Effect of the cross-linker length of thiophene units on photocatalytic hydrogen production of triazine-based conjugated microporous polymers

Conjugated microporous polymers (CMPs) have been investigated in the field of photocatalytic hydrogen production because of their extended π-conjugation, tunable chemical structure and excellent thermal stability. Herein, we construct three CMPs based on thiophenes and triazine, and prove the effect of cross-linker length on photocatalytic activity of CMPs. BTPT-CMP1 exhibits blue-shifted optical absorption compared to BTPT-CMP2 and BTPT-CMP3 with long cross-linkers, however, possesses higher photocurrent because of the large specific surface area and small interface charge transfer resistance of BTPT-CMP1. It was found that BTPT-CMP1 (5561.87 μmol g⁻¹ h⁻¹) with short cross-linkers exhibits better photocatalytic performance compared to BTPT-CMP2 (1840.86 μmol g⁻¹ h⁻¹) and BTPT-CMP3 (1600.48 μmol g⁻¹ h⁻¹). Also, BTPT-CMP1 possesses a higher hydrogen evolution rate than most reported 1,3,5-triazine based conjugated polymers. These results demonstrate that the cross-linker length has great influence on the photocatalytic properties of conjugated microporous polymers, which offers theoretical direction for designing high-performance CMPs.

Conjugated microporous polymers (CMPs) have been investigated in the field of photocatalytic hydrogen production because of their extended π-conjugation, tunable chemical structure and excellent thermal stability.     

Effect of glucose oxidase and pentosanase on the prebiotic potentials of wheat arabinoxylans in an in vitro fermentation system

Arabinoxylans (AXs) treated with enzymes, pentosanase (Pn) and glucose oxidase (GOX) not only offer a promising way to improve wheat product quality but also change their prebiotic potentials by modifying the structures of AXs. In the present study, the different crosslinking degrees of water-extracted arabinoxylans (WEAXs) treated with GOX alone or in combination with Pn + GOX were examined. The structural features and candidate prebiotic capabilities were investigated. It was demonstrated that WEAXs treated with 50 μg g⁻¹ (w/w, enzyme/WEAX) GOX and 200 μg g⁻¹ (w/w, enzyme/WEAX) Pn + 400 μg g⁻¹ (w/w, enzyme/WEAX) GOX exhibited weak gel formation, while WEAXs treated with 400 μg g⁻¹ (w/w, enzyme/WEAX) GOX and 25 μg g⁻¹ (w/w, enzyme/WEAX) Pn + 400 μg g⁻¹ (w/w, enzyme/WEAX) GOX formed strong gels. The ferulic acid content was significantly decreased due to the formation of ferulic acid crosslinking in the enzyme-treated WEAXs (p < 0.05). During in vitro fermentation, GOX and Pn + GOX treatments resulted in significantly (p < 0.05) increased amounts of bifidobacteria compared to WEAX alone. Pn + GOX-treated WEAXs had higher (p < 0.05) bifidobacteria populations than WEAXs treated with GOX alone. The bifidobacteria numbers and the SCFAs content of the weak gels were significantly higher than those in the strong gels under the same enzyme action (p < 0.05). These findings suggested that the increased bifidobacteria populations of GOX-treated WEAXs were due to the formation of ferulic acid crosslinking in contrast to a combination of ferulic acid crosslinking and degradation of the xylan backbone as seen in WEAXs treated with Pn + GOX. The reason the weak gels had better prebiotic potential than the corresponding strong gels was their high content of ferulic acid crosslinking.

GOX and Pn + GOX modification increased the prebiotic potential of WEAX. Pn + GOX treated WEAXs had higher prebiotic potentials than WEAXs treated with GOX. The prebiotic potential of the weak gel was higher than that in the strong gel.     

Hydrogen production rates of aluminum reacting with varying densities of supercritical water

Aluminum particles, spanning in size from 10 μm to 3 mm, were reacted with varying densities of water at 655 K. The density of the water is varied from 50 g L⁻¹ to 450 g L⁻¹ in order to understand the effect of density on both reaction rates and yields. Low-density supercritical water is associated with properties that make it an efficient oxidizer: low viscosity, high diffusion, and low relative permittivity. Despite this, it was found that the high-density (450 g L⁻¹) supercritical water was the most efficient oxidizer both in terms of reaction rate and hydrogen yield. The 10 μm powder had a peak reaction rate of approximately 675 cm_H2³ min⁻¹ g_Al⁻¹ in the high-density water, and a peak reaction rate below 250 cm_H2³ min⁻¹ g_Al⁻¹ in the low- and vapour-density water. A decline in peak reaction rate with decreasing water density was also observed for the 120 μm powder and the 3 mm slugs. These findings imply that the increased collision frequency, a property of the high-density water, outpaces reduction in the reaction enhancing properties associated with low-density supercritical water. Hydrogen yield was minimally affected by decreasing the oxidizer density from 450 g L⁻¹ to 200 g L⁻¹, but did drop off significantly in the vapour-density (50 g L⁻¹) water.

Hydrogen production rates of aluminum reacting with various densities of supercritical water are determined using a novel method. High-density supercritical water is found to be the most efficient oxidizer, in terms of both reaction rates and yields.     

Fabrication and application of a MIL-68(In)–NH2 incorporated high internal phase emulsion polymeric monolith as a solid phase extraction adsorbent in triazine herbicide residue analysis

In this work, a metal–organic framework MIL-68(In)–NH₂ incorporated high internal phase emulsion polymeric monolith (MIL-68(In)–NH₂/polyHIPE) was prepared and applied as a solid phase extraction adsorbent for the extraction and detection of trace triazine herbicides in environmental water samples by coupling with HPLC-UV detection. The fabricated material showed good adsorption for simazine, prometryn, and prometon in water samples because of π–π interactions and hydrogen bonding interactions. Under optimal conditions, the maximum adsorption capacity of simazine, prometon and prometryn was 800 μg g⁻¹, 800 μg g⁻¹ and 6.01 mg g⁻¹, respectively. The linearities were 10–800 ng mL⁻¹ for simazine, prometon and prometryn. The limits of detection were 31–97 ng L⁻¹, and the recoveries were 85.6–118.2% at four spiked levels with relative standard deviations lower than 5.0%. The method has a high sensitivity for the determination of three triazine herbicides in environmental water samples.

MIL-68(In)–NH₂ incorporated high internal phase emulsion polymeric monoliths were fabricated and applied to extract and determine triazine herbicide residues in environmental water samples.     

Retraction: One pot green preparation of Seabuckthorn silver nanoparticles (SBT@AgNPs) featuring high stability and longevity,antibacterial, antioxidant potential: a nano disinfectant future perspective

Retraction of ‘One pot green preparation of Seabuckthorn silver nanoparticles (SBT@AgNPs) featuring high stability and longevity, antibacterial, antioxidant potential: a nano disinfectant future perspective’ by Thiyagarajan Kalaiyarasan et al., RSC Adv., 2017, 7, 51130–51141, https://doi.org/10.1039/C7RA10262C.

I, the undersigned author, hereby wholly retract this RSC Advances article due to the following instances of matched/similar images that have been identified that weaken this article, which occurred due to honest human errors.Following the previous publication of a correction to correct errors in Fig. 1, 3, 7 and 9, further instances of duplicating images have been identified within the corrected Fig. 3 and 7, as well as additional errors in the original article, that undermine this article.In Fig. 3 of the correction notice:The panel for freshly prepared S. enterica MTCC-3219 2 μg ml⁻¹ 10⁻¹⁰ is identical to the panel for S. typhirmurium MTCC-3224 4 μg ml⁻¹ 10⁻⁵ after one year of storage, to the panel 1 h treated with SBT@AgNPs in Fig. 7, and to the panels E. coli MTCC No. 62 6 μg ml⁻¹ and 8 μg ml⁻¹ in Fig. 5 of ref. 1.The panel for freshly prepared S. typhirmurium MTCC-3224 6 μg ml⁻¹ 10⁻¹⁰ is identical to the panel for S. typhirmurium MTCC-3224 6 μg ml⁻¹ 10⁻¹⁰ after one year of storage and to the panel 0.5 h treated with SBT@AgNPs in Fig. 7.The panel for freshly prepared S. typhirmurium MTCC-3224 4 μg ml⁻¹ 10⁻⁵ is identical to the panel for freshly prepared S. enterica MTCC-3219 6 μg ml⁻¹ 10⁻¹⁰.The panel for freshly prepared S. typhirmurium MTCC-3224 2 μg ml⁻¹ 10⁻¹⁰ is identical to the panel for S. typhirmurium MTCC-3224 6 μg ml⁻¹ 10⁻⁵ after one year of storage.The panel for freshly prepared S. typhirmurium MTCC-3224 4 μg ml⁻¹ 10⁻¹⁰ is identical to the panel for S. typhirmurium MTCC-3224 2 μg ml⁻¹ 10⁻¹⁰ after one year of storage.The panel for S. enterica MTCC-3219 4 μg ml⁻¹ 10⁻⁵ after one year of storage is identical to the panel for S. enterica MTCC-3219 6 μg ml⁻¹ 10⁻¹⁰ after one year of storage.In Fig. 3a, a′, c and c′ of the original article, the error bars are erroneous.In Fig. 4 of the original article, both the panels for S. typhirmurium are identical.Thiyagarajan Kalaiyarasan and Vijay K. Bharti responded to all enquiries and submitted data related to the above concerns. However, to avoid any future ambiguity to the readers, the article is retracted.Vijay K. Bharti and O. P. Chaurasia were informed about the retraction of the article but have not responded.Signed: Kalaiyarasan ThiyagarajanDate: 1/6/2022Retraction endorsed by Laura Fisher, Executive Editor, RSC Advances     

Synthesis of alginate–polycation capsules of different composition: characterization and their adsorption for [As(iii)] and [As(v)] from aqueous solutions

The uptake of arsenite [As(iii)] and arsenate [As(v)] by functionalized calcium alginate (Ca-Alg) beads from aqueous solutions was investigated. Ca-Alg beads were protonated with poly-l-lysine (PLL) or polyethyleneimine (PEI) using 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide/N-hydroxysuccinimide (EDC/NHS) or glutaraldehyde (GA) as crosslinking agents. Four types of protonated beads were prepared: Ca-Alg-EDC/NHS (PLL or PEI) and Ca-Alg-GA (PLL or PEI). Fourier transform infrared spectroscopy in total attenuated reflection mode (FTIR-ATR), analysis showed presence and increased intensity of bands corresponding to OH, NH, CH₂ and CH₃ groups in modifications with both polycations. In addition, thermogravimetric analysis and atomic force microscopy of all modified capsules showed an increase in thermal stability and uniformity of the capsules, respectively. Ca-Alg-EDC/NHS-PLL beads had the maximum adsorption capacity of [As(v)] (312.9 ± 4.7 μg g⁻¹ of the alginate) at pH 7.0 and 15 minute exposure, while Ca-Alg-EDC/NHS-PEI beads had the maximum adsorption capacity of [As(iii)] (1052.1 ± 4.6 μg g⁻¹ of alginate). However, all these EDC containing beads were degraded in the presence of citrate. Ca-Alg-GA-PEI beads removed 252.8 ± 9.7 μg of [As(v)] μg g⁻¹ of alginate and 524.7 ± 5.3 de [As(iii)] μg g⁻¹ of alginate, resulting the most stable capsules and suitable for As removal.

A simple protonation of alginate beads allows the absorption of arsenate and arsenite.     

Novel chalcone derivatives containing a 1,2,4-triazine moiety: design,synthesis, antibacterial and antiviral activities

A series of novel chalcone derivatives containing the 1,2,4-triazine moiety were synthesized and their structures were confirmed by ¹H NMR, ¹³C NMR and elemental analyses. Antiviral bioassays revealed that most of the compounds exhibited good antiviral activity against tobacco mosaic virus (TMV) at a concentration of 500 μg mL⁻¹. The designated compound 4l was 50% effective in terms of curative and protective activities against TMV with 50% effective concentrations (EC₅₀) of 10.9 and 79.4 μg mL⁻¹, which were better than those of ningnanmycin (81.4 and 82.2 μg mL⁻¹). Microscale thermophoresis (MST) also showed that the binding of compound 4l to coat protein (TMV-CP) yielded a K_d value of 0.275 ± 0.160 μmol L⁻¹, which was better than that of ningnanmycin (0.523 ± 0.250 μmol L⁻¹). At the same time, molecular docking studies for 4l with TMV-CP (PDB code:1EI7) showed that the compound was embedded well in the pocket between the two subunits of TMV-CP. Meanwhile, compound 4a demonstrated excellent antibacterial activities against Ralstonia solanacearum (R. solanacearum), with an EC₅₀ value of 0.1 μg mL⁻¹, which was better than that of thiodiazole-copper (36.1 μg mL⁻¹) and bismerthiazol (49.5 μg mL⁻¹). The compounds act by causing folding and deformation of the bacterial cell membrane as observed using scanning electron microscopy (SEM). The chalcone derivatives thus synthesized could become potential alternative templates for novel antiviral and antibacterial agents.

A series of novel chalcone derivatives containing the 1,2,4-triazine moiety were synthesized and their structures were confirmed by ¹H NMR, ¹³C NMR and elemental analyses.     

TiO2–Au composite nanofibers for photocatalytic hydrogen evolution

TiO₂-based materials for photocatalytic hydrogen (H₂) evolution have attracted much interest as a renewable approach for clean energy applications. TiO₂–Au composite nanofibers (NFs) with an average fiber diameter of ∼160 nm have been fabricated by electrospinning combined with calcination treatment. In situ reduced gold nanoparticles (NPs) with uniform size (∼10 nm) are found to disperse homogenously in the TiO₂ NF matrix. The TiO₂–Au composite NFs catalyst can significantly enhance the photocatalytic H₂ generation with an extremely high rate of 12 440 μmol g⁻¹ h⁻¹, corresponding to an adequate apparent quantum yield of 5.11% at 400 nm, which is 25 times and 10 times those of P25 (584 μmol g⁻¹ h⁻¹) and pure TiO₂ NFs (1254 μmol g⁻¹ h⁻¹), respectively. Furthermore, detailed studies indicate that the H₂ evolution efficiency of the TiO₂–Au composite NF catalyst is highly dependent on the gold content. This work provides a strategy to develop highly efficient catalysts for H₂ evolution.

The H₂ production rate of TiO₂–Au nanofibers is dramatically improved to 12 440 μmol g⁻¹ h⁻¹, 10 times that of pure TiO₂.     

Synthesis of SrTiO3 submicron cubes with simultaneous and competitive photocatalytic activity for H2O splitting and CO2 reduction

Single crystalline strontium titanate (SrTiO₃) submicron cubes have been synthesized based on a molten salt method. The submicron cubes showed superior photocatalytic activity towards both water splitting and carbon dioxide reduction, in which methane (CH₄) and hydrogen (H₂) were simultaneously produced. The average production rate of methane up to 8 h is 4.39 μmol g⁻¹ h⁻¹ but drops to 0.46 μmol g⁻¹ h⁻¹. However, the average production rate of hydrogen is 14.52 before 8 h but then increases to 120.23 μmol g⁻¹ h⁻¹ after 8 h. The rate change of the two processes confirms the competition between the H₂O splitting and CO₂ reduction reactions. Band structure and surface characteristics of the SrTiO₃ submicron cubes were characterized by diffuse reflective UV-Vis spectroscopy, Mott–Schottky analysis, X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). The results reveal that the simultaneous and competitive production of methane and hydrogen is due to a thermodynamics factor, as well as the competition between the adsorption of carbon dioxide and water molecules on the surface of the faceted SrTiO₃. This work demonstrates that SrTiO₃ photocatalysts are efficient in producing sustainable fuels via water splitting and carbon dioxide reduction reactions.

There is a clear competitive relationship between water splitting and photocatalytic reduction of carbon dioxide in the whole process of photocatalytic reduction of carbon dioxide with the prepared cubic SrTiO₃ as a photocatalyst.     

Chemical structure and biological properties of a polysaccharide isolated from Pleurotus sajor-caju

Herein, a polysaccharide obtained from Pleurotus sajor-caju was fractionated via anion-exchange column chromatography and purified using gel permeation column chromatography. The chemical characterization of the polysaccharide indicated that it contained 90.16% total carbohydrate, 0% protein, 12.7% ash and 5.2% moisture; on the other hand, the carbon, hydrogen and nitrogen contents were found to be 31.53, 4.28 and 3.01%, respectively. The polysaccharide has the molecular weight of 79 kDa; the chemical structure of the polysaccharide is →6)α-d-Glc^iv(1→6)α-d-Glcⁱⁱⁱ(1→6)β-d-Glcⁱⁱ(1→6)α-d-Glcⁱ(1→units. The polysaccharide exhibited the DPPH radical scavenging activity of 21.67–68.35% at 10–160 μg ml⁻¹, ABTS radical scavenging activity of 16.01–70.09% at 25–125 μg ml⁻¹, superoxide radical scavenging activity of 24.31–73.64% at 50–250 μg ml⁻¹, hydroxyl radical scavenging activity of 16.64–63.51% at 25–125 μg ml⁻¹ and reducing power of 0.366–1.678% at 10–120 μg ml; further evaluation of the polysaccharide revealed its anticancer activity of 18.61–63.21% at 100–500 μg ml⁻¹ concentration against the AGS human gastric carcinoma cell line. The active principle of the polysaccharide may be used in the food and pharmacological industry in the future.

Herein, a polysaccharide obtained from Pleurotus sajor-caju was fractionated via anion-exchange column chromatography and purified using gel permeation column chromatography.     

Synthesis and antibacterial and antiviral activities of myricetin derivatives containing a 1,2,4-triazole Schiff base

A series of novel myricetin derivatives containing a 1,2,4-triazole Schiff base were designed and synthesized. Their structures were systematically characterized using ¹H NMR, ¹³C NMR, and HRMS. During antibacterial bioassays, 6f, 6i, and 6q demonstrated a good inhibitory effect against Xanthomonas axonopodis pv. citri (Xac), with half-maximal effective concentration (EC₅₀) values of 10.0, 9.4, and 8.8 μg mL⁻¹, respectively, which were better than those of bismerthiazol (54.9 μg mL⁻¹) and thiodiazole copper (61.1 μg mL⁻¹). Note that 6w demonstrated a good inhibitory effect against Ralstonia solanacearum (Rs) with and EC₅₀ value of 15.5 μg mL⁻¹, which was better than those of bismerthiazol (55.2 μg mL⁻¹) and thiodiazole copper (127.9 μg mL⁻¹). Similarly, 6a, 6d, and 6e demonstrated a good inhibitory effect against Xanthomonas oryzae pv. oryzae (Xoo) with EC₅₀ values of 47.1, 61.2, and 61.0 μg mL⁻¹, respectively, which were better than those of bismerthiazol (148.2 μg mL⁻¹) and thiodiazole copper (175.5 μg mL⁻¹). Furthermore, we used scanning electron microscopy (SEM) to study the possible sterilization process of the target compound 6q against Xac. The results indicated the possibility of destroying the bacterial cell membrane structure, resulting in an incomplete bacterial structure, and thus achieving inhibition. Furthermore, antiviral bioassays revealed that most compounds exhibited excellent antiviral activity against tobacco mosaic virus (TMV) at a concentration of 500 μg mL⁻¹. The results of the molecular docking studies for 6g with TMV-CP (PDB code: 1EI7) showed that compound 6g had partially interacted with TMV-CP. Therefore, mechanistic studies of the action of compound 6g could be further studied based on that.

The myricetin derivatives containing a 1,2,4-triazole Schiff base were designed and synthesized. Antibacterial mechanism was investigated through SEM.     

Pt-grown carbon nanofibers for detection of hydrogen peroxide

Removal of left-over catalyst particles from carbon nanomaterials is a significant scientific and technological problem. Here, we present the physical and electrochemical study of application-specific carbon nanofibers grown from Pt-catalyst layers. The use of Pt catalyst removes the requirement for any cleaning procedure as the remaining catalyst particles have a specific role in the end-application. Despite the relatively small amount of Pt in the samples (7.0 ± 0.2%), they show electrochemical features closely resembling those of polycrystalline Pt. In O₂-containing environment, the material shows two separate linear ranges for hydrogen peroxide reduction: 1–100 μM and 100–1000 μM with sensitivities of 0.432 μA μM⁻¹ cm⁻² and 0.257 μA μM⁻¹ cm⁻², respectively, with a 0.21 μM limit of detection. In deaerated solution, there is only one linear range with sensitivity 0.244 μA μM⁻¹ cm⁻² and 0.22 μM limit of detection. We suggest that the high sensitivity between 1 μM and 100 μM in solutions where O₂ is present is due to oxygen reduction reaction occurring on the CNFs producing a small additional cathodic contribution to the measured current. This has important implications when Pt-containing sensors are utilized to detect hydrogen peroxide reduction in biological, O₂-containing environment.

Application specific Pt-grown carbon nanofibers for H₂O₂ detection were characterized and the roles of dissolved oxygen and chloride ions on the electrochemical performance were assessed in detail.     

Magnetic solid-phase extraction of pyrethroid insecticides from tea infusions using ionic liquid-modified magnetic zeolitic imidazolate framework-8 as an adsorbent

A simple, sensitive, and reliable magnetic solid-phase extraction (SPE) method coupled with GC-MS/MS for the effective analysis of four pyrethroids from tea infusions was developed. A magnetic adsorbent, named ionic liquid-modified magnetic zeolitic imidazolate framework-8 (Fe₃O₄/ZIF-8/IL), was prepared by immobilizing an ionic liquid (IL) on the surface of Fe₃O₄/ZIF-8. The textures of Fe₃O₄/ZIF-8/IL were confirmed by material characterization, and the results suggested that the adsorbent possessed high magnetism (59.0 emu g⁻¹), an adequate Brunauer–Emmett–Teller (BET) surface area (104 m² g⁻¹), and a large pore volume (0.68 cm³ g⁻¹). To confirm the extraction performance of the prepared Fe₃O₄/ZIF-8/IL, several experimental conditions affecting the extraction efficiency were investigated. Under the optimum conditions, the limits of determination (LODs) for the four pyrethroids were in the range of 0.0065–0.1017 μg L⁻¹ (S/N = 3 : 1) with an intra-day relative standard deviation (RSD) of ≤9.70% and inter-day RSD of ≤11.95%. The linear ranges were 0.5–50 μg L⁻¹ for bifenthrin and 0.5–500 μg L⁻¹ for permethrin, cypermethrin, and flucythrinate, with determination coefficients higher than 0.999. Finally, the proposed technique was successfully applied for the determination of pyrethroids in real tea infusions. This work could be extended to other IL-modified metal–organic frameworks (MOFs) and to the development of different sample pretreatment techniques.

A MSPE-GC-MS/MS method was developed for the analysis of pyrethroids from tea infusions using Fe₃O₄/ZIF-8/IL as an adsorbent.     

Photo-induced synthesis,structure and in vitro bioactivity of a natural cyclic peptide Yunnanin A analog

A cyclic analog of natural peptide Yunnanin A was synthesized via photoinduced single electron transfer reaction (SET) in the paper. The resulting compound exhibited potent bioactivity (with IC₅₀ values 29.25 μg mL⁻¹ against HepG-2 cell lines and 65.01 μg mL⁻¹ against HeLa cell lines), but almost have no toxicity to normal cells (with IC₅₀ values 203.25 μg mL⁻¹ against L929 cell lines), which may be served as a potential antitumor drug for medical treatment. The spatial structure was examined by experimental electronic circular dichroism (ECD) and quantum chemistry calculations. Moreover, the theoretical study suggested that special intramolecular hydrogen bonds and γ, β-turn secondary structures may be possible sources affecting cyclic peptide''s bioactivity.

The photo-induced synthesis, structure and in vitro bioactivity study of a Yunnanin A cyclopeptide analog was presented.     

Preparation of a magnetic multiwalled carbon nanotube@polydopamine/zeolitic imidazolate framework-8 composite for magnetic solid-phase extraction of triazole fungicides from environmental water samples

A novel magnetic zinc-based zeolitic imidazolate framework (MMP/ZIF-8) has been prepared using a magnetic multiwalled carbon nanotube@polydopamine nanocomposite as the magnetic core and support. It was then used as an adsorbent for magnetic solid-phase extraction of triazole fungicides from environmental water samples. Successful synthesis of MMP/ZIF-8 was confirmed by material characterization, and the results showed that the synthetic composite has a high Brunauer–Emmett–Teller surface area (141.56 m² g⁻¹), large total pore volume (0.636 mL g⁻¹), and high superparamagnetism with a saturation magnetization of 44.1 emu g⁻¹. To evaluate the extraction performance of MMP/ZIF-8, the main parameters that affect the extraction efficiency were optimized. Under the optimal conditions, the developed method shows good linearity (R² ≥ 0.9915) in the concentration range 1–400 μg L⁻¹. Low limits of detection (0.08–0.27 μg L⁻¹, signal/noise = 3 : 1) and good precision (intraday relative standard deviation ≤ 7.73%, interday relative standard deviation ≤ 9.65%) are also achieved. The developed method was applied for analysis of triazole fungicides in environmental water samples.

A magnetic ZIF-8 composite was prepared based on Fe₃O₄/MWCNT@PDA and used as an adsorbent for MSPE of triazoles from environmental water samples.     

A new HPLC-UV derivatization approach for the determination of potential genotoxic benzyl halides in drug substances

Benzyl halides, widely used as alkylation reagents in drug synthesis, are potential genotoxic impurities (PGTIs) required to be controlled at trace levels. However, the existing analytical methods for benzyl halides often suffer from matrix interferences or low derivatization efficiency of benzyl chlorides. In this paper, a simple derivatization HPLC-UV method was developed for the analysis of these residual trace benzyl halides in drug substances. 1-(4-Nitrophenyl) piperazine (4-NPP) was selected as a new derivatization reagent because it shifted well the benzyl halides derivatives away to the near visible range (392 nm), which could minimize the matrix interferences from the drug substances and related impurities. Meanwhile, potassium iodide (KI) was used to convert the mixed benzyl halides into benzyl iodides before derivatization. The derivatization parameters were also optimized using the design of experiments (DoE) for achieving the best reaction efficiency. The results showed that the new approach had high specificity and sensitivity, and the LOQs were 7–9 μg g⁻¹ relative to 5 mg mL⁻¹ antipyrine and 17.5–22.5 μg g⁻¹ relative to 2 mg mL⁻¹ oroxylin A. The method is a valuable alternative for the determination of residual benzyl halides in the drug substances.

Benzyl halides, widely used as alkylation reagents in drug synthesis, are potential genotoxic impurities (PGTIs) required to be controlled at trace levels.     

Postsynthetic of MIL-101-NH2 MOFs supported on PVDF membrane for REEs recovery from waste phosphor

With the increasing demand for rare earth elements (REEs) due to their wide application in high technology, their recovery and separation from waste sources has gradually come onto the agenda. Herein, a new kind of MIL-101-NH₂ (M1N) MOF functionalized with diethanol anhydride (DGA) incorporated into a polyvinylidene fluoride (PVDF) membrane (DGA-M1N@PVDF) has been fabricated for the sorption of REEs from a simulated acid leaching solution of waste phosphor, which contains a large amount of REEs. FTIR, TGA, XRD, fluorescence spectra and XPS analysis were used to characterize the synthesized composite membrane. Batch tests were employed to determine the optimal sorption conditions for Y and Eu adsorbed on DGA-M1N@PVDF adsorbent, such as pH (1–5), content of M1N MOFs (0–40 wt%), contact time (10–180 min) and ion concentration (0–20 mg L⁻¹). Maximum adsorption capacities for Y and Eu on DGA-M1N@PVDF reached 991.7 μg g⁻¹ and 98.76 μg g⁻¹ for trace REE solution, respectively. Moreover, a pseudo-second-order kinetic model accurately described the sorption process, and the plotted isothermal data indicated that the Langmuir model was more suitable than the Freundlich model for Y and Eu sorption with monolayer and chemical adsorption. Meanwhile, FTIR and XPS analyses revealed that the Y and Eu adsorption on the DGA-M1N@PVDF composite membrane was mainly caused by the N and O atoms of the –CONH or –COOH groups coordinated with metal ions. Furthermore, after five cycles, the recovery efficiency by DGA-M1N@PVDF for REEs remains above 82% and the XRD patterns were consistent with the original sample, which implied that the DGA-M1N@PVDF membrane has preferable stability, recyclability and good efficiency in REE separation from waste phosphor solutions.

A new kind DGA modified MIL-101-NH₂ MOFs supported on PVDF composite membrane (DGA-M1N@PVDF) was synthesized, which had superior selectivity, good adsorption capacity and good recycling performance on REEs in waste phosphor.     

Biological activity evaluation and action mechanism of chalcone derivatives containing thiophene sulfonate

A series of novel chalcone derivatives containing a thiophene sulfonate group were designed and synthesized. The structures of all title compounds were determined by ¹H-NMR, ¹³C-NMR and HRMS. Antibacterial bioassays indicated that, compound 2l demonstrated excellent antibacterial activities against Xanthomonas axonopodis pv. citri (Xac), with an EC₅₀ value of 11.4 μg mL⁻¹, which is significantly superior to those of bismerthiazol (BT) (51.6 μg mL⁻¹) and thiodiazole-copper (TC) (94.7 μg mL⁻¹). Meanwhile, the mechanism of action of compound 2l was confirmed by using scanning electron microscopy (SEM). In addition, compound 2e showed remarkable inactivation activity against Tobacco mosaic virus (TMV), with an EC₅₀ value of 44.3 μg mL⁻¹, which was superior to that of ningnanmycin (120.6 μg mL⁻¹). Microscale thermophoresis (MST) also showed that the binding of compounds 2e and 2h to Tobacco mosaic virus coat protein (TMV-CP) yielded K_d values of 0.270 and 0.301 μmol L⁻¹, which are better than that of ningnanmycin (0.596 μmol L⁻¹). At the same time, molecular docking studies for 2e and 2h with TMV-CP (PDB code: 1EI7) showed that the compound was embedded well in the pocket between the two subunits of TMV-CP in each case. These results suggested that chalcone derivatives containing a thiophene sulfonate group may be considered as activators in the design of antibacterial and antiviral agents.

Synthesis, antibacterial, antiviral activities and action mechanism of chalcone derivatives containing thiophene sulfonate.     

Discovery of quinolone derivatives as antimycobacterial agents

Tuberculosis (TB), an infectious disease caused by Mycobacterium tuberculosis (M. tuberculosis), is an important public health issue. Current first-line drugs administered to TB patients have been in use for over 40 years, whereas second-line drugs display strong side effects and poor compliance. Additionally, designing effective regimens to treat patients infected with multi- and extremely-drug-resistant (MDR and XDR) strains of TB is challenging. In this report, we screened our compound library and identified compound 1 with antituberculosis activity and a minimal inhibitory concentration (MIC) against M. tuberculosis of 20 μg mL⁻¹. Structure optimization and the structure–activity relationship of 1 as the lead compound enabled the design and synthesis of a series of quinolone derivatives, 6a1–6a2, 6b1–6b36, 6c1, 6d1–6d14, 7a1–7a2, 7b1–7b2, 7c1, 8a1–8a5, 9a1–9a4 and 10a1–10a6. These compounds were evaluated in vitro for anti-tubercular activity against the M. tuberculosis H₃₇Rv strain. Among them, compounds 6b6, 6b12 and 6b21 exhibited MIC values in the range of 1.2–3 μg mL⁻¹ and showed excellent activity against the tested MDR-TB strain (MIC: 3, 2.9 and 0.9 μg mL⁻¹, respectively). All three compounds were non-toxic toward A549 and Vero cells (>100 and >50 μg mL⁻¹, respectively). In addition, an antibacterial spectrum test carried out using compound 6b21 showed that this compound specifically inhibits M. tuberculosis. These can serve as a new starting point for the development of anti-TB agents with therapeutic potential.

6b21: MIC against M. tb H₃₇Rv = 1.2 μg mL⁻¹, MIC against drug-resistant strains = 0.9 μg mL⁻¹, solubility = 132 μg mL⁻¹, non-cytotoxicity.