HfS2 mono-layer resulted in a significant change of the material properties. We found that the presence of LN dopant atoms in the HfS2 mono-layer significantly alters its electronic ground states by introducing defect states as well as changes in the overall density of states profile resulting in a metallic ground state for the doped mono-layers. The doped mono-layers are all magnetic with the exception of La and Lu dopant atoms. We found that LN dopant atoms in the HfS2 mono-layer influence the absorption and reflectivity spectra with the introduction of states in the lower frequency range (<1.30 eV). Furthermore, we showed that the applicability of doped HfS2 mono-layers as photo-catalysts is very different compared with the pristine HfS2 mono-layer.

Miesen, Thomas J.; Engstrom, Arek M.; Frost, Dane C.; Ajjarapu, Ramya; Ajjarapu, Rohan; Lira, Citlali Nieves; Mackiewicz, Marilyn R.

doi: 10.1039/d0ra01727bpmid: 35493639

The controlled synthesis of stable silver nanoparticles (AgNPs), that do not undergo surface oxidation and Ag+ ion dissolution, continues to be a major challenge. Here the synthesis of robust hybrid lipid-coated AgNPs, comprised of l-α-phosphatidylcholine (PC) membranes anchored by a stoichiometric amount of long-chained hydrophobic thiols and sodium oleate (SOA) as hydrophobic binding partners, that do not undergo surface oxidation and Ag+ ion dissolution, is described. UV-Visible (UV-Vis) spectroscopy, transmission electron microscopy (TEM), and inductively coupled plasma mass spectrometry (ICP-MS) demonstrate that in the presence of strong oxidants, such as potassium cyanide (KCN), the hybrid lipid-coated AgNPs are stable and do not undergo surface oxidation even in the presence of membrane destabilizing surfactants. UV-Vis studies show that the stability of hybrid lipid-coated AgNPs of various sizes and shapes is dependent on the length of the thiol hydrocarbon chain and can be ranked in the order of increasing stability as follows: propanethiol (PT) < hexanethiol (HT) ≤ decanethiol (DT). UV-Vis and ICP-MS studies show that the hybrid lipid-coated AgNPs do not change in size or shape confirming that the AgNPs do not undergo surface oxidation and Ag+ ion dissolution when placed in the presence of strong oxidants, chlorides, thiols, and low pH. Long-term stability studies, over 21 days, show that the hybrid lipid-coated AgNPs do not release Ag+ ions and are more stable. Overall, these studies demonstrate hybrid membrane encapsulation of nanomaterials is a viable method for stabilizing AgNPs in a “shape-locked” form that is unable to undergo surface oxidation, Ag+ ion release, aging, or shape conversion. More importantly, this design strategy is a simple approach to the synthesis and stabilization of AgNPs for a variety of biomedical and commercial applications where Ag+ ion release and toxicity is a concern. With robust and shielded AgNPs, investigators can now evaluate and correlate how the physical features of AgNPs influence toxicity without the confounding factor of Ag+ ions present in samples. This design strategy also provides an opportunity where the membrane composition can be tuned to control the release rate of Ag+ ions for optimizing antimicrobial activity.

Hejazian, Majid; Darmanin, Connie; Balaur, Eugeniu; Abbey, Brian

doi: 10.1039/d0ra00232apmid: 35493684

Serial femtosecond crystallography (SFX) methods used at X-ray free electron lasers (XFELs) offer a range of new opportunities for structural biology. A crucial component of SFX experiments is sample delivery. Microfluidic devices can be employed in SFX experiments to precisely deliver microcrystals to the X-ray beam and to trigger molecular dynamics via rapid mix-and-inject measurements. Here, for the first time, we have developed a process based on high-resolution photolithography using SU8 on glass to fabricate microfluidic mix-and-inject devices. In order to characterise these devices a broad range of flow rates are used and the mixing and jetting response of the devices monitored. We observe that a stable jet is formed using these devices when injecting DI-water. Three different jetting regimes, liquid column, ribbon, and cylindrical jet, were observed. Furthermore, fluorescence experiments confirm that rapid and uniform mixing of the two injected solutions is possible using these devices indicating that they could be used to probe molecular dynamics on sub-microsecond timescales.

He, Wen; Shi, Jia; Zhao, Hongkang; Wang, Hui; Liu, Xinfeng; Shi, Xinghua

doi: 10.1039/d0ra01676dpmid: 35493677

Band-gap engineering of molybdenum disulfide (MoS2) by introducing vacancies is of particular interest owing to the potential optoelectronic applications. In this work, systematic density functional theory (DFT) calculations were carried out for few-layered 3R-MoS2 with different concentrations of S vacancies. All results revealed that the defect energy levels introduced on both sides of the Fermi level formed an intermediate band in the band gap. Both the edges of the intrinsic and intermediate bands of the structures with the same type of vacancies were generally closer to the Fermi level, and the gaps decreased as the number of layers increased from 2 to 4. The preferentially formed S vacancies at the top layer and the transition of defect types from point to line led to similar indirect band gaps for 2- and 4-layered 3R-MoS2 with a low bulk concentration (around 5%) of S vacancies. This is different from most reported results about transition metal dichalcogenide (TMD) materials that the indirect band gap decreases as the number of layers increases and the low concentrations of vacancies show negligible influence on the band gap value.

Guo, Shaokui; Guo, Beibei; Ma, Ruguang; Zhu, Yufang; Wang, Jiacheng

doi: 10.1039/d0ra01705apmid: 35493673

Due to the dilemma of rapid consumption of fossil fuels and environmental pollution, development of clean, efficient and renewable energy conversion and storage technology has become an urgent need. Supercapacitors and hydrogen–oxygen fuel cells as typical representatives have become the focus of scientific research, in which the electrode materials are of much importance to their improved activity. In this work, a series of porous carbons (PCs) with high specific surface areas were prepared using natural coals as carbon precursors coupled with KOH activation. The effects of the mass ratio of coal and KOH as well as different activation temperatures on the microstructures of the PCs and electrochemical properties were studied in detail. The optimal PC4 (KOH: coal = 4) possessed a high specific surface area (SSA) of 2092 m2 g−1 and a well-developed microporous structure. As the electrocatalyst, it exhibited a positive onset potential of 0.88 V (vs. reversible hydrogen electrode (RHE)) and half-wave potential of 0.78 V (vs. RHE) towards the oxygen reduction reaction (ORR) in an alkaline solution. PC4 also showed the highest specific capacitance of 128 F g−1 at a current density of 0.5 A g−1 among all the samples in this work. The relatively good performance of PC4 resulted from its well-developed microporous structure and large SSA, enabling fast mass transfer of electrolytes.

Lian, Qi; Liu, Han; Zheng, Xuefang; Jia, Dandan; Liu, Chun; Wang, Dongjun

doi: 10.1039/d0ra01427cpmid: 35493646

A novel controlled drug release system based on pH sensitive polyacrylonitrile (PAN) nanoflowers in different kinds of solvents was successfully prepared with azobisisobutyronitrile (AIBN) as the initiator and without any emulsifier or stabilizer by a one step static polymerization method. The composition and structure of the PAN nanoflowers were analyzed by FTIR, XRD, SEM, TEM, and laser particle size analysis. The polymer particles consisted of a number of lamellae, with a sheet thickness of about 10 nm, and were similar to the shape of flowers with a particle diameter of about 350 nm. The mechanism of the polymerization reaction and the formation were studied. Moreover, the effects of monomer ratio, initiator concentration, reaction time, dispersion medium and co-monomer on the morphology and particle size of the nanoflowers were also discussed. A relatively large specific surface area was formed during the formation of the nanoflowers, which favored drug adsorption. The results of the in vitro experiments revealed that PAN(TBP) nanoflowers, containing BSA in buffer solution of pH 7.4, demonstrated good sustained-release and the cumulative release rate was about 83% after 260 h. The results also showed that the sustained-release from the PAN(TBP) nanoflowers best fitted the Riger-Peppas model. This study indicated that PAN(TBP) nanoflowers provided a theoretical base for the development of carriers for sustainable drug-release.

Söftje, Martin; Acker, Sophie; Plarre, Rudy; Namyslo, Jan C.; Kaufmann, Dieter E.

doi: 10.1039/d0ra02071kpmid: 35493663

Timber is constantly exposed to environmental influences under outdoor conditions which limits its lifetime and usability. In order to counteract the damaging processes caused by insects, we have developed a novel and more environmentally friendly method to protect wood materials via covalent modification by organic insecticides. Starting with an important class of synthetic insecticides which are derived from the natural insecticide nicotine, various new carboxylic acid derivatives of imidacloprid were made accessible. These activated neonicotinoids were utilized for the chemical modification of wood hydroxy groups. In contrast to conventional wood preservation methods in which biocides are only physically bound to the surface for a limited time, the covalent fixation of the preservative guarantees a permanent effect against wood pests, demonstrated in standardized biological tests. Additionally, the environmental interaction caused by non-bound neonicotinoids is significantly reduced, since both, a smaller application rate is required and leaching of the active ingredient is prevented. By minimizing the pest infestation, the lifetime of the material increases while preserving the natural appearance of the material.

Takekuma, Yuya; Ikeda, Nobuhiro; Kawakami, Keisuke; Kamiya, Nobuo; Nango, Mamoru; Nagata, Morio

doi: 10.1039/d0ra01793kpmid: 35493643

Photosynthesis is a process used by algae and plants to convert light energy into chemical energy. Due to their uniquely natural and environmentally friendly nature, photosynthetic proteins have attracted attention for use in a variety of artificial applications. Among the various types, biophotovoltaics based on dye-sensitized solar cells have been demonstrated in many studies. Although most related works have used n-type semiconductors, a p-type semiconductor is also a significant potential component for tandem cells. In this work, we used mesoporous NiO as a p-type semiconductor substrate for Photosystem I (PSI) and demonstrated a p-type PSI-biophotovoltaic and tandem cell based on dye-sensitized solar cells. Under visible light illumination, the PSI-adsorbed NiO electrode generated a cathodic photocurrent. The p-type biophotovoltaic cell using the PSI-adsorbed NiO electrode generated electricity, and the IPCE spectrum was consistent with the absorption spectrum of PSI. These results indicate that the PSI-adsorbed NiO electrode acts as a photocathode. Moreover, a tandem cell consisting of the PSI-NiO photocathode and a PSI-TiO2 photoanode showed a high open-circuit voltage of over 0.7 V under illumination to the TiO2 side. Thus, the tandem strategy can be utilized for biophotovoltaics, and the use of other biomaterials that match the solar spectrum will lead to further progress in photovoltaic performance.