RSC Advances最新文献

Hot-pressed saloplastics are dense and transparent polyelectrolyte complex materials governed by ionic crosslinking. Such plastics have several advantages, for example, salt water processibility and recyclability. Here, we demonstrate a simple but effective post-treatment method to incorporate lysozyme as a biocatalytic component into the hot-pressed saloplastics. Changes in salt concentration can be used for annealing and curing the saloplastics, where the temporary opening allows for lysozyme loading. This process was carefully examined by two different routes and the salt concentrations and incubation times were varied systematically. Optimised saloplastics showed an enzymatic activity against Micrococcus lysodeikticus of 4.44 ± 0.37 U cm⁻² and remained partially active (∼72% activity preserved) after 7 days. This approach opens new routes to incorporate enzymes or other biological functionality into saloplastics which is difficult to achieve for conventional plastics.

Oral squamous cell carcinoma (OSCC) is the most common type of oral cancer. In recent years, researchers have found a close relationship between microRNAs (miRNAs) and OSCC. In addition, miRNAs are highly stable in tissues and circulation, and are also considered potential biomarkers for cancer detection and prognosis. Among a variety of tools for miRNAs with low abundance, single red-emitting UCNP-based biosensors have attracted special interest due to their unique properties, including deep organizational penetration, weak radiation damage, and low autofluorescence. Additionally, the measurement of low-abundance analytes via enzyme-free signal amplification is also an effective means. Herein, by taking advantage of red-emitting UCNPs and an enzyme-toehold-mediated strand displacement cascade, a dual-signal amplification biosensor was constructed. The recycled miRNA can be regarded as a catalyst for the assembly of multiple H1/H2 duplexes, which promoted the response signal of augmented analyte expression. Moreover, the proposed biosensors improved the measurement accuracy via a dual-signal response to obviously avert false-positive signals. The proposed method was applied to measure miRNA-222 (a model analyte) in serum samples, and the results were similar to those of polymerase chain reaction (PCR), with spiked recoveries ranging from 91.2% to 101.7%. The proposed assay has the merits of high sensitivity, strong recognition, and low background, indicating broad potential for the measurement of diverse analytes in biological samples.

Herein, we describe the synthesis of new hybrids linked to 1,2,3- and 1,2,4-triazole units. Hybrids connected to a 1,2,3-triazole ring were synthesized using the well-known click reaction. The synthesis of the 1,2,4-triazole-based hybrids was carried out using 2-[(4-cyano-1-methyl(2-furyl)-5,6,7,8-tetrahydroisoquinolin-3-yl)oxy]acetohydrazides as starting compounds. The compounds were evaluated for their anticonvulsive activity via antagonism towards pentylenetetrazole (PTZ) – and thiosemicarbazide (TSC)-induced convulsion and maximal electroshock-induced seizure (MES). Furthermore, the most active compounds were studied for their locomotory and anxiolytic activity via the “open field” and elevated plus maze (EPM) assays. Finally, their antidepressant activity was studied via the “forced swim” method. All the hybrids displayed pentylenetetrazole antagonism, ranging from 40% to 80%, while in the TSC model, the most active compounds increased latency of thiosemicarbazide seizures to 1.9–4.65 times compared to that of the control. Some of the tested compounds exhibited a pronounced anxiolytic and antidepressant effect. Docking study demonstrated complete agreement with experimental pharmacological data. It was revealed that the most active compounds have a pyrano[3,4-c]pyridine ring in their structure.

Application of redox-active polymers (RAPs) in redox flow batteries (RFBs) can potentially reduce the stack cost through substitution of costly ion-exchange membranes by cheap size-exclusion membranes. However, intermolecular interactions of polymer molecules, i.e., entanglements, particularly in concentrated solutions, result in relatively high electrolyte viscosities. Furthermore, the large size and limited mobility of polymers lead to slow diffusion and more sluggish heterogeneous electron transfer rates compared to quickly diffusing small molecules. Although a number of RAPs with varying electrolyte viscosities have been reported in the literature, the relation between the RAP structure and the hydrodynamic properties has not been thoroughly investigated. Herein, hyperbranched 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO)-based polymers intended for application as low-viscosity catholytes for RFBs are presented and the influence of the structure and the molar mass distribution on the hydrodynamic properties is investigated. A new synthesis approach for TEMPO-based polymers is established based on step-growth polymerization of a TEMPO-containing monomer using an aza-Michael addition followed by a postpolymerization modification to improve solubility in aqueous solutions. The compact structure of hyperbranched polymers was demonstrated using size-exclusion chromatography (SEC) with viscometric detection and the optimum molar mass was found based on the results of viscometric and crossover investigations. The resulting RAP revealed a viscosity of around 21 mPas at a concentration corresponding to around 1 M TEMPO-containing units, according to the calculated mass of the repeating unit, showing potential for high capacity polymer-based catholytes for RFBs. Nevertheless, possible partial deactivation of TEMPO units lowered the active TEMPO concentration of the hyperbranched RAPs. A faster diffusion and higher charge transfer rate were observed for the hyperbranched polymer compared to the previously reported linear polymers. However, in RFB tests, a poor performance was observed, which is attributed to the side reactions of the oxidized TEMPO moieties. Finally, pathways for overcoming the main remaining challenges, i.e., high loss of material during dialysis as an indication of being prone to crossover, the partial deactivation of TEMPO moieties, and the subsequent side reactions under battery conditions, are suggested.

The pursuit of efficient and sustainable energy storage solutions has fueled significant interest in the development of advanced materials for supercapacitors. Among these, two-dimensional (2D) materials undoubtingly have emerged as promising candidates due to their unique structural and electrochemical properties. To address the inherent challenges such as restacking, limited ion-accessibility, limited scalability, stability under operational conditions, and the intricate balance between surface area and conductivity that hinder the practical application of 2D materials, this article delves into innovative approaches and emerging strategies and prospects that aim to enhance their performance and durability. A systematic exploration of synthesis methods, structural characteristics, and electrochemical performance as supercapacitor electrodes of key 2D materials, including graphene, MXenes, transition metal dichalcogenides (TMDCs), black phosphorous and phosphorene and their composites has been discussed. The discussion will extend to recent breakthroughs and innovations, shedding light on how researchers are leveraging the unique properties of 2D materials to overcome existing challenges in supercapacitor technology. Beyond mere documentation, this review seeks to inspire future research directions, foster interdisciplinary collaborations, and contribute to the ongoing evolution of energy storage technologies towards a more sustainable and efficient future.

A photoelectrochemical (PEC) sensor based on the poly-2,2,5,2-terthiophene (pTTh)/Cu₂O heterojunction was constructed and applied for the detection of long non-coding RNA (lncRNA) TROJAN, a biomarker of triple-negative breast cancer. Cu₂O and pTTh were electrodeposited in situ and sequentially onto an indium tin oxide substrate. The bandgap of the resultant type II heterojunction was measured spectroscopically and the morphology was found to effectively separate photogenerated holes from electrons. A photocurrent density as high as 250 μA cm⁻² was attained, which is about three times higher than those of only pTTh or Cu₂O. Owing to the close contact between pTTh and Cu₂O, this PEC sensor is highly stable. Oligonucleotide probes for lncRNA can be cross-linked to carboxyl moieties of mercaptopropionic acid molecules adsorbed on pTTh/Cu₂O. The desirable band structure and the high density of probe molecules collectively yielded a linear range of 0.1–10 000 pM. Our PEC sensor has been demonstrated to be amenable for detection of lncRNA markers with excellent analytical performance.

Breast cancer treatment has made tremendous progress in recent years and new therapies are emerging continuously. Alpelisib (ALP) is a novel phosphoinositide-3-kinase (PI3K) inhibitor recently approved for human receptor-positive, human epidermal growth factor receptor 2-negative, PIK3CA-mutated metastatic breast cancer in combination with fulvestrant. ALP has been the subject of only a limited number of preclinical in vitro and in vivo studies using different chromatographic techniques. However, no research has been published on analyzing ALP using capillary electrophoresis (CE). The absence of pharmacopoeial monographs for ALP in both the European and United States Pharmacopoeias highlights the urgent need to develop a reliable analytical method for its quality control in both industry and regulatory authorities. In this work, we have developed a first-ever CE method for the determination of ALP in pharmaceutical dosage forms in just 1.4 minutes. This was achieved with a 25 mM borate buffer at pH 9.3, 30 kV separation voltage and 30 °C capillary temperature. The proposed method was validated according to the ICH guidelines regarding selectivity, linearity (r = 0.9988), precision (RSD < 5.9%), accuracy (bias < 3.0%) and robustness (RSD < 3.2%). It was applied to the pharmaceutical dosage form of ALP and was shown to be suitable for the reliable determination of ALP. Furthermore, to demonstrate the applicability of the CE as an alternative technique to more commonly used HPLC in the analysis of drugs, cross-validation of CE and HPLC methods was performed. Bland–Altman analysis showed that the average difference in determined concentrations between CE and HPLC over a range of 10–100 μg mL⁻¹ was 0.87 μg mL⁻¹ (p = 0.6390, N = 19) meaning that there is no difference in the performance of CE and HPLC in the determination of ALP in pharmaceutical dosage forms. The environmental impact of both methods was assessed using AGREE software and scores for CE and HPLC were calculated to be 0.74 and 0.51, respectively. Because of equally reliable analytical performance and greener analysis, CE should be considered as an alternative technique to HPLC in the analysis of ALP pharmaceutical dosage forms.

The intermolecular carbonyl-ene reaction of ketones is still considered a challenge in organic chemistry, particularly with reusable solid catalysts, and implemented in a domino reaction. Herein, we show that the extremely cheap and non-toxic solid salt MgCl₂ catalyzes the reaction of trifluoromethyl pyruvates not only during the conventional carbonyl-ene reaction with various aromatic and alkyl alkenes (in very high yields, up to >99%) but also in a domino reaction with the corresponding alcohols (precursors to the alkenes) in similar good yields. The solid can be reused in both cases without any erosion of the catalytic activity and can be employed in an in-flow process to maximize the reaction throughput. Besides, the reaction can be performed under solventless reaction conditions. Addition of a catalytic amount of chiral binaphthyl hydrogen phosphate allows carrying out the reaction with a reasonable enantiomeric excess (up to >70%) and in flow, in a rare example of enantioselective solid-catalyzed domino carbonyl-ene reaction using a cheap, simple, readily available and physically mixed catalytic solid. The MgCl₂-catalytic system is also active in the industrially relevant citronellal-to-isopulegol carbonyl-ene reaction. These results pave the way to design sustainable domino carbonyl-ene reactions with extremely cheap solid catalysts.

Overbased sulfonate plays a crucial role in calcium sulfonate complex grease, significantly impacting the grease's performance characteristics. Herein, the calcium sulfonate complex grease was formulated using overbased calcium sulfonate (T106D) and overbased magnesium sulfonate (T107) in ratios of 1 : 2, 1 : 1, and 2 : 1, labeled as CMSCG (1 : 2), CMSCG (1 : 1), and CMSCG (2 : 1), respectively. This study examined the effects of overbased sulfonates on the physicochemical, anti-corrosion, rheological, and tribological properties of the grease. Results showed that CMSCG (1 : 2) exhibited superior physicochemical properties, with the highest dropping point (354 °C), the lowest penetration (161 (0.1 mm)), and the least oil separation (1.25%). Exposure to a salt spray environment significantly altered the grease's rheological properties. The combination of T106D and T107 enhanced the corrosion resistance of the grease, attributed to the formation of a corrosion inhibition layer. Incorporating T107 increased both the yield stress and hysteresis area of the calcium sulfonate complex grease. The CMSCG (1 : 2), CMSCG (1 : 1), and MSCG showed the high thixotropic ring area, indicating the poor thixotropy. The calcium sulfonate complex grease formulated with T107 showed the highest yield stress (558 Pa). The friction mechanism revealed that MSCG showed the optimal friction reduction properties, and CMSCG (1 : 1) demonstrated the optimal wear resistance, which are attributed to the synergistic effects of tribo-chemical films composed of CaO, CaCO₃, FeSO₄, MgCO₃, and iron oxide.

The photophysical properties of the β-barrel superfolder green fluorescent protein (sfGFP) arise from the chromophore that forms post-translationally in the interior of the protein. Specifically, the protonation state of the side chain of tyrosine 66 in the chromophore, in addition to the network of hydrogen bonds between the chromophore and surrounding residues, is directly related to the electronic absorbance and emission properties of the protein. The pH dependence of the photophysical properties of this protein were modulated by the genetic, site-specific incorporation of 3-nitro-L-tyrosine (mNO₂Y) at site 66 in sfGFP. The altered photophysical properties of this noncanonical amino acid (ncAA) sfGFP construct were assessed by absorbance and fluorescence spectroscopies. Notably, a comparison of the pK_a of the 3-nitrophenol side chain of mNO₂Y incorporated in the protein relative to the phenol side chain of the tyrosine at site 66 in the native chromophore as well as the pK_a of the 3-nitrophenol side chain of the free ncAA were measured and are compared. A structural analysis of the ncAA containing sfGFP construct is presented to yield molecular insight into the origin of the altered absorbance and fluorescence properties of the protein.