Correction: Ascorbic acid/Fe0 composites as an effective persulfate activator for improving the degradation of rhodamine B

Correction for ‘Ascorbic acid/Fe⁰ composites as an effective persulfate activator for improving the degradation of rhodamine B’ by Xiangyu Wang et al., RSC Adv., 2018, 8, 12791–12798.

The authors regret that the unit on the x-axis of Fig. 1 was incorrectly written as “% wt” rather than “‰ wt” in the original article. The correct version of Fig. 1 is presented below.Open in a separate windowFig. 1(a) Comparison of removal efficiency of RhB in different systems (C₀ = 50 mg L⁻¹, PS dosage = 1.4 g L⁻¹, Fe⁰ dosage = 1 g L⁻¹, H₂A/Fe⁰ dosage = 1 g L⁻¹, H₂A dosage = 1.6 g L⁻¹ and T = 298 K); (b) effect of H₂A concentration on removal efficiency of RhB in the H₂A/Fe⁰–PS system (C₀ = 50 mg L⁻¹, Fe⁰ dosage = 0.8 g L⁻¹, T = 298 K and the solution volume is 50 mL).The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers.     

Developing a screen-printed graphite–polyurethane composite electrode modified with gold nanoparticles for the voltammetric determination of dopamine

A screen-printed electrode (SPGPUE) was prepared with graphite–polyurethane composite ink containing gold nanoparticles (AuNPs), resulting in a screen-printed graphite–polyurethane composite electrode modified with gold nanoparticles (SPGPUE–AuNPs). Gold nanoparticles were prepared by the citrate method and extracted from the water medium since polyurethane is not compatible with humidity. After extraction to chloroform, they were characterized via transmission electron microscopy (TEM). The presence of gold on the SPGPUE–AuNP surface was confirmed via SEM and EDX analyses, while thermogravimetry revealed the presence of approximately 3.0% (m/m) gold in the composite. An electrochemical pretreatment in 0.10 mol L⁻¹ phosphate buffer (pH 7.0) with successive cycling between −1.0 V and 1.0 V (vs. pseudo-Ag/AgCl) under a scan rate of 200 mV s⁻¹ and 150 cycles was required in order to provide a suitable electrochemical response for the voltammetric determination of dopamine. After the optimization of the parameters of differential pulse voltammetry (DPV), an analytical curve was obtained within a linear dynamic range of 0.40–60.0 μmol L⁻¹ and detection limit (LOD) of 1.55 ×10⁻⁸ mol L⁻¹ for dopamine at the SPGPUE–AuNP. A non-modified SPGPUE was used for comparison and a linear range was obtained between 2.0 and 10 μmol L⁻¹ with an LOD of 2.94 × 10⁻⁷ mol L⁻¹. During the dopamine determination in cerebrospinal synthetic fluid (CSF), recoveries between 89.3 and 103% were achieved. There were no significant interferences from ascorbic acid and uric acid, but some from epinephrine due to the structural similarity.

A screen-printed modified composite electrode (SPGPUE) was prepared with graphite–polyurethane ink containing gold nanoparticles (AuNPs), resulting in a sensor with improved sensitivity regarding the unmodified device in dopamine determination.     

Magnetic solid-phase extraction using a mixture of two types of nanoparticles followed by gas chromatography-mass spectrometry for the determination of six phthalic acid esters in various water samples

Two types of magnetic microspheres (Fe₃O₄@MIL-100 and Fe₃O₄@SiO₂@polythiophene) were prepared and characterized as mixed sorbents for magnetic solid-phase extraction (MSPE) of six phthalic acid esters (PAEs), including dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), benzyl butyl phthalate (BBP), di-2-ethylhexyl phthalate (DEHP), and di-n-octyl phthalate (DnOP) from water samples prior to gas chromatography-mass spectrometry (GC-MS) analysis. The synthetic magnetic nanocomposites exhibited good repeatability and chemical stability, and improved extraction efficiency for the tested PAEs. The mixture of the two types of nanoparticles substantially improved the extraction efficiency of both DMP and DEP. The key parameters affecting the extraction efficiency, such as the type and the amount of sorbent, eluent (desorption solvent), adsorption and desorption time, pH of sample solution, and sample volume, were investigated and optimized, respectively. Under optimized conditions, the developed method showed satisfactory linearity in the range of 5–5000 μg L⁻¹ with coefficients of determination (R²) > 0.9935. The method detection limits (MDLs) and limits of quantitation (LOQs) were between 0.35–0.91 μg L⁻¹ and 1.1–2.9 μg L⁻¹, respectively. At three fortification levels (1.0, 10.0, and 50.0 μg L⁻¹), the mean recoveries ranged from 76.9–109.1% with favorable relative standard deviations (RSDs) < 9%. The feasibility of the method was evaluated by analysis of water samples from various sources (tap, drinking, and mineral water). The results show that the developed method is suitable for determination of trace level PAEs in water samples.

A mixture of Fe₃O₄@MIL-100 and Fe₃O₄@SiO₂@polythiophene nanoparticles exhibit high extraction efficiency for PAEs in water.     

A novel resource utilization method using wet magnesia flue gas desulfurization residue for simultaneous removal of ammonium nitrogen and heavy metal pollutants from vanadium containing industrial wastewater

In the present study, a novel resource utilization method using wet magnesia flue gas desulfurization (FGD) residue for the simultaneous removal of ammonium nitrogen (NH₄–N) and heavy metal pollutants from vanadium (V) industrial wastewater was proven to be viable and effective. In this process, the wet magnesia FGD residue could not only act as a reductant of hexavalent chromium [Cr(vi)] and pentavalent vanadium [V(v)], but also offered plenty of low cost magnesium ions to remove NH₄–N using struvite crystallization. The optimum experimental conditions for Cr(vi) and V(v) reduction are as follows: the reduction pH = 2.5, the wet magnesia FGD residue dose is 42.5 g L⁻¹, t = 15.0 min. The optimum experimental conditions for NH₄–N and heavy metal pollutants removal are as follows: the precipitate pH = 9.5, the n(Mg²⁺) : n(NH₄⁺) : n(PO₄³⁻) = 0.3 : 1.0 : 1.0, t = 20.0 min. Finally the NH₄–N, V and Cr were separated from the vanadium containing industrial wastewater by forming the difficult to obtain, soluble coprecipitate containing struvite and heavy metal hydroxides. The residual pollutant concentrations in the wastewater were as follows: Cr(vi) was 0.047 mg L⁻¹, total Cr was 0.1 mg L⁻¹, V was 0.14 mg L⁻¹, NH₄–N was 176.2 mg L⁻¹ (removal efficiency was about 94.5%) and phosphorus was 14.7 mg L⁻¹.

A novel resource utilization method using wet magnesia flue gas desulfurization residue for the simultaneous removal of ammonium nitrogen and heavy metal pollutants from vanadium industrial wastewater was proven to be viable and effective.     

Improving the corrosion resistance of micro-arc oxidation coated Mg–Zn–Ca alloy

Four additives (Na₂WO₄, nano-hydroxyapatite, K₂TiF₆ and NaF) were added into the Na₅P₃O₁₀ + NaOH + C₃H₈O₃ base electrolyte according to the orthogonal design of four factors three levels (L₉ (3⁴)). Nine different micro-arc oxidation (MAO) coatings were fabricated on Mg–2Zn–0.5Ca alloys through orthogonal experiments. The effects of four additives on the microstructure, mechanical properties, corrosion resistance and biocompatibility of MAO coatings were investigated through X-ray diffraction (XRD), scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS), electrochemical corrosion test and in vitro degradation test. The addition of nano-hydroxyapatite and K₂TiF₆ showed self-sealing effects and contributed to the corrosion resistance of the samples significantly. The addition of 0.5 g L⁻¹ Na₂WO₄ markedly elevated the bonding strength of the coatings with the substrate. The optimal combination of factors and levels considering both mechanical properties and corrosion resistance was: 0.5 g L⁻¹ Na₂WO₄, 0 g L⁻¹ NaF, 5 g L⁻¹ n-HAp, 5 g L⁻¹ K₂TiF₆. The growth mechanism of MAO coatings combining with the visual phenomenon was discussed as well.

Large amount of micro-pores formed in MAO coatings were interconnected and sealed.     

Nanoarchitectonics of p-type BiSbTe with improved figure of merit via introducing PbTe nanoparticles

Bi_0.4Sb_1.6Te₃ (BST) is known to be a unique p-type commercial thermoelectric (TE) alloy used at room temperatures, but its figure of merit (ZT) is relatively low for wide industrial applications. To improve its ZT value is vitally important. Here, we show that the incorporation of 0.5 wt% PbTe nanoparticles into BST concurrently causes a large enhancement of power factor (PF) and a significant reduction of lattice thermal conductivity κ_L. The increase in PF mainly benefits from the optimization of carrier concentration, maintenance of high carrier mobility and constant rise in Seebeck coefficient. The decrease in κ_L can be attributed to the enhanced phonon scattering by the dispersed PbTe nanoparticles and the interfaces between PbTe and the BST matrix by using the Callaway model. Specifically, an ultralow κ_L of 0.26 W m⁻¹ K⁻¹ at 429 K is achieved for the composites incorporating 0.5 wt% PbTe nanoinclusions. Consequently, an excellent ZT = 1.6 at 482 K and a high average ZT_ave = 1.38 at 300–500 K are achieved, indicating that incorporation of PbTe in BST is an effective approach to improve its thermoelectric performance.

We introduce 0.5 wt% PbTe nanoparticles into the Bi_0.4Sb_1.6Te₃ matrix and possess an ultralow lattice thermal conductivity of 0.26 W m⁻¹ K⁻¹ at 429 K and an excellent ZT value of 1.6 at 482 K as well as a high average ZT_ave of 1.38 at 300–500 K.     

Production of rhamnolipids with different proportions of mono-rhamnolipids using crude glycerol and a comparison of their application potential for oil recovery from oily sludge

The use of efficient green cleaning agents, such as biosurfactants, is important in oil sludge treatment. Enhanced oil recovery from oily sludge by different rhamnolipids was comparatively evaluated. Using crude glycerol, the wild-type strain Pseudomonas aeruginosa SG and the recombinant strains P. aeruginosa PrhlAB and P. stutzeri Rhl produced 1.98 g L⁻¹, 2.87 g L⁻¹ and 0.87 g L⁻¹ of rhamnolipids, respectively. The three bacterial strains produced different rhamnolipid mixtures under the same conditions. The proportions of mono-rhamnolipids in the three rhamnolipid products were 55.92%, 94.92% and 100%, respectively. These rhamnolipid products also possessed different bioactivities. Emulsifying activity became higher as the proportion of mono-rhamnolipids increased. The three rhamnolipid products were stable at temperatures lower than 121 °C, pH values from 5–11 and NaCl concentrations from 0–15%. All three rhamnolipid products could recover oil from oily sludge, but oil recovery efficiency was positively related to the proportion of mono-rhamnolipids. Mono-rhamnolipids produced by the recombinant strain Rhl exhibited the best oil recovery efficiency (53.81%). The results reveal that mono-rhamnolipids are the most promising for oil recovery from oily sludge.

Oil recovery from oily sludge is positively related to the proportion of mono-rhamnolipids.     

A Bi2WO6/Ag2S/ZnS Z-scheme heterojunction photocatalyst with enhanced visible-light photoactivity towards the degradation of multiple dye pollutants

A novel visible-light-driven Z-scheme heterojunction, Bi₂WO₆/Ag₂S/ZnS, was synthesized and its photocatalytic activity was evaluated for the treatment of a binary mixture of dyes, and its physicochemical properties were characterized using FT-IR, XRD, DRS and FE-SEM techniques. The Bi₂WO₆/Ag₂S/ZnS Z-scheme heterojunctions not only facilitate the charge separation and transfer, but also maintain the redox ability of their components. The superior photocatalytic activity demonstrated by the Z-scheme Bi₂WO₆/Ag₂S/ZnS attributes its unique properties such as the rapid generation of electron–hole pairs, slow recombination rate, and narrow bandgap. The performance of the Bi₂WO₆/Ag₂S/ZnS was evaluated for the simultaneous degradation of methyl green (MG) and auramine-O (AO) dyes, while the influences of the initial MG concentration (4–12 mg L⁻¹), initial AO concentration (2–6 mg L⁻¹), pH (3–9), irradiation time (60–120 min) and photocatalyst dosage (0.008–0.016 g L⁻¹) were investigated through the response surface methodology. The desirability function approach was applied to optimize the process and results revealed that maximum photocatalytic degradation efficiency was obtained at optimum conditions including 6.08 mg L⁻¹ of initial MG concentration, 4.04 mg L⁻¹ of initial AO concentration, 7.25 of pH, 90.58 min of irradiation time and 0.013 g L⁻¹ of photocatalyst dosage. In addition, a possible photocatalytic mechanism of the Bi₂WO₆/Ag₂S/ZnS heterojunction was proposed based on the photoinduced charge carriers.

A Z-scheme Bi₂WO₆/Ag₂S/ZnS heterojunction was successfully synthesized as a novel visible-light-driven photocatalyst for the degradation of multiple dye pollutants.     

Catalytic activation of peroxymonosulfate with manganese cobaltite nanoparticles for the degradation of organic dyes

In this work, we report the facile hydrothermal synthesis of manganese cobaltite nanoparticles (MnCo₂O_4.5 NPs) which can efficiently activate peroxymonosulfate (PMS) for the generation of sulfate free radicals (SO₄˙⁻) and degradation of organic dyes. The synthesized MnCo₂O_4.5 NPs have a polyhedral morphology with cubic spinel structure, homogeneously distributed Mn, Co, and O elements, and an average size less than 50 nm. As demonstrated, MnCo₂O_4.5 NPs showed the highest catalytic activity among all tested catalysts (MnO₂, CoO) and outperformed other spinel-based catalysts for Methylene Blue (MB) degradation. The MB degradation efficiency reached 100% after 25 min of reaction under initial conditions of 500 mg L⁻¹ Oxone, 20 mg L⁻¹ MnCo₂O_4.5, 20 mg L⁻¹ MB, unadjusted pH, and T = 25 °C. MnCo₂O_4.5 NPs showed a great catalytic activity in a wide pH range (3.5–11), catalyst dose (10–60 mg L⁻¹), Oxone concentration (300–1500 mg L⁻¹), MB concentration (5–40 mg L⁻¹), and temperature (25–55 °C). HCO₃⁻, CO₃²⁻ and particularly Cl⁻ coexisting anions were found to inhibit the catalytic activity of MnCo₂O_4.5 NPs. Radical quenching experiments revealed that sulfate radicals are primarily responsible for MB degradation. A reaction sequence for the catalytic activation of PMS was proposed. The as-prepared MnCo₂O_4.5 NPs could be reused for at least three consecutive cycles with small deterioration in their performance due to low metal leaching. This study suggests a facile route for synthesizing MnCo₂O_4.5 NPs with high catalytic activity for PMS activation and efficient degradation of organic dyes.

Catalytic degradation of organic dyes via manganese cobaltite nanoparticles-activated peroxymonosulfate.     

Gum acacia-based silver nanoparticles as a highly selective and sensitive dual nanosensor for Hg(ii) and fluorescence turn-off sensor for S2− and malachite green detection

A facile and green method was adopted to synthesize highly selective gum acacia-mediated silver nanoparticles as dual sensor (fluorescence turn-on and colorimetric) for Hg(ii) and fluorescence turn-off sensor for S²⁻ and malachite green. The mechanism proposed for a dual response towards Hg(ii) is the redox reaction between Ag(0) and Hg(ii), resulting in the formation of Ag(i) and Hg(0) and electron transfer from gum acacia to Ag(i), which further leads to the formation of an Ag@Hg nanoalloy. The enhanced fluorescence signal was quenched selectively by S²⁻ owing to the formation of Ag₂S and HgS. The reported nanosensor was found to be useful for sensing malachite green via the inner filter effect. The linear ranges were 3 nmol L⁻¹ to 13 μmol L⁻¹ for Hg(ii), 3–170 μmol L⁻¹ for S²⁻ and 7–80 μmol L⁻¹ for malachite green, and the corresponding detection limits were 2.1 nmol L⁻¹ for Hg(ii), 1.3 μmol L⁻¹ for S²⁻ and 1.6 μmol L⁻¹ for malachite green.

Gum acacia-stabilized silver nanoparticles for the detection of Hg(ii), S²⁻ and malachite green.     

Synthesis of Fe3O4@PVBC–TMT nanoparticles for the efficient removal of heavy metals ions

Core–shell magnetic Fe₃O₄@PVBC–TMT (Fe₃O₄@polyvinylbenzyl chloride–trithiocyanuric acid) nanoparticles containing trithiocyanuric acid groups were fabricated and employed for the fast removal of heavy metals from an aquatic environment. The morphology, structure and properties of Fe₃O₄@PVBC–TMT nanoparticles were characterized by a series of modern analytical tools. The adsorption behavior of the Fe₃O₄@PVBC–TMT nanoparticles for heavy metals ions in aqueous solutions was investigated by batch experiments. The maximum removal capacities of the Fe₃O₄@PVBC–TMT nanoparticles toward Mn²⁺, Ni²⁺, Cu²⁺, Cd²⁺ and Pb²⁺ ions were 127.4, 146.6, 180.5, 311.5, and 528.8 mg g⁻¹, respectively. Importantly, it is found that Pb²⁺ ions can be completely and quickly removed by the Fe₃O₄@PVBC–TMT nanoparticles. The equilibrium was established within 6 min, and the removal efficiencies were found to be 99.9%, 99.8% and 99.5% for Pb²⁺ ions at the initial concentrations of 100 mg L⁻¹, 200 mg L⁻¹ and 300 mg L⁻¹, respectively. It is hoped that the core–shell magnetic Fe₃O₄@PVBC–TMT nanoparticles may find application in wastewater treatment.

Core–shell Fe₃O₄@PVBC–TMT nanoparticles were fabricated and served as a valid magnetic adsorbent for the removal of heavy metals ions.     

Novel copper sulfide doped titania nanoparticles as a robust fiber coating for solid-phase microextraction for determination of polycyclic aromatic hydrocarbons

Immobilized TiO₂ nanoparticles modified by nanoscale CuS (CuS@TiO₂NPs) were successfully synthesized and used as fibers for solid-phase microextraction (SPME) for the determination of some polycyclic aromatic hydrocarbons (PAHs) in water samples. A novel fiber has been developed by postprecipitation of CuS coated the titania nanoparticles in situ grown on a titanium wire annealed at 550 °C in a nitrogen ambient atmosphere. Its morphology and surface properties were characterized by scanning electron microscopy and energy dispersive X-ray spectrometry. It was connected to high performance liquid chromatography-ultraviolet detector (HPLC-UV) equipment by replacing the sample loop of a six-port injection valve, building the online SPME-HPLC-UV system. Variables affecting extraction procedures, including desorption time, stirring speed, extraction temperature, extraction time and ionic strength were investigated and the parameters were optimized. The SPME fiber exhibits high selectivity for the five PAHs studied. The linear ranges varied between 0.15 μg L⁻¹ and 200 μg L⁻¹ with correlation coefficients ranging from 0.9913 to 0.9985. LODs and LOQs ranged from 0.02–0.04 μg L⁻¹ and 0.07–0.13 μg L⁻¹. RSDs for one fiber and fiber-to-fiber were in the range of 3.2–4.3% and 4.6–6.8%, respectively. Additionally, the fiber possessed advantages such as resistance to organic solvent, high mechanical strength and difficult breakage, making it have strong potential applications in the selective extraction of PAHs from complex water samples at trace levels.

Immobilized TiO₂ nanoparticles modified by nanoscale CuS (CuS@TiO₂NPs) were successfully synthesized and used as fibers for solid-phase microextraction (SPME) for the determination of some polycyclic aromatic hydrocarbons (PAHs) in water samples.     

Effect of lignocellulose-derived weak acids on butanol production by Clostridium acetobutylicum under different pH adjustment conditions

The effects of formic acid, acetic acid and levulinic acid on acetone–butanol–ethanol (ABE) fermentation under different pH adjustment conditions were investigated using Clostridium acetobutylicum as the fermentation strain. CaCO₃ supplementation can alleviate the inhibitory effect of formic acid on ABE production. The ABE titers from the medium containing 0.5 g L⁻¹ formic acid with pH adjusted by CaCO₃ and KOH were 11.08 g L⁻¹ and 1.04 g L⁻¹, which reached 64.8% and 6.3% of the control group, respectively. Compared with CaCO₃ pH adjustment, fermentation results with higher ABE titers and yields were obtained from the medium containing acetic acid or levulinic acid, when the pH was adjusted by KOH. When formic acid, acetic acid, and levulinic acid co-existed in the medium, better fermentation result was achieved by adjusting the pH by CaCO₃. Moreover, 12.50 g L⁻¹ ABE was obtained from the medium containing 2.0 g L⁻¹ acetic acid, 0.4 g L⁻¹ formic acid, and 1.0 g L⁻¹ levulinic acid as compared to 3.98 g L⁻¹ ABE obtained from the same medium when the pH was adjusted by KOH. CaCO₃ supplementation is a more favorable pH adjustment method for ABE medium preparation from lignocellulosic hydrolysate.

The effects of formic acid, acetic acid and levulinic acid on acetone–butanol–ethanol (ABE) fermentation under different pH adjustment conditions were investigated using Clostridium acetobutylicum as the fermentation strain.     

Effect of morphology on larvicidal activity of chemically synthesized zinc oxide nanoparticles against mosquito vectors

We report the larvicidal effects of four different morphologies of zinc oxide nanoparticles (ZnO NPs) [star-shaped (S), needle-like (N), plate-like (P) and cubical (C)] on larvae of Aedes albopictus and Anopheles vagus; the mosquitoes causing dengue fever and malaria, respectively. The nanoparticles were characterized by several analytical techniques, and their sizes and shapes were determined. Second instar larvae of the two types of mosquitoes were exposed to several concentrations of nanoparticles (25 mg L⁻¹, 50 mg L⁻¹, 75 mg L⁻¹, 100 mg L⁻¹) at 25 ± 2 °C and 84 ± 5% R.H, separately, for each morphology. Larval mortality was reported at 24 h intervals up to 21 days. The resulting LC₅₀ for Aedes albopictus were, respectively, 38.90 mg L⁻¹, 47.53 mg L⁻¹, 68.38 mg L⁻¹, 50.24 mg L⁻¹ for S-, N-, P- and C-shaped nanoparticles. The LC₅₀ of Anopheles vagus is lower (LC₅₀ 4.78 mg L⁻¹, 6.51 mg L⁻¹, 13.64 mg L⁻¹, 10.47 mg L_⁻¹), respectively, for S-, N-, P- and C-shaped nanoparticles indicating that the nanoparticles are more toxic to Anopheles vagus larvae. The highest larvicidal effect was obtained from star-shaped nanoparticles [Aedes albopictus (38.90 mg L⁻¹) on Anopheles vagus (4.78 mg L⁻¹)], and the lowest was shown by the plate-like nanoparticles [Aedes albopictus (68.38 mg L⁻¹), Anopheles vagus (13.64 mg L⁻¹)]. The rate of development of surviving mosquito larvae was retarded when exposed to ZnO nanoparticles suggesting the possibility for these nanoparticles to kill and delay the growth of Aedes albopictus and Anopheles vagus larvae.

We report the larvicidal impacts of four different morphologies of zinc oxide nanoparticles (ZnO NPs) [star-shaped (S), needle-like (N), plate-like (P), and cubical (C)] on mosquito larvae of Aedes albopictus and Anopheles vagus.     

In situ hydrothermal synthesis of nickel cobalt sulfide nanoparticles embedded on nitrogen and sulfur dual doped graphene for a high performance supercapacitor electrode

Nickel cobalt sulfide nanoparticles (NCS) embedded onto a nitrogen and sulfur dual doped graphene (NS-G) surface are successfully synthesized via a two-step facile hydrothermal process. The electrical double-layer capacitor of NS-G acts as a supporting host for the growth of pseudocapacitance NCS nanoparticles, thus enhancing the synergistic electrochemical performance. The specific capacitance values of 1420.2 F g⁻¹ at 10 mV s⁻¹ and 630.6 F g⁻¹ at 1 A g⁻¹ are achieved with an impressive capability rate of 76.6% preservation at 10 A g⁻¹. Furthermore, the integrating NiCo₂S₄ nanoparticles embedding onto the NS-G surface also present a surprising improvement in the cycle performance, maintaining 110% retention after 10 000 cycles. Owing to the unique morphology an impressive energy density of 19.35 W h kg⁻¹ at a power density of 235.0 W kg⁻¹ suggests its potential application in high-performance supercapacitors.

Newly developed in situ hydrothermal synthesis governs morphology of Ni–Co–S embedded on N–S doped graphene thus providing exceptional capacitive behavior.     

Silica-coated magnetic iron oxide functionalized with hydrophobic polymeric ionic liquid: a promising nanoscale sorbent for simultaneous extraction of antidiabetic drugs from human plasma prior to their quantitation by HPLC

Herein, silica-coated iron oxide nanoparticles modified with imidazolium-based polymeric ionic liquid (Fe₃O₄@SiO₂@PIL) were fabricated as a sustainable sorbent for magnetic solid-phase extraction (MSPE) and simultaneous determination of trace antidiabetic drugs in human plasma by high-performance liquid chromatography-ultraviolet detection (HPLC-UV). The Fe₃O₄ core was functionalized by silica (SiO₂) and vinyl layers where the ionic liquid 1-vinyl-3-octylimidazolium bromide (VOIM-Br) was attached through a free radical copolymerization process. In order to achieve hydrophobic magnetic nanoparticles and increase the merits of the sorbent, Br⁻ anions were synthetically replaced with PF₆⁻. The properties and morphology of the sorbent were characterized by various techniques and all the results illustrated the prosperous synthesis of Fe₃O₄@SiO₂@PIL. A comprehensive study was carried out to investigate and optimize various parameters affecting the extraction efficiency. The limit of detection (LOD, S/N = 3) for empagliflozin, metformin and canagliflozin was 1.3, 6.0 and 0.8 ng mL⁻¹, respectively. Linearity (0.997 ≥ r² ≥ 0.993) and linear concentration ranges of 5.0–1200.0, 20.0–1800.0 and 5.0–1000.0 ng mL⁻¹ were obtained for empagliflozin, metformin and canagliflozin, respectively. Intra-assay (3.8–7.5%, n = 9) and inter-assay (3.2–8.5%, n = 12) precisions as well as accuracies (≤9.1%) displayed good efficiency of the method. Finally, the method was applied for the quantitation of antidiabetic drugs in human plasma after oral administration and main pharmacokinetic data including T_max (h), C_max (ng mL⁻¹), AUC_0–24 (ng h mL⁻¹), AUC_0–∞ (ng h mL⁻¹), and T_1/2 (h) were evaluated.

A sustainable nanoscale core–shell modified with hydrophobic polymeric ionic liquid was fabricated for simultaneous extraction and determination of antidiabetic drugs.     

Identification of aldehyde oxidase 3 as a binding protein for squid ink polysaccharides using magnetic nanoparticles

To explore the interactive molecules of squid ink polysaccharides (SIP) for further understanding the action mechanisms of SIP bio-function, this study prepared SIP binding proteins from mouse liver using superparamagnetic nanometer beads. Michaelis–Menten constant (K_m) was detected from a Lineweaver–Burk double reciprocal plot to assess effect of SIP on activity of aldehyde oxidase (AOX). Results showed that three proteins, AOX-3, regucalcin (RGN) and α1-antitrypsin (A1AT3) were separated from mouse liver by magnetic nanoparticles conjugated with SIP. Contents of AOX-3 were much more than RGN and A1AT3. SIP (0.5 mg mL⁻¹) reduced K_m value of aldehyde oxidase of mouse liver from 91.79 μmol L⁻¹ to 43.70 μmol L⁻¹.

Superparamagnetic nanometer beads bonding SIP was employed to pull down the binding protein from the liver of mouse, which was identified as aldehyde oxidase 3. By means of enzyme kinetics analysis, SIP was found to activate AOX3 enzyme activity.     

Fullerene–porphyrin hybrid nanoparticles that generate activated oxygen by photoirradiation

The preparation of water-dispersible hybrid nanoparticles comprising fullerene and porphyrin from cyclodextrin complexes is described. In the presence of polyethylene glycol, C₆₀ fullerene and porphyrin were expelled from the cyclodextrin cavity to form fullerene–porphyrin hybrid nanoparticles in water. The fullerene–porphyrin hybrid nanoparticles exhibit improved singlet oxygen generation ability under photoirradiation compared with that of C₆₀ nanoparticles.

Hybrid nanoparticles comprising fullerene and porphyrin are formed via guest exchange reaction of cyclodextrin complexes. The hybrid nanoparticles exhibit singlet oxygen generation ability under photoirradiation.

Water-dispersible colloidal fullerene assemblies, referred to as fullerene nanoparticles (NPs), have recently received increasing attention.^1–3 Fullerene NPs are negatively charged and can be dispersed in water in the absence of any solubilizer. Fullerene NPs demonstrate promise within biological and medical applications, as radical scavengers and photosensitizers for photodynamic therapy. To further extend the applications of fullerene NPs, additional hybridization with desired functional molecules is required. Porphyrin and associated derivatives are highly promising candidates for hybridization with fullerenes to increase photoactivity.⁴ Numerous studies on the complexation of fullerenes with porphyrin molecules using synthetic organic chemistry^5–7 or supramolecular chemistry^8–10 have been reported. Although fullerene NPs have been intensively studied over the last decade, no reliable method to achieve the hybridization of porphyrins with fullerene NPs has been proposed.Poly(ethylene glycol) monomethyl ether (PEG) was recently observed to accelerate the decomposition of fullerene C₆₀–γ-CD complexes in water, which leads to the rapid aggregation of C₆₀ to form water-dispersible C₆₀ NPs.¹¹ In this method, C₆₀–γ-CD complexes can exist as stable isolated molecules in water, enabling the precise size control and step-wise growth of C₆₀ NPs.^12,13 Herein, the preparation of hybrid NPs comprising C₆₀ and hydrophobic porphyrin molecules are reported. C₆₀–γ-CD and porphyrin-trimethyl-β-cyclodextrin (por–TMe-β-CD) complexes are mixed in water in the presence of PEG. Both complexes decompose through the interaction of PEG with the CDs, leading to the formation of C₆₀–porphyrin hybrid NPs (denoted as C₆₀–por NPs). The C₆₀–por NPs are negatively charged and easily disperse in water. Additionally, the ability of C₆₀–por NPs to generate activated oxygen is also evaluated.The C₆₀–γ-CD complex^14,15 and 1–TMe-β-CD complex (Fig. 1)^16–18 were prepared according to a previously described procedure (see the ESI^† for details). The ¹H NMR spectrum of the mixed solution comprising the C₆₀–γ-CD complex and PEG after 1 h incubation at 80 °C shows that the peaks attributed to the C₆₀–γ-CD complexes completely disappeared (Fig. S1^†). Hence, the ¹H NMR data confirm the decomposition of the C₆₀–γ-CD complexes and the formation of water-dispersible C₆₀ NPs, as previously reported.^11–13 The effect of PEG on 1–TMe-β-CD complexes was also investigated by ¹H-NMR as shown in Fig. S2.^† After incubating the mixed solution of 1–TMe-β-CD complex and PEG ([1] = 0.1 mM, [PEG] = 5.0 g L⁻¹) for 1 h at room temperature, peaks attributed to the 1–TMe-β-CD complex were still evident at 4.97 ppm and above 7.7 ppm (Fig. S2(i)^†). Hence, PEG has no influence upon the 1–TMe-β-CD structure at room temperature. Conversely, after incubating for 1 h at 80 °C, a dark purple precipitate formed and the aforementioned ¹H NMR peaks completely disappeared (Fig. S2(ii)^†). In the absence of PEG, the 1–TMe-β-CD complex was stable in water both at room temperature (Fig. S2(iii)^†) and 80 °C (Fig. S2(iv)^†). These results suggest a decomposition route of 1–TMe-β-CD by interaction with PEG at 80 °C, with a concomitant formation of non-dispersible large aggregates.Open in a separate windowFig. 1Chemical structures of porphyrin derivatives used in this study.To obtain hybrid NPs comprising C₆₀ and 1 (C₆₀–1 NPs), PEG (M_w = 2000) was added to an aqueous solution containing C₆₀–γ-CD and 1–TMe-β-CD complexes ([C₆₀] = [1] = 0.1 mM, [PEG] = 5.0 g L⁻¹), which were thereafter incubated at room temperature or 80 °C. The ¹H NMR spectrum of the mixed solution at room temperature shows peaks attributed to γ-CD in the C₆₀–γ-CD complex at 5.03 ppm, TMe-β-CD in the 1–TMe-β-CD complex at 4.97 ppm, and 1 in the 1–TMe-β-CD complex in the region of 7.6–8.5 ppm (Fig. 2a(i)). The data indicate that PEG fails to induce the decomposition of the C₆₀–γ-CD and 1–TMe-β-CD complexes at room temperature. Conversely, after the mixture was heated at 80 °C for 1 h, the peaks attributed to the C₆₀–γ-CD and 1–TMe-β-CD complexes completely disappeared (Fig. 2a(ii)). Hence, C₆₀–γ-CD and 1–TMe-β-CD were decomposed at 80 °C, in the presence of PEG. The solution after being subjected to heat treatment at 80 °C for 1 h, was dark purple in the absence of any precipitate. The hydrodynamic diameter and ζ-potential of the reacted solution were 125 nm (polydispersity index = 0.21) and −20.2 mV, respectively. Water dispersible fullerene NPs typically exhibit negative ζ-potentials, the origin of which still requires elucidating.^19,20 Hence, the formation of water-dispersible nano-composites, C₆₀–1 NPs, is suggested.Open in a separate windowFig. 2(a) ¹H NMR spectra of mixed solutions comprising fullerene C₆₀–γ-cyclodextrin (CD) and 1–trimethyl (TMe)-β-CD complexes ([C₆₀] = [1] = 0.1 mM) (i) before and (ii) after heating at 80 °C for 1 h, in the presence of polyethylene glycol (PEG) (5 g L⁻¹). Open circles: free γ-CD, filled circles: C₆₀–γ-CD, open diamonds: free TMe-β-CD, and filled diamonds: porphyrin–TMe-β-CD (por–TMe-β-CD) complex. The spectra at 7.6–8.5 ppm, are amplified five-fold. (b) Ultraviolet-visible (UV/Vis) absorption spectra of the mixed solution comprising C₆₀–γ-CD and 1–TMe-β-CD complexes ([C₆₀] = [1] = 0.1 mM) with PEG (5 g L⁻¹), before (dashed line) and after (solid line) heating at 80 °C for 1 h. (c) UV/Vis absorption spectra of the mixed solution comprising the C₆₀–γ-CD complex as a function of the 1–TMe-β-CD complex concentration ([C₆₀] = 0.1 mM, [1] = 0–0.2 mM) with PEG (5 g L⁻¹) after heating at 80 °C for 1 h.The por–TMe-β-CD complexes using 2–6 (Fig. 1), were also prepared adopting the same procedure as that for the 1–TMe-β-CD complex. Each por–TMe-β-CD complex solution was mixed with C₆₀–γ-CD and PEG ([C₆₀] = [por] = 0.1 mM, [PEG] = 5.0 g L⁻¹). The ¹H NMR spectrum of each individual mixed solution after being incubated for 1 h at 80 °C, is shown in Fig. S3.^† In the ¹H NMR spectrum of the mixture comprising C₆₀–γ-CD and 2–TMe-β-CD, the peaks attributed to these complexes at 5.03, 4.98, and 7.60–8.50 ppm, completely disappeared after being subjected to incubation for 1 h at 80 °C, without precipitation (Fig. S3a^†). Similar changes in the ¹H NMR spectrum of the mixture comprising C₆₀–γ-CD and 3–TMe-β-CD complexes are observed, as shown in Fig. S3b.^† The data suggest that the 2–TMe-β-CD and 3–TMe-β-CD complexes can be decomposed in a similar manner as the C₆₀–γ-CD complexes, and imply the formation of C₆₀–2 and C₆₀–3 NPs.The ¹H NMR spectra of the mixed solutions comprising C₆₀–γ-CD and 4, 5, or 6–TMe-β-CD complexes failed to show peaks attributed to the C₆₀–γ-CD complex, and peaks associated with the respective por–TMe-β-CD complexes were observed after incubation for 1 h at 80 °C (Fig. S3c–e,^† respectively). Hence, the data suggest that the C₆₀–γ-CD complex decomposed in the presence of PEG, and the 4, 5, and 6–TMe-β-CD complexes were observed to be stable without decomposition at 80 °C. There have been reports suggesting the strong interaction of water-soluble tetraphenyl porphyrins with TMe-β-CDs.^21,22 Polar substituents prompt the penetration of the polarized porphyrin rims into the TMe-β-CD cavity. Porphyrins 4–6 possess polar substituents, which are suggested to enable the formation of stable TMe-β-CD complexes. Furthermore, the size of the β-CD cavity is sufficiently narrow to prevent any strong interaction with PEG.²³ Thus, PEG-induced decomposition of the 4, 5, and 6–TMe-β-CD complexes is not possible.The absorption behavior of C₆₀–1 NPs was investigated using ultraviolet-visible (UV/Vis) spectroscopy. In the UV/Vis spectra, the characteristic peak of solvated C₆₀–γ-CD, at 333 nm shifted to 344 nm after heating at 80 °C for 1 h (Fig. 2b). An additional broad absorption at 400–550 nm is also apparent, which is characteristic of solid-state crystalline C₆₀ and arises from the electronic interactions between adjacent C₆₀ molecules.^24,25 The characteristic peak of the solvated 1–TMe-β-CD complex at 415 nm, shifted to 432 nm, with induced broadening after being subjected to heat treatment at 80 °C for 1 h (Fig. 2b). In the absence of C₆₀–γ-CD complexes, the characteristic absorption peak attributed to the solvated 1–TMe-β-CD complex completely disappeared after heating for 1 h at 80 °C, in the presence of PEG (Fig. S4^†). The data show that 1, when expelled from the TMe-β-CD cavities, forms non-dispersible precipitates in the absence of C₆₀. For 1 dispelled from the TMe-β-CD cavities to be stably dispersed in water, formation of co-aggregates with C₆₀ may be a prerequisite. C₆₀–2 and C₆₀–3 NPs also show similar UV-Vis absorption spectra after being subjected to heating at 80 °C for 1 h, as shown in Fig. S5a and b,^† respectively.To further elucidate the composite formation of C₆₀ and 1, the influence of 1 concentration on C₆₀–1 NP formation was investigated by UV/Vis spectroscopy (Fig. 2c). The intensity of the absorption peak at 432 nm increased as a function of 1 concentration from 0.05 to 0.1 mM. Conversely, the absorption peak at 345 nm, derived from the formation of fullerene NPs, shifted to 338 nm, with increasing concentration of 1. This absorption peak derives from the fullerene nanoparticle size, and as the size decreased (i.e., the NPs became smaller), the peak blue-shifted.¹¹ The results suggest that in the presence of 1, the fullerene interaction might be disturbed, or smaller C₆₀ NPs might form. For C₆₀–1 NPs formulated with 0.2 mM of 1 ([C₆₀] = 0.1 mM, [1] = 0.2 mM), the absorption peak derived from the Soret band of 1 split into two peaks (Fig. 2c). The absorption peak at the shorter wavelength of 415 nm is consistent with that of the 1–TMe-β-CD complex. The absorption peak at the longer wavelength of 431 nm is almost consistent with the absorption peaks in the UV/Vis spectra of C₆₀–1 NPs fabricated with 0.05 and 0.1 mM of 1. The findings indicate that in the sample comprising 0.2 mM of 1, a portion of the 1–TMe-β-CD complexes remained in the complex state after heating for 1 h at 80 °C, in the presence of PEG. The absorption peak at 338 nm, which reflects the state of fullerene NPs, is similar to that of C₆₀–1 NPs fabricated with 0.1 mM of 1. When C₆₀ and 1 form co-aggregated NPs, the ratio of 1 to C₆₀ is thought to be limited to ∼1 : 1.Morphological observations of the hybrid NPs were also undertaken. In the absence of the por–TMe-β-CD complex, C₆₀ NPs possessing fairly monodisperse size distributions were observed (Fig. S6a^†). The average diameter of the individual NPs, determined from the transmission electron microscopy (TEM) images, is 82 nm. C₆₀ NPs have been previously reported to exhibit lattice fringes and diffraction patterns, which suggests that C₆₀ NPs maintain the face-centered cubic (fcc) crystalline structure.¹¹ C₆₀–1 NPs prepared with 0.05 mM C₆₀ and 0.1 mM 1, possessed irregular shapes (Fig. 3a and b, respectively). The average diameter of C₆₀–1 NPs, determined by TEM, is 119 nm (Fig. 3a and S6b^†), demonstrating the larger C₆₀–1 NP size than that of the C₆₀ NPs (82 nm). Increasing the concentration of 1 to 0.1 mM results in the average diameter of C₆₀–1 NPs to increase to 131 nm (Fig. 3b and S6c^†). Similar morphology is observed from the TEM micrographs of C₆₀–2 and C₆₀–3 NPs having average diameters of 109 nm and 144 nm, respectively (Fig. 3c and d, respectively). A lower PEG molecular weight or a lower reaction temperature during C₆₀ NP formation via C₆₀–γ-CD complexes have been reported to induce an increase in the diameter of the C₆₀ NPs.^11,12 Thus, the findings suggest that slower reaction conditions result in less nucleation and a larger NP formation. Porphyrin 3 possesses a methoxy substituent at the para position of the phenyl group and is more polar than 1 or 2. Previous reports have demonstrated that the higher the polarity of the phenyl group, the more stable the complex with TMe-β-CD,^21,22 which indicates that 3–TMe-β-CD is more stable than 1– or 2–TMe-β-CD in water. Thus, the aforementioned decomposition, which results from the interaction with PEG, is slower in 3 with a concomitant increase in the NP size.Open in a separate windowFig. 3Transmission electron microscopy (TEM) images of C₆₀–1 nanoparticles (NPs) prepared with (a) 0.05 and (b) 0.1 mM of the 1–TMe-β-CD complex. TEM images of (c) C₆₀–2 and (d) C₆₀–3 NPs. Scale bars in images (a–d) are 100 nm. (e) High resolution TEM micrograph and selected-area electron diffraction pattern of C₆₀–1 NP. Scale bar is 10 nm. (f) ¹³C NMR spectra of (i) C₆₀ NPs and (ii) C₆₀–1 NPs. (g) Illustration of a C₆₀–por NP. A portion of C₆₀ form crystalline structures, while a portion of the porphyrin molecules interact with C₆₀ at the molecular level.In the high-resolution TEM micrograph (Fig. 3e), the C₆₀–1 NPs only exhibited partial lattice fringes, and hence did not show clear diffraction patterns compared with the C₆₀ NPs (inset in Fig. 3e).¹¹ The findings demonstrate the highly amorphous nature of the C₆₀–1 NPs, and that the C₆₀ crystal structure was only retained in part. ¹³C NMR spectra also provide important information about the structure of the C₆₀–1 NPs. A characteristic C₆₀ cluster signal at 142.4 ppm was detected in both C₆₀ NPs and C₆₀–1 NPs (Fig. 3f).²⁶ The C₆₀–1 NP dispersions also exhibited several small new signals at 141.5, 143.3, and 143.7 ppm, as shown in Fig. 3f(ii). When a fullerene and a porphyrin molecule form a stable complex in solution, the C₆₀ signal shifts depending on the interaction type between the fullerene and the porphyrin molecule.²⁷ Thus, the porphyrin molecule interacted with the aggregate of C₆₀ in C₆₀–1, as illustrated in Fig. 3g.Some porphyrin molecules can form a co-crystal with fullerene C₆₀.²⁸ To form a crystal structure, not only the interaction between molecules but also the relationship with the solvent, such as gradually changing the polarity of the solvent or removing the solvent, are important. In our system, porphyrin molecules that are pseudo-dissolved by TMe-β-CDs are added to water, which is a poor solvent for porphyrins, through the interaction of PEG with TMe-β-CDs. The porphyrin molecule should immediately aggregate and have difficulty forming a crystal structure. Furthermore, because water is also a poor solvent for fullerene C₆₀, C₆₀ also immediately aggregates in water. Thus, it should be extremely difficult for C₆₀ and porphyrin molecules to regularly associate to form a co-crystal structure.The concentration of singlet oxygen molecules (¹O₂, Type-II energy transfer pathway) generated by photoirradiation was measured according to a chemical method using 9,10-anthracenediyl-bis(methylene) dimalonic acid (ABDA)^15,29 as a marker to determine the biological activities of C₆₀ NPs, C₆₀–1 NPs, C₆₀–2 NPs, and C₆₀–3 NPs. The absorption of ABDA at the absorption maximum (380 nm) was monitored as a function of irradiation time ([C₆₀] = 0.1 mM, [por] = 0 or 0.1 mM). Under visible-light irradiation at wavelengths > 620 nm, C₆₀–1 NPs, C₆₀–2 NPs, and C₆₀–3 NPs generated higher levels of ¹O₂ than C₆₀ (Fig. 4a). These results show that the ¹O₂ photoproduction abilities of the C₆₀–por NPs were higher than that of the C₆₀ NPs. There are no significant differences in the ¹O₂ photoproduction abilities of C₆₀–1 NPs, C₆₀–2 NPs, and C₆₀–3 NPs, which suggests that the structure of the porphyrin has an insignificant influence on the ability of the hybrid NPs. The generation of formazan, via the reduction of nitroblue tetrazolium (NBT) by oxygen radicals (O₂˙⁻), is observed as an increase of absorption intensity at 560 nm.³⁰ The reduction of NBT by O₂˙⁻ was scarcely detected in solutions containing C₆₀–1 NPs, C₆₀–2 NPs, and C₆₀–3 NPs under photoirradiation, even though formazan was readily detected in the positive control sample in the presence of reduced nicotinamide adenine dinucleotide (NADH) (Fig. 4b). The results suggest that the reactive oxygen species produced by C₆₀–1 NPs, C₆₀–2 NPs, and C₆₀–3 NPs are predominantly ¹O₂ generated by a Type-II reaction.¹⁸Open in a separate windowFig. 4(a) ¹O₂ generation by NPs. Bleaching of 9,10-anthracenediyl-bis(methylene) dimalonic acid (ABDA) was monitored as a function of the decrease in the absorbance at 380 nm, for C₆₀ NPs (black circles and solid line), C₆₀–1 NPs (red circles and solid line), C₆₀–2 NPs (blue circles and solid line), and C₆₀–3 NPs (green circles and solid line) ([C₆₀] = 15 μM, [por] = 0 or 15 μM, [ABDA] = 25 μM). (b) O₂˙⁻ generation by NPs. The amount of formazan generated by the reduction of nitroblue tetrazolium (NBT) in the presence of O₂˙⁻ was analyzed by the absorbance at 560 nm, of C₆₀–1 NPs (red circles) and C₆₀–2 NPs (blue circles) in the absence (solid lines) and presence (dashed lines) of NADH ([C₆₀] = 15 μM, [por] = 15 μM, [NBT] = 200 μM, [NADH] = 0 or 625 μM). All samples were photoirradiated at >620 nm, in O₂-saturated aqueous solutions.In summary, the preparation of hybrid C₆₀–porphyrin NPs was achieved via a guest exchange reaction comprising porphyrin CD complexes and C₆₀. Seven C₆₀–por NP derivatives with various moieties were prepared. CD porphyrin complexes possessing phenyl and methoxyphenyl moieties were decomposed in the presence of PEG at the same time as C₆₀–γ-CD complexes and formed NPs with C₆₀. Porphyrins containing a hydrophilic moiety form stable complexes with TMe-β-CD and fail to co-aggregate with C₆₀. The C₆₀–por NPs are negatively charged and are easily dispersed and stable in water. The ¹O₂ generation ability of C₆₀–por NPs under photoirradiation (>620 nm) is greater than that of C₆₀ NPs. The findings herein demonstrate a new method to fabricate fullerene–porphyrin composite materials, which provides a route to highly functional fullerene-based materials.     

Ag decorated silica nanostructures for surface plasmon enhanced photocatalysis

In this article, we present a novel synthesis of mesoporous SiO₂/Ag nanostructures for dye (methylene blue) adsorption and surface plasmon mediated photocatalysis. Mesoporous SiO₂ nanoparticles with a pore size of 3.2 nm were synthesized using cetyltrimethylammonium bromide as a structure directing agent and functionalized with (3-aminopropyl)trimethoxysilane to introduce amine groups. The adsorption behavior of non-porous SiO₂ nanoparticles was compared with that of the mesoporous silica nanoparticles. The large surface area and higher porosity of mesoporous SiO₂ facilitated better adsorption of the dye as compared to the non-porous silica. Ag decorated SiO₂ nanoparticles were synthesized by attaching silver (Ag) nanoparticles of different morphologies, i.e. spherical and triangular, on amine functionalized silica. The photocatalytic activity of the mesoporous SiO₂/Ag was compared with that of non-porous SiO₂/Ag nanoparticles and pristine Ag nanoparticles. Mesoporous SiO₂ nanoparticles (k_d = 31.3 × 10⁻³ g mg⁻¹ min⁻¹) showed remarkable improvement in the rate of degradation of methylene blue as compared to non-porous SiO₂ (k_d = 25.1 × 10⁻³ g mg⁻¹ min⁻¹) and pristine Ag nanoparticles (k_d = 19.3 × 10⁻³ g mg⁻¹ min⁻¹). Blue Ag nanoparticles, owing to their better charge carrier generation and enhanced surface plasmon resonance, exhibited superior photocatalysis performance as compared to yellow Ag nanoparticles in all nanostructures.

In this article, we present a novel synthesis of mesoporous SiO₂/Ag nanostructures for dye (methylene blue) adsorption and surface plasmon mediated photocatalysis.     

Surface blocking of azolla modified copper electrode for trace determination of phthalic acid esters as the molecular barricades by differential pulse voltammetry: response surface modelling optimized biosensor

In this work, a sensitive and efficient voltammetric biosensor was introduced for differential pulse voltammetric (DPV) determination of some phthalic acid esters (PAEs) including dibutyl phthalate (DBP), dimethyl phthalate (DMP), di(2-ethylhexyl)phthalate (DEHP) and dicyclohexyl phthalate (DCHP) in aqueous solutions. Briefly, the surface of a copper electrode was modified by azolla paste prepared using azolla powder and electroencephalography gel (EEG). The modified surface was characterized by electrochemical impedance spectroscopy (EIS), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), Brunauer–Emmett–Teller (BET) analysis and energy dispersive X-ray (EDX) methods. Determination of PAEs was conducted based on their blocking effect on the electrode surface for ferrous ion oxidation. The central composite design (CCD) was conducted to optimize the effects of four experimental parameters including the concentration of Fe²⁺ ions (C_Fe²⁺) and supporting electrolyte (C_{sup. elec}), solution pH and modifier/gel mass ratio on the decrease in the anodic peak current of ferrous ions as the response. Predicted optimal conditions (C_Fe²⁺= 319 μM, C_{sup. elec}= 0.125 M, pH = 7.52 and modifier/gel mass ratio = 0.19) were validated by experimental checking which resulted in an error of 1.453%. At the optimum conditions, linear relationships were found between the DPV responses and PAEs concentrations and the limit of detection (LOD) and limit of quantification (LOQ) values were in the ranges of 0.2–0.4 μg L⁻¹ and 0.5–1.0 μg L⁻¹, respectively. Good recovery percentages ranging from 97.3 to 100.3% with RSD < 3.2% suggested the proposed method for efficient, accurate and quick determination of PAEs in real water samples.

In this work, a sensitive and efficient voltammetric biosensor was introduced for differential pulse voltammetric (DPV) determination of dibutyl phthalate, dimethyl phthalate, di(2-ethylhexyl)phthalate and dicyclohexyl phthalate in aqueous solutions.