A co-assembly process for high strength and injectable dual network gels with sustained doxorubicin release performance.

Adopting a non-covalent co-assembly strategy shows great potential in loading drugs efficiently and safely in drug delivery systems. However, finding an efficient method for developing high strength gels with thixotropic characteristics is still challenging. In this work, by hybridizing the low molecular weight gelator fluorenylmethyloxycarbonyl-phenylalanine (Fmoc-F) (first single network, 1st SN) and alginate (second single network, 2nd SN) into a dual network (DN) gel, gels with high strength as well as thixotropy were prepared efficiently. The DN gels showed high strength (103 Pa in SN gels and 105 Pa in DN gels) and thixotropic characteristics (yield strain <25%; recovery ratio >85% within 100 seconds). The application performance was verified by loading doxorubicin (DOX), showing better encapsulation capacity (77.06% in 1st SN, 59.11% in 2nd SN and 96.71% in DN) and sustained release performance (lasting one week under physiological conditions) than single network gels. Experimental and DFT results allowed the elaboration of the specific non-covalent co-assembly mechanism for DN gel formation and DOX loading. The DN gels were formed by co-assembly driven by H-bond and π-π stacking interactions and then strengthened by Ca2+-coupling. Most DOX molecules co-assembled with Fmoc-F and alginate through π-π stacking and H-bond interactions (DOX-I), with a few free DOX molecules (DOX-II) left. Proven by the release dynamics test, DOX was released through a diffusion-erosion process, in an order of DOX-I first and then DOX-II. This work suggests that non-covalent co-assembly is a useful technique for effective material strengthening and drug delivery.

Environment-Friendly Carbon Quantum Dots/ZnFe2O4 Photocatalysts: Characterization, Biocompatibility, and Mechanisms for NO Removal.

A highly efficient and environmentally-friendly oxidation process is always desirable for air purification. This study reported a novel carbon quantum dots (CQDs)/ZnFe2O4 composite photocatalyst for the first time through a facile hydrothermal process. The CQDs/ZnFe2O4 (15 vol %) composite demonstrates stronger transient photocurrent response, approximately 8 times higher than that of ZnFe2O4, indicating superior transfer efficiency of photogenerated electrons and separation efficiency of photogenerated electron-hole pairs. Compared with pristine ZnFe2O4 nanoparticles, CQDs/ZnFe2O4 displayed enhanced photocatalytic activities on gaseous NOx removal and high selectivity for nitrate formation under visible light (λ > 420 nm) irradiation. Electron spin resonance analysis and a series of radical-trapping experiments showed that the reactive species contributing to NO elimination were ·O2- and ·OH radicals. The possible mechanisms were proposed regarding how CQDs improve the photocatalytic performance of ZnFe2O4. The CQDs are believed to act as an electron reservoir and transporter as well as a powerful energy-transfer component during the photocatalysis processes over CQDs/ZnFe2O4 samples. Furthermore, the toxicity assessment authenticated good biocompatibility and low cytotoxity of CQDs/ZnFe2O4. The results of this study indicate that CQDs/ZnFe2O4 is a promising photocatalyst for air purification.

Molecular structure-dependent contribution of reactive species to organic pollutant degradation using nanosheet Bi2Fe4O9 activated peroxymonosulfate.

Iron-based catalysts have attracted increasing attention in heterogeneous activation of peroxymonosulfate (PMS). However, the activity of most iron-based heterogenous catalysts is not satisfactory for practical application and the proposed activation mechanisms of PMS by iron-based heterogenous catalyst vary case by case. This study prepared Bi2Fe4O9 (BFO) nanosheet with super high activity toward PMS, which was comparable to its homogeneous counterpart at pH 3.0 and superior to its homogeneous counterpart at pH 7.0. Fe sites, lattice oxygen and oxygen vacancies on BFO surface were believed to be involved in the activation of PMS. By using electron paramagnetic resonance (EPR), radical scavenging tests, 57Fe Mössbauer and 18O isotope-labeling technique, the generation of reactive species including sulfate radicals, hydroxyl radicals, superoxide and Fe (IV) were confirmed in BFO/PMS system. However, the contribution of reactive species to the elimination of organic pollutants very much depends on their molecular structure. The effect of water matrices on the elimination of organic pollutants also hinges on their molecular structure. This study implies that the molecular structure of organic pollutants governs their oxidation mechanism and their fate in iron-based heterogeneous Fenton-like system and further broadens our knowledge on the activation mechanism of PMS by iron-based heterogeneous catalyst.

Oxygen vacancy mediated α-MoO3 bactericidal nanocatalyst in the dark: Surface structure dependent superoxide generation and antibacterial mechanisms.

Understanding bacteria inactivation mechanisms of nanomaterials on the surface molecular level is of prime importance for the development of antibacterial materials and their application in restraining the transmission of pathogenic microorganisms. This study prepared an oxygen vacancy-mediated bactericidal nanocatalyst α-MoO3 which exhibited excellent antibacterial activity against Escherichia coli and Staphylococcus aureus in the dark. By manipulating the surface structure of α-MoO3, the facile tuning of superoxide radical (•O2-) generation can be achieved, which was confirmed by electron paramagnetic resonance. •O2- disrupted bacterial membrane through attacking lipopolysaccharide (LPS) and phosphatidylethanolamine (PE). Intracellular reactive oxygen species (ROS) experiments confirm that oxidative stress induced by •O2- also played a vital role in bacterial inactivation, which might account for DNA damage verified by comet assays. The α-MoO3 with rich oxygen vacancies also exhibited good antibacterial efficiency (＞99.00 %) toward airborne microbes under dark conditions, indicating its potential to impede the transmission of pathogenic microbes.

Photodegradation of N-nitrosodimethylamine under 365 nm Light Emitting Diode Irradiation.

The photodegradation of NDMA has been extensively investigated under the irradiation of low-pressure or medium-pressure Hg lamps and xenon lamp. However, NDMA photolysis remains unknown under 365 nm ultraviolet light-emitting diode (UV-LED) irradiation. This study conducted a comprehensive investigation on NDMA photodegradation by 365 nm UV-LED illumination. The quantum yield of NDMA photolysis under 365 nm UV-LED irradiation was determined to be 0.0312 ± 0.0047. The influence of pH on NDMA photodegradation was found to be wavelength dependent. Compared with distilled and deionized water (DDW), tap water inhibited NDMA photodegradation, but secondary wastewater effluent did not. Based on the quantification of NDMA photolysis products and pH influence, the photooxidation of the excited NDMA in the nonprotonated form was proposed to be a major pathway for NDMA photodegradation under the irradiation of UV-LED lamp at 365 nm. This study further enhances our knowledge on NDMA photodegradation. PRACTITIONER POINTS: Quantum yield of NDMA photolysis at 365 nm was determined to be 0.0312 ± 0.0047. The influence of pH on NDMA photodegradation was wavelength dependent. NDMA photodegradation was inhibited in tap water compared with that in DDW. NDMA photodegradation in SWE was similar to that in DDW. Excited nonprotonated NDMA photooxidation is a major degradation pathway.

Magnetically assembled electrodes based on Pt, RuO2-IrO2-TiO2 and Sb-SnO2 for electrochemical oxidation of wastewater featured by fluctuant Cl- concentration.

Magnetically assembled electrode (MAE) flexibly attracts magnetic particles (auxiliary electrodes, AEs) on a main electrode (ME) by the magnetic force, where the role of ME is always ignored. In this study, Ti/Pt, Ti/RuO2-IrO2-TiO2 and Ti/Sb-SnO2 were selected as the ME for comparison in treating synthetic wastewater (acid red G or phenol) with variable Cl- content. The effects of ME type, loading amount of Fe3O4/Sb-SnO2 AEs, and Cl- concentration were investigated, followed by varied electrochemical characterizations. Results show that AEs played a vital role in electrode activity and selectivity, and MEs also exerted an unignorable influence on the performance of the MAEs. Among the three MEs, Ti/RuO2-IrO2-TiO2 has the best OER/CER ability, activating more extra active sites with same AEs loading amount, leading to higher organics degradation efficiency under chlorine-free condition. However, this MAE is featured by the noticeable accumulation of intermediate products under chlorine-free condition even if 0.3 g·cm-2 of AEs are loaded. All electrodes' performances were enhanced in the presence of Cl-. With high concentration chloride (0.5 M NaCl), the accumulation of intermediate products was reduced significantly, especially on Ti/RuO2-IrO2-TiO2 based MAE, and no chlorinated compound was identified. Finally, the structure-activity relationships of these MAEs were proposed.

The oxidative degradation of Caffeine in UV/Fe(II)/persulfate system-Reaction kinetics and decay pathways.

In this study, the degradation of caffeine was investigated by UV/Fe2+ /persulfate (PS) process. Caffeine (CAF) degradation in sole-UV, UV/Fe2+ , UV/PS, and Fe2+ /PS systems was also conducted to examine the contribution of isolated processes to CAF degradation. The effects of pH levels, the concentration of Fe2+ and PS, inorganic anions, and initial concentration of CAF on the performance of UV/Fe2+ /PS process were evaluated. Radical competitive reactions indicated both hydroxyl radicals and sulfate radicals played important roles in CAF degradation in UV/Fe2+ /PS system. Nine intermediates, among which three were detected for the first time, were identified by ultra-performance liquid chromatography/electrospray-time-of-flight mass spectrometry (UPLC/ESI-TOF-MS) and SPME (solid-phase microextraction)/GC/MS. The possible degradation pathways of CAF were proposed, among which demethylation, hydroxylation, the oxidation of olefinic double bond, and the cleavage of pyrimidine ring and imidazole ring were involved in the degradation of CAF in UV/Fe2+ /PS system. PRACTITIONER POINTS: Caffeine degradation by UV/Fe2+ /PS process was investigated. Caffeine degradation did not follow a simple pseudo-first order kinetics Chloride ions promoted CAF degradation. The anions NO3 - , SO4 2- , and H2 PO4 - exerted a negative influence on caffeine degradation. Nine intermediates were detected, and decay pathways were proposed.

Efficient degradation of diclofenac by LaFeO3-Catalyzed peroxymonosulfate oxidation---kinetics and toxicity assessment.

Diclofenac was frequently found in various waters, indicating conventional wastewater treatment methods ineffective in its removal. In this study, LaFeO3 (LFO) was synthesized and its catalytic activity of LFO as the activator of different oxidants such as persulfate (PS), hydrogen peroxide and peroxylmonosulfate (PMS) was evaluated in terms of DCF degradation. The influence of calcination temperature was examined on the catalytic activity of LFO. The effects of various parameters including pH levels, PMS concentration, LFO dose and initial DCF concentration were investigated on DCF degradation rate. The marginal effects of PMS concentration and LFO dose were compared. Langmuir-Hinshelwood (LH) model was used to quantitatively describe DCF degradation reaction in LFO/PMS system. The two constants, k (Limiting reaction rate at maximum coverage) and K (Equilibrium adsorption constant), were determined on the basis of LH model. The performance of LFO/PMS process was also estimated in the presence of various inorganic anions. The potential toxicity of LFO and PMS were evaluated using phytoplankton and the toxicity evolution during DCF degradation was also investigated using luminescent bacteria. This contribution provides a basic study regarding the potential application of heterogeneous PMS activation by perovskite LFO for both DCF removal and toxicity elimination.

Sonolytic and sonophotolytic degradation of Carbamazepine: Kinetic and mechanisms.

An in-depth investigation on the ultrasonic decomposition of Carbamazepine (CBZ), one of the most regularly identified drugs in the environment, was conducted. The effects of diverse variables were evaluated, such as frequency, power, solution pH, initial CBZ concentration and varied inorganic anions. Reaction order was determined on the basis of analyzing reaction kinetics of CBZ degradation. The sonophotolysis and photolysis of CBZ was also examined in this contribution. The influence of water composition on the sonolytic and sonophotolytic elimination of CBZ was analyzed. Additionally, 21 intermediates were identified during sonolytic degradation of CBZ based on LC/ESI-MS/MS analysis, among which two escaped from the detection in previous studies. Possible decay pathways were proposed accordingly. The epoxidation, cleavage of double bond, hydration, hydroxylation, ring contraction and intramolecular cyclization were believed to be involved in sonochemical degradation of CBZ.

Removal of simazine in a UV/TiO2 heterogeneous system.

The degradation of simazine by photocatalytic oxidation in a TiO2 suspension was studied. The influence of various parameters such as wavelength sources, light intensity, TiO2 dosage, and initial pH has been investigated, and the optimum conditions for the degradation of simazine have been identified. The photocatalytic degradation of simazine was observed to follow a pseudo-first-order reaction. The overdose of light intensity and photocatalyst does not always guarantee a beneficial effect on the photocatalytic reaction, and the optimum TiO2 dosage was found to be 0.1 g/L in this study. The optimum pH value is 9.0 for the photocatalytic degradation of simazine, whereas extremely acidic and alkaline conditions inhibit photocatalytic efficiency. Simazine can be fully destroyed, but ring-opening and mineralization are not observed in this system. In addition, seven simazine derivatives (CEAT, OEET, CAAT, ODET, OEAT, OAAT, OOOT) were detected by LC-ESI/MS. It is suggested that dealkylation is the major pathway of simazine photodecay in UV/TiO2 systems. The final product was found to be cyanuric acid.