Asbestos and Zeolites: from A to Z via a Common Ion.

Asbestos and zeolites are silicate-based minerals, linked inextricably via paradoxical similarities and differences which have emanated from different geological epochs. Both have been employed in the service of humanity through millennia: asbestos, for its "inextinguishable" quality of being an insulator against heat and fire; zeolite, a "boiling stone" with its volcanic and marine sedimentary rock origins, for its propensity to adsorb water and remove metals and toxins. Serious adverse health effects observed in asbestos miners as long ago as the 1st Century AD did not halt the rising popularity of asbestos. As the miracle material of the 1900s, asbestos production and consumption exploded, culminating in its ubiquity in ships, vehicles, homes, commercial buildings, and over 3000 different industrial and household products. Through the 1940s and 1950s, epidemiological studies concluded that asbestos was a likely cause of asbestosis, lung cancer, and malignant mesothelioma, and it is now banned in many but far from all countries. The long latency between exposure to asbestos and the occurrence of cancer has obscured the deadly consequences of asbestos exposure for centuries. Even today, a considerable part of the world population is insufficiently aware of the dangers of asbestos, and millions of tons of this carcinogen continue to be mined and used worldwide. Zeolites, both natural and synthetic, are microporous aluminosilicate minerals commonly used in a myriad of processes, in the petrochemical industry, in domestic appliances and cleaning agents, as commercial adsorbents and exchangers for toxins and pollutants, and as catalysts. Zeolites are found in agriculture, veterinary science, and human health. More recently, new materials such as carbon nanotubes are being employed in materials requiring durability and thermal and electrical conductivity, yet nanotubes are now joining the ranks of more established particulates such as asbestos and silica, in causing human disease. In this review, we compare and contrast the similarities and differences of these two groups of silicate minerals and their waxing and waning use in the employ of humanity.

Structural characterization of a non-heme iron active site in zeolites that hydroxylates methane.

Iron-containing zeolites exhibit unprecedented reactivity in the low-temperature hydroxylation of methane to form methanol. Reactivity occurs at a mononuclear ferrous active site, α-Fe(II), that is activated by N2O to form the reactive intermediate α-O. This has been defined as an Fe(IV)=O species. Using nuclear resonance vibrational spectroscopy coupled to X-ray absorption spectroscopy, we probe the bonding interaction between the iron center, its zeolite lattice-derived ligands, and the reactive oxygen. α-O is found to contain an unusually strong Fe(IV)=O bond resulting from a constrained coordination geometry enforced by the zeolite lattice. Density functional theory calculations clarify how the experimentally determined geometric structure of the active site leads to an electronic structure that is highly activated to perform H-atom abstraction.

A Biocatalytic Cascade in an Ultrastable Mesoporous Hydrogen-Bonded Organic Framework for Point-of-Care Biosensing.

Herein, we report the first example of using mesoporous hydrogen-bonded organic frameworks (MHOFs) as the protecting scaffold to organize a biocatalytic cascade. The confined microenvironment of MHOFs has robust and large transport channels, allowing the efficient transport of a wide range of biocatalytic substrates. This new MHOF-confined cascade system shows superior activity, extended scope of catalytic substrates, and ultrahigh stability that enables the operation of complex chemical transformations in a porous carrier. In addition, the advantages of MHOF-confined cascades system for point-of-care biosensing are also demonstrated. This study highlights the advantages of HOFs as scaffold for multiple enzyme assemblies, which has huge potential for mimicking complex cellular transformation networks in a controllable manner.

ZIF-8-Assisted NaYF4:Yb,Tm@ZnO Converter with Exonuclease III-Powered DNA Walker for Near-Infrared Light Responsive Biosensor.

This work reports a ZIF-8 (ZIF: Zeolitic Imidazolate Framework)-assisted NaYF4:Yb,Tm@ZnO upconverter for the photoelectrochemical (PEC) biosensing of carcinoembryonic antigen (CEA) under near-infrared (NIR) irradiation on a homemade 3D-printed device with DNA walker-based amplification strategy. The composite photosensitive material NaYF4:Yb,Tm@ZnO, as converter to transfer NIR import to photocurrent output, was driven from annealed NaYF4:Yb,Tm@ZIF-8. Yb3+ and Tm3+-codoped NaYF4 (NaYF4:Yb,Tm) converted NIR excitation into UV emission, matching with the absorption of ZnO for in situ excitation to generate the photocurrent. Upon target CEA introduction, the swing arm of DNA walker including the sequence of CEA aptamer carried out the sandwiched bioassembly with CEA capture aptamer on the G-rich anchorage DNA tracks-functionalized magnetic beads. Thereafter, DNA walker was triggered, and the swing arm DNA was captured by the G-rich anchorage DNA according to partly complementary pairing and Exonuclease III (Exo III) consumed anchorage DNA by a burnt-bridge mechanism to go into the next cycle. The released guanine (G) bases from DNA walker enhanced the photocurrent response on a miniature homemade 3D-printed device consisting of the detection cell, dark box, and light platform. Under optimal conditions, NaYF4:Yb,Tm@ZnO-based NIR light-driven PEC biosensor presented high sensitivity and selectivity for CEA sensing with a detection limit of 0.032 ng mL-1. Importantly, our strategy provides a new horizon for the development of NIR-based PEC biosensors in the aspect of developing MOF-derived photoelectric materials, flexible design of a 3D-printed device, and effective signal amplification mode.

Effects of plant on denitrification pathways in integrated vertical-flow constructed wetland treating swine wastewater.

Plant is an important part of constructed wetland (CW), while, its potential effect on nitrogen cycling is complicated. Herein, integrated vertical-flow constructed wetland (IVCW) in pilot-scale planted with Arundo donax (Planted System, PS) was constructed to treat swine wastewater. The removal performance of nitrogen in PS, effects of plant on the microbial community structure and nitrogen related function genes were revealed. Results showed that, Arundo donax planting enhanced the removal rate of TN, compared to unplanted IVCWs, the absolute abundance of Pseudomonas, Acinetobacter and Bacillus in PS was significantly increased, as well as the absolute abundance of functional gene (amoA, nxrA, nirK, nirS and nosZ). The denitrification process was mainly occurred in down-flow cell of PS with significantly higher abundant of nirK and nosZ (P < 0.05). These findings suggested that Arundo donax planting in IVCWs with zeolite as substrate promoted the growth of denitrifying microorganisms under higher pollutant load. In addition, the increased abundant of nosZ and the ratio of nosZ/∑nir indicating a lower genetic potential for N2O release. Our research provides new insight into the potential application of plant on the purification of swine wastewater.

Modulating the Biofunctionality of Metal-Organic-Framework-Encapsulated Enzymes through Controllable Embedding Patterns.

Embedding an enzyme within a MOF as exoskeleton (enzyme@MOF) offers new opportunities to improve the inherent fragile nature of the enzyme, but also to impart novel biofunctionality to the MOF. Despite the remarkable stability achieved for MOF-embedded enzymes, embedding patterns and conversion of the enzymatic biofunctionality after entrapment by a MOF have only received limited attention. Herein, we reveal how embedding patterns affect the bioactivity of an enzyme encapsulated in ZIF-8. The enzyme@MOF can maintain high activity when the encapsulation process is driven by rapid enzyme-triggered nucleation of ZIF-8. When the encapsulation is driven by slow coprecipitation and the enzymes are not involved in the nucleation of ZIF-8, enzyme@MOF tends to be inactive owing to unfolding and competing coordination caused by the ligand, 2-methyl imidazole. These two embedding patterns can easily be controlled by chemical modification of the amino acids of the enzymes, modulating their biofunctionality.

Enzyme Encapsulation in a Porous Hydrogen-Bonded Organic Framework.

Protection of biological assemblies is critical to applications in biotechnology, increasing the durability of enzymes in biocatalysis or potentially stabilizing biotherapeutics during transport and use. Here we show that a porous hydrogen-bonded organic framework (HOF) constructed from water-soluble tetra-amidinium (1·Cl4) and tetracarboxylate (2) building blocks can encapsulate and stabilize biomolecules to elevated temperature, proteolytic and denaturing agents, and extend the operable pH range for catalase activity. The HOF, which readily retains water within its framework structure, can also protect and retain the activity of enzymes such as alcohol oxidase, that are inactive when encapsulated within zeolitic imidazolate framework (ZIF) materials. Such HOF coatings could provide valid alternative materials to ZIFs: they are metal free, possess larger pore apertures, and are stable over a wider, more biologically relevant pH range.

A metal-organic zeolitic framework with immobilized urease for use in a tapered optical fiber urea biosensor.

A tapered single-mode coreless single-mode (SCS) structure with high sensitivity for sensing refractive index is described. In order to achieve high specificity of optical biosensors, here enzyme capsulation film was achieved by embedding urease in zeolitic imidazolate framework (ZIF-8/urease) through in situ growth approach on the coreless fibers. Determination of urea is achieved through online monitoring of its binding to the urease in zeolitic imidazolate framework. Refractive index change result in wavelength shifts of the optical fiber biosensor. The resonance wavelength exhibits a good linear relationship with urea concentration in the range of 1 to 10 mM with detection limit of 0.1 mM and sensitivity of 0.8 mM/RIU (refractive index unit) if operated with broadband light ranging from 1525 nm to 1590 nm. Final assessment of optical biosensor in real sample was performed where excellent performance in terms of sensitivity and selectivity was observed. Schematic representation of experimental setup and mechanism for urea detection. A tapered single-mode coreless single-mode (SCS) structure is placed between a broadband light source ranging (BBS) and optical spectrum analyzer (OSA). ZIF-8/urease composites are applied as a recognition layer for urea detection.

Manganese soil and foliar fertilization of olive plantlets: the effect on leaf mineral and phenolic content and root mycorrhizal colonization.

BACKGROUND: The present study aimed to examine the effect of foliar (Mn_fol) and soil Zeolite-Mn (Mn_ZA) application on leaf mineral, total phenolic and oleuropein content, and mycorrhizae colonization of self-rooted cv. Leccino plantlets grown on calcareous soil. RESULTS: The dissolution of zeolite was 97% when citric acid was applied at 0.05 mM dm-3 , suggesting that organic acids excreted by roots can dissolve modified zeolite (Mn_ZA), making Mn available for plant uptake. The leaf Mn concentration was the highest for Mn_fol treatment at 90 days after transplanting (DAT) (172 mg kg-1 ) and 150 DAT (70 mg kg-1 ) compared to other treatments. Mn_ZA soil application increased leaf Mn concentration at 150 DAT compared to control and NPK treatments. The oleuropein leaf content was highest for Mn_fol compared to other treatments at 90 DAT and lowest at 150 DAT. Arbuscular mycorrhizal colonization was higher for Mn_fol treatment at 150 DAT compared to all other treatments. CONCLUSION: Changes in the arbuscular colonization percentage and oleuropein content may be connected to stress conditions provoked by a high leaf Mn concentration in the Mn_fol treatment at 90 DAT. Mn_ZA application increased leaf Mn concentration at 150 DAT compared to control and NPK treatments. It can be assumed that the dominant mechanism in Mn uptake from modified zeolite is Mn_ZA dissolution through root exudates. © 2018 Society of Chemical Industry.

GOx@ZIF-8(NiPd) Nanoflower: An Artificial Enzyme System for Tandem Catalysis.

We report a facile approach to prepare an artificial enzyme system for tandem catalysis. NiPd hollow nanoparticles and glucose oxidase (GOx) were simultaneously immobilized on the zeolitic imidazolate framework 8 (ZIF-8) via a co-precipitation method. The as-prepared GOx@ZIF-8(NiPd) nanoflower not only exhibited the peroxidase-like activity of NiPd hollow nanoparticles but also maintained the enzymatic activity of GOx. A colorimetric sensor for rapid detection of glucose was realized through the GOx@ZIF-8(NiPd) based multi-enzyme system. Moreover, the GOx@ZIF-8(NiPd) modified electrode showed good bioactivity of GOx and high electrocatalytic activity for the oxygen reduction reaction (ORR), which could also be used for electrochemical detection of glucose.

Fast Targeting and Cancer Cell Uptake of Luminescent Antibody-Nanozeolite Bioconjugates.

Understanding the targeted cellular uptake of nanomaterials is an essential step to engineer and program functional and effective biomedical devices. In this respect, the targeting and ultrafast uptake of zeolite nanocrystals functionalized with Cetuximab antibodies (Ctxb) by cells overexpressing the epidermal growth factor receptor are described here. Biochemical assays show that the cellular uptake of the bioconjugate in the targeted cancer cells already begins 15 min after incubation, at a rate around tenfold faster than that observed in the negative control cells. These findings further show the role of Ctxb exposed at the surfaces of the zeolite nanocrystals in mediating the targeted and rapid cellular uptake. By using temperature and pharmacological inhibitors as modulators of the internalization pathways, the results univocally suggest a dissipative uptake mechanism of these nanomaterials, which seems to occur using different internalization pathways, according to the targeting properties of these nanocrystals. Owing to the ultrafast uptake process, harmless for the cell viability, these results further pave the way for the design of novel theranostic tools based on nanozeolites.

Natural zeolites in diet or litter of broilers.

This study aims to analyse the influence of adding natural zeolites (clinoptilolite) to the diet or litter of broilers and their effects on growth performance, carcass yield and litter quality. Three consecutive flocks of broilers were raised on the same sawdust litter, from d 1 to d 42 of age, and distributed in three treatments (control with no added zeolites, addition of 5 g/kg zeolite to diet and addition of 100 g/kg zeolites to litter). The addition of zeolites to the diet or litter did not affect growth performance or carcass yield. The addition of zeolites to the diet did not influence moisture content of the litter, ammonia volatilisation was reduced only in the first flock and pH of litter was reduced in the second and third flock. However, the addition of zeolites to the litter reduced moisture content, litter pH and ammonia volatilisation in all flocks analysed. The addition of 5 g/kg zeolite to the diet in three consecutive flocks was not effective in maintaining litter quality, whereas the addition of 100 g/kg natural zeolites to sawdust litter reduced litter moisture and ammonia volatilisation in three consecutive flocks raised on the same litter.

Ammonium removal from groundwater using a zeolite permeable reactive barrier: a pilot-scale demonstration.

In situ remediation of ammonium-contaminated groundwater is possible through a zeolite permeable reactive barrier (PRB); however, zeolite's finite sorption capacity limits the long-term field application of PRBs. In this paper, a pilot-scale PRB was designed to achieve sustainable use of zeolite in removing ammonium (NH(4)(+)-N) through sequential nitrification, adsorption, and denitrification. An oxygen-releasing compound was added to ensure aerobic conditions in the upper layers of the PRB where NH(4)(+)-N was microbially oxidized to nitrate. Any remaining NH(4)(+)-N was removed abiotically in the zeolite layer. Under lower redox conditions, nitrate formed during nitrification was removed by denitrifying bacteria colonizing the zeolite. During the long-term operation (328 days), more than 90% of NH(4)(+)-N was consistently removed, and approximately 40% of the influent NH(4)(+)-N was oxidized to nitrate. As much as 60% of the nitrate formed in the PRB was reduced in the zeolite layer after 300 days of operation. Removal of NH(4)(+)-N from groundwater using a zeolite PRB through bacterial nitrification and abiotic adsorption is a promising approach. The zeolite PRB has the advantage of achieving sustainable use of zeolite and immediate NH(4)(+)-N removal.

Internalization pathways of anisotropic disc-shaped zeolite L nanocrystals with different surface properties in HeLa cancer cells.

Information about the mechanisms underlying the interactions of nanoparticles with living cells is crucial for their medical application and also provides indications of the putative toxicity of such materials. Here the uptake and intracellular delivery of disc-shaped zeolite L nanocrystals as porous aminosilicates with well-defined crystal structure, uncoated as well as with COOH-, NH2 -, polyethyleneglycol (PEG)- and polyallylamine hydrochloride (PAH) surface coatings are reported. HeLa cells are used as a model system to demonstrate the relation between these particles and cancer cells. Interactions are studied in terms of their fates under diverse in vitro cell culture conditions. Differently charged coatings demonstrated dissimilar behavior in terms of agglomeration in media, serum protein adsorption, nanoparticle cytotoxicity and cell internalization. It is also found that functionalized disc-shaped zeolite L particles enter the cancer cells via different, partly not yet characterized, pathways. These in vitro results provide additional insight about low-aspect ratio anisotropic nanoparticle interactions with cancer cells and demonstrate the possibility to manipulate the interactions of nanoparticles and cells by surface coating for the use of nanoparticles in medical applications.

Enhanced aerobic granulation and nitrogen removal by the addition of zeolite powder in a sequencing batch reactor.

The aim of this study was to evaluate the impact of zeolite powders on feasibility of rapid aerobic granulation in the column-type sequencing batch reactors. After 90 days' operation, aerobic granular sludge was formed in both reactors by altering influent chemical oxygen demand/nitrogen (COD/N) ratios. R1 with zeolite powders had better removal capabilities of COD and total nitrogen than R2, which was without zeolite powders. Mixed liquor volatile suspended solid concentrations of the two reactors were 7.36 and 5.45 g/L, while sludge volume index (SVI30) values were 34.9 and 47.9 mg/L, respectively. The mean diameters of aerobic granular sludge in the above two reactors were 2.5 and 1.5 mm, respectively. Both reactors achieved the largest simultaneous nitrification and denitrification (SND) efficiency at an influent COD/N ratio of 8; however, R1 exhibited more excellent SND efficiency than R2. The obtained results could provide a novel technique for rapid aerobic granulation and N removal simultaneously, especially when treating nitrogen-rich industrial wastewater.

Composition and dynamics of microbial community in a zeolite biofilter-membrane bioreactor treating coking wastewater.

In this study, a lab-scale anaerobic/anoxic/zeolite biofilter-membrane bioreactor (A1/A2/ZB-MBR) was designed to treat coking wastewater. The 454 pyrosequencing was used to obtain the composition and dynamics of microbial community about the treatment system. The results showed that the system yielded stable effluent chemical oxidation demand (158.5 ± 21.8 mg/L) and ammonia (8.56 ± 7.30 mg/L), but fluctuant total nitrogen (31.4-165.1 mg/L) concentrations. In addition, 66,256 16S rRNA gene sequences were obtained from A2 and ZB-MBR, and the microbial diversity and richness for five samples were determined. Although community compositions in the five samples were quite different, bacteria assigned to phylum Proteobacteria and class Flavobacteria commonly existed and dominated the microbial populations. The pyrosequencing analysis revealed that the microbial community shifted in the ZB-MBR with the presence of zeolite. Some taxa began to appear in ZB-MBR and contributed to the system performance. Additionally, Nitrosomonas and Nitrobacter gradually became the dominant ammonia-oxidizing bacteria and nitrite-oxidizing bacteria during the operation, respectively, which are favorable for the stabilized ammonia removal. Our results proved that the ZB-MBR is an alternative technique for treating coking wastewater.

Targeting telomerase utilizing zeolitic imidazole frameworks as non-viral gene delivery agents across different cancer cell types.

Telomerase, a ribonucleoprotein coded by the hTERT gene, plays an important role in cellular immortalization and carcinogenesis. hTERT is a suitable target for cancer therapeutics as its activity is highly upregulated in most of cancer cells but absent in normal somatic cells. Here, by employing the two Metal-Organic Frameworks (MOFs), viz. ZIF-C and ZIF-8, based biomineralization we encapsulate Clustered Regularly Interspaced Short Palindromic Repeat (CRISPR)/Cas9 plasmid system that targets hTERT gene (CrhTERT) in cancer cells. When comparing the two biocomposites, ZIF-C shows the better loading capacity and cell viability. The loaded plasmid in ZIF-C is highly protected against enzymatic degradation. CrhTERT@ZIF-C is efficiently endocytosed by cancer cells and the subcellular release of CrhTERT leads to telomerase knockdown. The resultant inhibition of hTERT expression decreases cellular proliferation and causing cancer cell death. Furthermore, hTERT knockdown shows a significant reduction in tumour metastasis and alters protein expression. Collectively we show the high potential of ZIF-C-based biocomposites as a promising general tool for gene therapy of different types of cancers.

Treatment of secondary urban wastewater with a low ammonium-tolerant marine microalga using zeolite-based adsorption.

The low tolerance of marine microalgae to ammonium and hyposalinity limits their use in urban wastewater (UWW) treatments. In this study, using the marine microalga Amphidinium carterae, it is demonstrated for the first time that this obstacle can be overcome by introducing a zeolite-based adsorption step to obtain a tolerable UWW stream. The maximum ammonium adsorption capacities measured in the natural zeolite used are among the highest reported. The microalga grows satisfactorily in mixtures of zeolite-treated UWW and seawater at a wide range of proportions, both with and without adjusting the salinity, as long as the ammonium concentration is below the threshold tolerated by the microalgae (6.3 mg L-1). A proof of concept performed in 10-L bubble column photobioreactors with different culture strategies, including medium recycling, showed an enhanced biomass yield relative to a control with no UWW. No noticeable effect was observed on the production of specialty metabolites.

Effect of Zeolite Supplementation on Gene Expression in the Intestinal Mucosa in the Context of Immunosafety Support in Poultry.

Zeolite is an effective and non-toxic silicate mineral. Its properties are widely used in industry due to its sorption and ion exchange properties. Due to its excellent chemical properties, it has also great potential in poultry production as a food additive or supplement to bedding. This is of great importance for the biosafety and hygiene of production. The study aimed to analyse the effects of simultaneous application of zeolite to feed and bedding on production parameters and expression of genes related to intestinal tightness, organism defence, and immune response. Male Ross 308 broiler chickens were used in the experiment. In the experimental group, an external factor in the form of a powdery zeolite was used for feed and pelleted bedding. On the day of slaughter, the caecal mucosa was collected for gene expression analysis. We showed no significant changes in the tissue composition of the carcasses, but zeolite had a beneficial effect on the carcass yield. The analysis of the immune gene panel showed a significant increase in the expression of the interleukins and interferons genes. We have demonstrated the effect of zeolite on the improvement of the intestinal barrier and increasing the tightness of the intestines. There were no changes in gene expression related to the host's defence against infections; therefore, based on the obtained results, it was concluded that zeolite can be considered an immunomodulating factor of the immune system.

Rumen Parameters, Nutrients Digestibility and Milk Production of Lactating Boer Goats Fed Diets Containing Clay Minerals.

<b>Background and Objective:</b> The inclusion of clay minerals in dairy nutrition is getting attention owing to their proven beneficial effects. The current study aimed to evaluate the effect of dietary supplementation of three different clay minerals (bentonite, zeolite and humic acid) on the performance of lactating Boer goats. <b>Materials and Methods:</b> Twenty lactating Boer goats (having an average body weight ~42.7 kg) were divided into four groups (5 animals each) by using a completely randomized design (CRD). Each group was fed with one of four dietary treatments: Control group with basal ration R1: Consisting of concentrate feed mixture (CFM) and clover hay (50:50%, C:R) on a dry matter (DM) basis, R2: Basal ration plus 1% bentonite, R3: Basal ration plus 1.25% zeolite and R4: Basal ration plus 0.5% humic acid. <b>Results:</b> The results revealed that bentonite and humic acid increased (p<0.05) the nutrient digestibility and nutritive values compared to zeolite and control groups. Ruminal ammonia and total volatile fatty acids (TVFAs) contents increased (p<0.05) with supplementation of bentonite. No effect of clays supplementation was observed on plasma total protein, urea and creatinine, however, it increased (p<0.05) the albumin concentration and albumin/globulin ratios compared to the control while decreasing the plasma globulin contents. Supplementation of humic acid increased (p<0.05) the AST concentrations. Bentonite supplementation recorded the highest milk yield (p<0.05) and composition, while the zeolite group had the lowest values. <b>Conclusion:</b> The present study indicated that the inclusion of clay minerals particularly bentonite (at 1%) can positively affect the performance of lactating Boer goats.