Treatment of pharmaceutical industry wastewater for water reuse in Jordan using hybrid constructed wetlands.

Developing cost-efficient wastewater treatment technologies for safe reuse is essential, especially in developing countries simultaneously facing water scarcity. This study developed and evaluated a hybrid constructed wetlands (CWs) approach, incorporating tidal flow (TF) operation and utilising local Jordanian zeolite as a wetland substrate for real pharmaceutical industry wastewater treatment. Over 273 days of continuous monitoring, the results revealed that the first-stage TFCWs filled with either raw or modified zeolite performed significantly higher reductions in Chemical Oxygen Demand (COD, 58 %-60 %), Total Nitrogen (TN, 32 %-37 %), and Phosphate (PO4, 46 %-64 %) compared to TFCWs filled with normal sand. Water quality further improved after the second stage of horizontal subsurface flow CWs treatment, achieving log removals of 1.09-2.47 for total coliform and 1.89-2.09 for E. coli. With influent pharmaceutical concentrations ranging from 275 to 2000 µg/L, the zeolite-filled hybrid CWs achieved complete removal (>98 %) for ciprofloxacin, ofloxacin, erythromycin, and enrofloxacin, moderate removal (43 %-81 %) for flumequine and lincomycin, and limited removal (<8 %) for carbamazepine and diclofenac. The overall accumulation of pharmaceuticals in plant tissue and substrate adsorption accounted for only 2.3 % and 4.3 %, respectively, of the total mass removal. Biodegradation of these pharmaceuticals (up to 61 %) through microbial-mediated processes or within plant tissues was identified as the key removal pathway. For both conventional pollutants and pharmaceuticals, modified zeolite wetland media could only slightly enhance treatment without a significant difference between the two treatment groups. The final effluent from all hybrid CWs complied with Jordanian treated industry wastewater reuse standards (category III), and systems filled with raw or modified zeolite achieved over 95 % of samples meeting the highest water reuse category I. This study provides evidence of using hybrid CWs technology as a nature-based solution to address water safety and scarcity challenges.

Changing the order and ratio of substrate filling reduced CH4 and N2O emissions from the aerated constructed wetlands.

Constructed wetlands (CWs) have been used to enhance pollutant removal by filling several types of material as substrates. However, research on substrate filling order remains still limited, particularly regarding the effects of greenhouse gas (GHG) emissions. In this study, six CWs were constructed using zeolite and ferric­carbon micro-electrolysis (Fe-C) fillers to evaluate the effect of changing the filling order and ratio on pollutant removal, GHGs emissions, and associated microbial structure. The results showed that the order of substrate filling significantly impacted pollutant removal performance on CWs. Specifically, CWs filled with zeolite in the top layer exhibited superior NH4+-N removal compared to those filled in the lower layer. Moreover, the highest NH4+-N removal (95.0 % ± 1.9 %) was observed in CWs with a zeolite to Fe-C volume ratio of 8:2 (CWZe-1). Moreover, zeolite-filled at the top had lower GHGs emissions, with the lowest CH4 (0.22 ± 0.10 mg m-2 h-1) and N2O (167.03 ± 61.40 µg m-2 h-1) fluxes in the CWZe-1. In addition, it is worth noting that N2O is the major contributor to integrated global warming potential (GWP) in the six CWs, accounting for 81.7 %-90.8 %. The upper layer of CWs filled with zeolite exhibited higher abundances of nirK, nirS and nosZ genes. The order in which the substrate was filled affected the microbial community structure and the upper layer of CWs filled with zeolite had higher relative abundance of nitrifying genera (Nitrobacter, Nitrosomonas) and denitrifying genera (Zoogloea, Denitratisoma). Additionally, N2O emission was reduced by approximately 41.2 %-64.4 % when the location of the aeration of the CWs was changed from the bottom to the middle. This study showed that both the order of filling the substrate and the aeration position significantly affected the GHGs emissions from CWs, and that CWs had lower GHGs emissions when zeolites were filled in the upper layer and the aeration position was in the middle.

Production of vanillin via oxidation depolymerization of lignin over Fe- and Mn-modified TS-1 zeolites.

Converting lignin into specific aromatic chemicals for utilization through depolymerization of lignin is an effective way to achieve high-value applications. There are many depolymerization methods that can do this, but there are problems such as harsh reaction conditions, low depolymerization efficiency and uncontrollable target products that need to be solved. This study reports a novel system for the oxidative depolymerization of alkali lignin using Fe- and Mn- modified TS-1 as a catalyst to assist in the highly selective production of vanillin. We also proposed a possible reaction pathway for the oxidative depolymerization of alkali lignin to produce vanillin catalyzed by Fe-Mn/TS-1 catalyst. The catalytic effects of TS-1, Fe/TS-1, and Fe-Mn/TS-1 catalysts on the oxidative depolymerization of lignin to produce phenolic monomers and vanillin were investigated. The results show that the modified catalysts can effectively improve the efficiency of linkage bond breaking in lignin, especially the ß-O-4 bond, in which the inter-band transitions of Fe and Mn play an important role. The synergistic effect of the bimetallic-loaded catalyst (Fe-Mn/TS-1) could catalyze the oxidative depolymerization of lignin more efficiently than the monometallic-loaded catalyst (Fe/TS-1). This lignin oxidative depolymerization system produced 40.59 wt% bio-oil including 12.24 wt% phenolic monomers and 16.17 wt% re-lignin after the addition of Fe-Mn/TS-1 catalyst, owning the highest phenolic monomer yield. Surprisingly, this lignin oxidative depolymerization system exhibited high yield for vanillin (8.36 wt%) production. These results demonstrated that the Fe-Mn/TS-1 catalytic system has potential to produce vanillin from lignin under mild conditions.

Magnetic Rubber@Ni-Co layered double hydroxide derived from ZIF-67 template as nanostructured sorbent; application in determination of anticancer drugs in plasma samples.

In this study, a magnetic three-dimensional nano-composite based on Rubber-Fe3O4@Ni-Co Layered double hydroxide derived from ZIF-67 template was synthesized by a hydrothermal method. The proposed nano-composite was used as a sorbent for the enrichment of trace amounts of anti-cancer drugs (dasatinib and erlotinib hydrochloride) from plasma samples followed by determination using high-performance liquid chromatographic analysis (HPLC-UV). The synthesized nano-sorbent was characterized by X-ray diffraction, field emission scanning electron microscopy, Fourier transform infrared spectroscopy, vibrating-sample magnetometer, Brunauer-Emmett-Teller surface analysis, Barrett-Joyner-Halenda pore size analysis and energy dispersive X-ray spectroscopy. Under optimal experimental conditions, factors affecting on extraction efficiency such as pH, ionic strength, extraction temperature and time, desorption solvent and time, the limit of detection (LODs) and the limit of quantification (LOQs) were obtained as 0.6, 2 µg/L for both of dasatinib and erlotinib, respectively. Also, linear range of the method were 2-500 and 2-1000 µg/L for dasatinib and erlotinib, respectively. Relative standard deviations (RSD%) for the repeatability of extraction on sorbent to sorbent were obtained as 3.59, 1.97 %, and one sorbent reusability were investigated and relative standard deviation values were obtained 5.35, 3.30 % for dasatinib and erlotinib, respectively.

Enhanced removal of ciprofloxacin and associated antibiotic-resistant genes from wastewater using a biological aeration filters in combination with Fe3O4-modified zeolite.

Antibiotics release into the water environment through sewage discharge is a significant environmental concern. In the present study, we investigated the removal of ciprofloxacin (CIP) in simulated sewage by biological aeration filter (BAF) equipped with Fe3O4-modified zeolite (Fe3O4@ZF). Fe3O4@ZF were prepared with impregnation method, and the Fe3O4 particles were successfully deposited on the surface of ZF in an amorphous form according to the results of XPS and XRD analysis. The modification also increased the specific surface area (from 16.22 m²/g to 22 m²/g) and pore volume (from 0.0047 cm³/g to 0.0063 cm³/g), improving the adsorption efficiency of antibiotics. Fe3O4 modified ZF improved the treatment performance significantly, and the removal efficiency of CIP in BAF-Fe3O4@ZF was 79%±2.4%. At 10ml/L CIP, the BAF-Fe3O4@ZF reduced the relative abundances of antibiotics resistance genes (ARGs) int, mexA, qnrB and qnrS in the effluent by 57.16%, 39.59%, 60.22%, and 20.25%, respectively, which effectively mitigate the dissemination risk of ARGs. The modification of ZF increased CIP-degrading bacteria abundance, such as Rhizobium and Deinococcus-Thermus, and doubled bacterial ATP activity, promoting CIP degradation. This study offers a viable, efficient method to enhance antibiotic treatment and prevent leakage via sewage discharge.

Visual and photoelectrochemical analysis of antibiotic resistance genes enabled by surface-engineered ZIF-8@Au cascade nanozymes.

The aggravation of antibiotic resistance genes (ARGs) in the environment has posed a significant global health crisis. Accurate evaluation of ARGs levels in a facile manner is a pressing issue for environmental surveillance. Here, we demonstrate a unique dumbbell-shaped cascade nanozyme for visual/photoelectrochemical (PEC) dual-mode detection of ARGs. Gold nanoparticles (AuNPs) with tunable exposed facets are controllably anchored onto ZIF-8 dodecahedrons, exhibiting glucose oxidase (GOx)-like (ZIF-8@Au/G) and peroxidase (POD)-like (ZIF-8@Au/P) activities. Upon the occurrence of ARGs, an asymmetric cascade-amplified "dumbbell" configuration is spontaneously generated via target-induced DNA hybridization, comprising GOx-like ZIF-8@Au/G with capture DNA on one side and POD-like ZIF-8@Au/P with signal DNA on the opposite side. Such a cascade nano-system can efficiently oxidize colorless 2, 2'-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) into its green oxidation state and synergistically decompose H2O2, realizing colorimetric/PEC dual-mode ARGs detection with a detection limit of 0.112 nM. The applicability of the present bioassay is validated through measuring ARGs in real sludge samples. This work suggests the possibility to rationally design task-specific nanozymes and develop target-responsive nano-cascade assays for environmental monitoring.

Nano-enzyme hydrogels for cartilage repair effectiveness based on ternary strategy therapy.

Designing artificial nano-enzymes for scavenging reactive oxygen species (ROS) in chondrocytes (CHOs) is considered the most feasible pathway for the treatment of osteoarthritis (OA). However, the accumulation of ROS due to the amount of nano-enzymatic catalytic site exposure and insufficient oxygen supply seriously threatens the clinical application of this therapy. Although metal-organic framework (MOF) immobilization of artificial nano-enzymes to enhance active site exposure has been extensively studied, artificial nano-enzymes/MOFs for ROS scavenging in OA treatment are still lacking. In this study, a biocompatible lubricating hydrogel-loaded iron-doped zeolitic imidazolate framework-8 (Fe/ZIF-8/Gel) centrase was engineered to scavenge endogenous overexpressed ROS synergistically generating dissolved oxygen and enhancing sustained lubrication for CHOs as a ternary artificial nano-enzyme. This property enabled the nano-enzymatic hydrogels to mitigate OA hypoxia and inhibit oxidative stress damage successfully. Ternary strategy-based therapies show excellent cartilage repair in vivo. The experimental results suggest that nano-enzyme-enhanced lubricating hydrogels are a potentially effective OA treatment and a novel strategy.

Enhanced Enzymatic Performance of Immobilized Pseudomonas fluorescens Lipase on ZIF-8@ZIF-67 and Its Application to the Synthesis of Neryl Acetate with Transesterification Reaction.

In this study, hybrid skeleton material ZIF-8@ZIF-67 was synthesized by the epitaxial growth method and then was utilized as a carrier for encapsulating Pseudomonas fluorescens lipase (PFL) through the co-precipitation method, resulting in the preparation of immobilized lipase (PFL@ZIF-8@ZIF-67). Subsequently, it was further treated with glutaraldehyde to improve protein immobilization yield. Under optimal immobilization conditions, the specific hydrolytic activity of PFL@ZIF-8@ZIF-67 was 20.4 times higher than that of the free PFL. The prepared biocatalyst was characterized and analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared (FT-IR). Additionally, the thermal stability of PFL@ZIF-8@ZIF-67 at 50 °C was significantly improved compared to the free PFL. After 7 weeks at room temperature, PFL@ZIF-8@ZIF-67 retained 78% of the transesterification activity, while the free enzyme was only 29%. Finally, PFL@ZIF-8@ZIF-67 was applied to the neryl acetate preparation in a solvent-free system, and the yield of neryl acetate reached 99% after 3 h of reaction. After 10 repetitions, the yields of neryl acetate catalyzed by PFL@ZIF-8@ZIF-67 and the free PFL were 80% and 43%, respectively.

Hierarchical Micro- and Mesoporous Zeolitic Imidazolate Framework-8-Based Enzyme Hybrid for Combination Antimicrobial by Lysozyme and Lactoferrin.

Pathogenic bacteria have consistently posed a formidable challenge to human health, creating the critical need for effective antibacterial solutions. In response, enzyme-metal-organic framework (MOF) composites have emerged as a promising class of antibacterial agents. This study focuses on the development of an enzyme-MOF composite based on HZIF-8, incorporating the advantages of simple synthesis, ZIF-8 antibacterial properties, lysozyme hydrolysis, and high biological safety. Through a one-pot method, core-shell nanoparticles (HZIF-8) were synthesized. This structure enables efficient immobilization of lysozyme and lactoferrin within the HZIF-8, resulting in the formation of the lysozyme-lactoferrin@HZIF-8 (LYZ-LF@HZIF-8) composite. Upon exposure to light irradiation, HZIF-8 itself possessed antibacterial properties. Lysozyme initiated the degradation of bacterial peptidoglycan and lactoferrin synergistically enhanced the antibacterial effect of lysozyme. All of the above ultimately contributed to comprehensive antibacterial activity. Antibacterial assessments demonstrated the efficacy of the LYZ-LF@HZIF-8 composite, effectively eradicating Staphylococcus aureus at a cell density of 1.5 × 106 CFU/mL with a low dosage of 200 µg/mL and completely inactivating Escherichia coli at 400 µg/mL with the same cell density. The enzyme-MOF composite exhibited significant and durable antibacterial efficacy, with no apparent cytotoxicity in vitro, thereby unveiling expansive prospects for applications in the medical and food industries.

In vivo biodistribution and tumor uptake of [64Cu]-FAU nanozeolite via positron emission tomography Imaging.

Nanoparticles have emerged as promising theranostic tools for biomedical applications, notably in the treatment of cancers. However, to fully exploit their potential, a thorough understanding of their biodistribution is imperative. In this context, we prepared radioactive [64Cu]-exchanged faujasite nanosized zeolite ([64Cu]-FAU) to conduct positron emission tomography (PET) imaging tracking in preclinical glioblastoma models. In vivo results revealed a rapid and gradual accumulation over time of intravenously injected [64Cu]-FAU zeolite nanocrystals within the brain tumor, while no uptake in the healthy brain was observed. Although a specific tumor targeting was observed in the brain, the kinetics of uptake into tumor tissue was found to be dependent on the glioblastoma model. Indeed, our results showed a rapid uptake in U87-MG model while in U251-MG glioblastoma model tumor uptake was gradual over the time. Interestingly, a [64Cu] activity, decreasing over time, was also observed in organs of elimination such as kidney and liver without showing a difference in activity between both glioblastoma models. Ex vivo analyses confirmed the presence of zeolite nanocrystals in brain tumor with detection of both Si and Al elements originated from them. This radiolabelling strategy, performed for the first time using nanozeolites, enables precise tracking through PET imaging and confirms their accumulation within the glioblastoma. These findings further bolster the potential use of zeolite nanocrystals as valuable theranostic tools.

Unlocking Mixed-Metal Oxides Active Centers via Acidity Regulation for K&SO2 Poisoning Resistance: Self-Detoxification Mechanism of Zeolite-Confined deNOx Catalysts.

Selective catalytic reduction of nitrogen oxides (NOx) with ammonia (NH3-SCR) is an efficient NOx reduction strategy, while the denitrification (deNOx) catalysts suffer from serious deactivation due to the coexistence of multiple poisoning substances, such as alkali metal (e.g., K), SO2, etc., in industrial flue gases. It is essential to understand the interaction among various poisons and their effects on the deNOx process. Herein, the ZSM-5 zeolite-confined MnSmOx mixed (MnSmOx@ZSM-5) catalyst exhibited better deNOx performance after the poisoning of K, SO2, and/or K&SO2 than the MnSmOx and MnSmOx/ZSM-5 catalysts, the deNOx activity of which at high temperature (H-T) increased significantly (>90% NOx conversion in the range of 220-480 °C). It has been demonstrated that K would occupy both redox and acidic sites, which severely reduced the reactivity of MnSmOx/ZSM-5 catalysts. The most important, K element is preferentially deposited at -OH on the surface of ZSM-5 carrier due to the electrostatic attraction (-O-K). As for the K&SO2 poisoning catalyst, SO2 preferred to be combined with the surface-deposited K (-O-K-SO2ads) according to XPS and density functional theory (DFT) results, the poisoned active sites by K would be released. The K migration behavior was induced by SO2 over K-poisoned MnSmOx@ZSM-5 catalysts, and the balance of surface redox and acidic site was regulated, like a synergistic promoter, which led to K-poisoning buffering and activity recovery. This work contributes to the understanding of the self-detoxification interaction between alkali metals (e.g., K) and SO2 on deNOx catalysts and provides a novel strategy for the adaptive use of one poisoning substance to counter another for practical NOx reduction.

Adsorption efficiency of chitosan/clinoptilolite (CS/CZ) composite for effective removal of Cd+2 and Cr+6 ions from wastewater effluents of dairy cattle farms.

The wastewater effluent is responsible for the major ecological impact of the dairy sectors. To avoid the negative consequences of heavy metal pollution on the ecosystem, creative, affordable, and efficient treatment methods are now required before the effluent flows into the surrounding area. This study was aimed at assessing the effectiveness of three different adsorbents for Cd+2 and Cr+6 ions from wastewater effluents of dairy farms, including chitosan (CS), clinoptilolite zeolite (CZ), and chitosan/clinoptilolite zeolite (CS/CZ) composite. The adsorption kinetics of the CS/CZ composite were established using the effects of the key variables (pH, agitation speed, adsorbent concentrations, and contact durations). The removal (%) and adsorption capacities, qe (mg/g), were calculated using the data from the adsorption kinetics. Wastewater samples (n = 60) were collected from the wastewater effluents of five farms. Cd+2 and Cr+6 ion concentrations in all collected samples were determined. Following the CS/CZ composite creation, it was characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (X-RD), and Fourier-transform infrared spectrum (FT-IR). The CS/CZ composite had an adsorption capacity of 92.4 and 96.5 mg/g for both Cd+2 and Cr+6 ions at a concentration of 2.0 g/100 ml, respectively, while the CZ adsorption capacities for the two ions were 87.5 mg/g and 61.0 mg/g, respectively, at 4.0 g/100 ml concentration. The CS was achieved at 55.56 mg/g and 33.3 mg/g, respectively, at the same concentration. The efficiency of heavy metal removal was enhanced by increasing adsorbent concentration, agitation speed, and contact duration. Using CS/CZ composite at 2.0 g/100 ml concentration, 180 min of contact time, and 300 rpm agitation speed, the greatest removal efficiencies for Cd+2 and Cr+6 ions (96.43 and 98.75%, respectively) were demonstrated.

Synthesis and characterization of faujasite zeolite membrane for selective enrichment of Arthrobacter sp. in synthetic wastewater.

This paper centers on the preparation and characterization of both a clay support and a faujasite zeolite membrane. Additionally, the study explores the development of bacterial media to assess the performance of these prepared membranes. The faujasite zeolite membrane was created using the hydrothermal method, involving the deposition of a faujasite layer to fine-tune the pore sizes of the clay support. The clay supports were crafted from clay which was sieved to particle size Φ ≤ 63 µm, and compacted with 3.0 wt.% activated carbon, then sintered at 1,000 °C. Distilled water fluxes revealed a decrease from 1,500 L m-2 h-1 to a minimum of 412 L m-2 h-1 after 180 min of filtration. Both membranes were characterized by XRF, XRD, FTIR, adsorption-desorption of nitrogen (N2), and SEM-EDS. PCR technique was used for the identification of the isolated Arthrobacter sp., and the retention of the bacteria on the clay support and the faujasite zeolite membrane were found to be 96 and 99%, respectively. The results showed that the faujasite zeolite membrane passed the clay support due to a narrow pore size of the faujasite zeolite membrane of 2.28 nm compared to 3.55 nm for the clay supports.

Lean methane combustion over zeolite-supported Pd catalysts: Structure-performance relationship and deactivation mechanism.

Zeolites are a promising support for Pd catalysts in lean methane (CH4) combustion. Herein, three types of zeolites (H-MOR, H-ZSM-5 and H-Y) were selected to estimate their structural effects and deactivation mechanisms in CH4 combustion. We show that variations in zeolite structure and surface acidity led to distinct changes in Pd states. Pd/H-MOR with external high-dispersing Pd nanoparticles exhibited the best apparent activity, with activation energy (Ea) at 73 kJ/mol, while Pd/H-ZSM-5 displayed the highest turnover frequency (TOF) at 19.6 × 10-3 sec-1, presumably owing to its large particles with more step sites providing active sites in one particle for CH4 activation. Pd/H-Y with dispersed PdO within pore channels and/or Pd2+ ions on ion-exchange sites yielded the lowest apparent activity and TOF. Furthermore, Pd/H-MOR and Pd/H-ZSM-5 were both stable under a dry condition, but introducing 3 vol.% H2O caused the CH4 conversion rate on Pd/H-MOR drop from 100% to 63% and that on Pd/H-ZSM-5 decreased remarkably from 82% to 36%. The former was shown to originate from zeolite structural dealumination, and the latter principally owed to Pd aggregation and the loss of active PdO.

Design of double-core-shell structural materials for the extraction of non-steroidal anti-inflammatory drugs.

In this work, core-shell material with a special structure was designed and applied in solid-phase extraction (SPE) for non-steroidal anti-inflammatory drugs (NSAIDs) combined with high-performance liquid chromatography. Based on the advantages of core-shell ZIF-8@ZIF-67 (Zeolite imidazole ester framework materials [ZIFs]), effective derivatization treatment was carried out to partially vulcanize the original ZIFs, resulting in a special and new double-core-shell structural material CoS/ZIF-67/ZnS/ZIF-8 (ZIFs@ZnS@CoS) with porous surface and center hollow. The multiple forces caused by the rich chemical structure, the large specific surface area caused by the special pore structure, and the effective protection of the ZIFs core by sulfide shell make the designed material have higher extraction efficiency and longer service life, compared with ZIF-8@ZIF-67 and ZIF-8. At the same time, the established analytical method for non-steroidal drugs had a high recovery rate (98.93%-102.10%), low detection limit (0.11-0.27 µg/L), and wide linear range (1-200 µg/L) within a good correlation coefficient R2 (0.9978-0.9993). Satisfactory results were also obtained from the extraction of NSAIDs from the Yellow River water samples. These results indicate that the designed double-core-shell structure material can effectively exert its structural advantages and become a promising extraction material.

Enhancement of Biodegradability of Chicken Manure via the Addition of Zeolite in a Two-Stage Dry Anaerobic Digestion Configuration.

Leach bed reactors (LBRs) are dry anaerobic systems that can handle feedstocks with high solid content, like chicken manure, with minimal water addition. In this study, the chicken manure was mixed with zeolite, a novel addition, and packed in the LBR to improve biogas production. The resulting leachate was then processed in a continuous stirred tank reactor (CSTR), where most of the methane was produced. The supernatant of the CSTR was returned to the LBR. The batch mode operation of the LBR led to a varying methane production rate (MPR) with a peak in the beginning of each batch cycle when the leachate was rich in organic matter. Comparing the MPR in both systems, the peaks in the zeolite system were higher and more acute than in the control system, which was under stress, as indicated by the acetate accumulation at 2328 mg L-1. Moreover, the presence of zeolite in the LBR played a crucial role, increasing the overall methane yield from 0.142 (control experiment) to 0.171 NL CH4 per g of volatile solids of chicken manure entering the system at a solid retention time of 14 d. Zeolite also improved the stability of the system. The ammonia concentration increased gradually due to the little water entering the system and reached 3220 mg L-1 (control system) and 2730 mg L-1 (zeolite system) at the end of the experiment. It seems that zeolite favored the accumulation of the ammonia at a lower rate (14.0 mg L-1 d-1) compared to the control experiment (17.3 mg L-1 d-1). The microbial analysis of the CSTR fed on the leachate from the LBR amended with zeolite showed a higher relative abundance of Methanosaeta (83.6%) compared to the control experiment (69.1%). Both CSTRs established significantly different bacterial profiles from the inoculum after 120 days of operation (p < 0.05). Regarding the archaeal communities, there were no significant statistical differences between the CSTRs and the inoculum (p > 0.05).

Synthesis and Application of a pH-Responsive Functional Metal-Organic Framework: In Vitro Investigation for Delivery of Oridonin in Cancer Therapy.

Oridonin (Ori) is a naturally existing diterpenoid substance that mainly exists in the Chinese medicinal plant Rabdosia rubescens. It was previously found to possess intriguing biological properties; however, the quick clearance from plasma and limited solubility in water restricts its use as a drug. Several metal-organic frameworks (MOFs), having big surfaces and large pores, have recently been considered promising drug transporters. The zeolitic imidazolate framework-8 (ZIF-8), a form of MOF consisting of 2-methylimidazole with zinc ions, is structurally stable under physiologically neutral conditions, while it can degrade at low pH values such as in tumor cells. Herein, a nanosized drug delivery system, Ori@ZIF-8, was successfully designed for encapsulating and transporting oridonin to the tumor site. The drug loading of the prepared Ori@ZIF-8 was 26.78%, and the particles' mean size was 240.5 nm. In vitro, the release of Ori@ZIF-8 exhibited acid sensitivity, with a slow release under neutral conditions and rapid release of the drug under weakly acidic conditions. According to the in vitro anti-tumor experiments, Ori@ZIF-8 produced higher cytotoxicity than free Ori and induced apoptosis in A549 cancer cells. In conclusion, Ori@ZIF-8 could be a potential pH-responsive carrier to accurately release more oridonins at the tumor site.

CRISPR/Cas12a trans-cleavage mediated photoelectrochemical biosensor based on zeolitic imidazolate framework-67 for ATP determination.

An efficient PEC biosensor is proposed for ATP detection based on exciton energy transfer from CdTe quantum dots (CdTe QDs) to Au nanoparticles (AuNPs), integrating CRISPR/Cas12a trans-cleavage activity and specific recognition of ZIF-67 to ATP. Exciton energy transfer between CdTe QDs and AuNPs system is firstly constructed as photoelectrochemical (PEC) sensing substrate. Then, the activator DNAs, used to activate CRISPR/Cas12a, are absorbed on the surface of ZIF-67. In the presence of ATP, the activator DNAs are released due to more efficient adsorption of ZIF-67 to ATP. The released activator DNA activates trans-cleavage activity of CRISPR/Cas12a to degrade ssDNA on the electrode, leading to the recovery of photocurrent due to the interrupted energy transfer. Benefiting from the specific recognition of ZIF-67 to ATP and CRISPR/Cas12a-modulated amplification strategy, the sensor is endowed with excellent specificity and high sensitivity.

Zeolite and Neurodegenerative Diseases.

Neurodegenerative diseases (NDs), characterized by progressive degeneration and death of neurons, are strongly related to aging, and the number of people with NDs will continue to rise. Alzheimer's disease (AD) and Parkinson's disease (PD) are the most common NDs, and the current treatments offer no cure. A growing body of research shows that AD and especially PD are intricately related to intestinal health and the gut microbiome and that both diseases can spread retrogradely from the gut to the brain. Zeolites are a large family of minerals built by [SiO4]4- and [AlO4]5- tetrahedrons joined by shared oxygen atoms and forming a three-dimensional microporous structure holding water molecules and ions. The most widespread and used zeolite is clinoptilolite, and additionally, mechanically activated clinoptilolites offer further improved beneficial effects. The current review describes and discusses the numerous positive effects of clinoptilolite and its forms on gut health and the gut microbiome, as well as their detoxifying, antioxidative, immunostimulatory, and anti-inflammatory effects, relevant to the treatment of NDs and especially AD and PD. The direct effects of clinoptilolite and its activated forms on AD pathology in vitro and in vivo are also reviewed, as well as the use of zeolites as biosensors and delivery systems related to PD.

Liquid Interfacial Gating of Superhydrophobic Plasmonic Metal-Organic Frameworks for Three-in-One Separation, Enrichment, and Recognition in Bacterial Quorum Sensing.

Poor adsorption properties of nonadsorbing targets and competing adsorption of nontargets at a liquid interface always hamper the development of interface sensing techniques. There is a need to fabricate materials that are applicable to various interface assemblies and, meanwhile, could be employed as interfacial gating to improve the performance of interface sensing by separating, enriching, and recognizing targets at the liquid interface. Here, superhydrophobic zeolite imidazole frameworks-8@gold nanoparticles-1H,1H,2H,2H-perfluorodecanethiol (ZIF-8@GNPs-PFDT) with a static water contact angle (WCA) of 155° was constructed via electrostatic self-assembly and surface graft modification. The plasmonic metal-organic framework (PMOF) nanohybrid realized all-purpose self-assembly at air/liquid and liquid/liquid interfaces and also facilely assembled on the surface of liquid droplets, hydrogels, and foams. The self-assembled porous materials displayed the capability for separating, enriching, and recognizing analytes at various oil/water interfaces and thus could be used to adsorb nonadsorbing targets and block the competing adsorption of nontargets. The self-assembled ZIF-8@GNPs-PFDT structures were employed as a three-in-one interfacial gating to endow the excellent surface-enhanced Raman scattering (SERS) sensing capability and has become a promising tool for dye molecular analysis, oil/water separation, organic phase identification, and in situ cultivation and monitoring of bacterial quorum sensing (QS).