Biomimetic Mineralization of Large Enzymes Utilizing a Stable Zirconium-Based Metal-Organic Frameworks.

Enzymes are natural catalysts for a wide range of metabolic chemical transformations, including selective hydrolysis, oxidation, and phosphorylation. Herein, we demonstrate a strategy for the encapsulation of enzymes within a highly stable zirconium-based metal-organic framework. UiO-66-F4 was synthesized under mild conditions using an enzyme-compatible amino acid modulator, serine, at a modest temperature in an aqueous solution. Enzyme@UiO-66-F4 biocomposites were then formed by an in situ encapsulation route in which UiO-66-F4 grows around the enzymes and, consequently, provides protection for the enzymes. A range of enzymes, namely, lysozyme, horseradish peroxidase, and amano lipase, were successfully encapsulated within UiO-66-F4. We further demonstrate that the resulting biocomposites are stable under conditions that could denature many enzymes. Horseradish peroxidase encapsulated within UiO-66-F4 maintained its biological activity even after being treated with the proteolytic enzyme pepsin and heated at 60 °C. This strategy expands the toolbox of potential metal-organic frameworks with different topologies or functionalities that can be used as enzyme encapsulation hosts. We also demonstrate that this versatile process of in situ encapsulation of enzymes under mild conditions (i.e., submerged in water and at a modest temperature) can be generalized to encapsulate enzymes of various sizes within UiO-66-F4 while protecting them from harsh conditions (i.e., high temperatures, contact with denaturants or organic solvents).

Thermodynamic Insights into Phosphonate Binding in Metal-Azolate Frameworks.

Organophosphorus chemicals, including chemical warfare agents (CWAs) and insecticides, are acutely toxic materials that warrant capture and degradation. Metal-organic frameworks (MOFs) have emerged as a class of tunable, porous, crystalline materials capable of hydrolytically cleaving, and thus detoxifying, several organophosphorus nerve agents and their simulants. One such MOF is M-MFU-4l (M = metal), a bioinspired azolate framework whose metal node is composed of a variety of divalent first-row transition metals. While Cu-MFU-4l and Zn-MFU-4l are shown to rapidly degrade CWA simulants, Ni-MFU-4l and Co-MFU-4l display drastically lower activities. The lack of reactivity was hypothesized to arise from the strong binding of the phosphate product to the node, which deactivates the catalyst by preventing turnover. No such study has provided detailed insight into this mechanism. Here, we leverage isothermal titration calorimetry (ITC) to monitor the binding of an organophosphorus compound with the M-MFU-4l series to construct a complete thermodynamic profile (Ka, ΔH, ΔS, ΔG) of this interaction. This study further establishes ITC as a viable technique to probe small differences in thermodynamics that result in stark differences in material properties, which may allow for better design of first-row transition metal MOF catalysts for organophosphorus hydrolysis.

Divinylanthracene-Containing Tetracationic Organic Cyclophane with Near-Infrared Photoluminescence.

Near-infrared (NIR) light is known to have outstanding optical penetration in biological tissues and to be non-invasive to cells compared with visible light. These characteristics make NIR-specific light optimal for numerous biological applications, such as the sensing of biomolecules or in theranostics. Over the years, significant progress has been achieved in the synthesis of fluorescent cyclophanes for sensing, bioimaging, and making optoelectronic materials. The preparation of NIR-emissive porphyrin-free cyclophanes is, however, still challenging. In an attempt for fluorescence emissions to reach into the NIR spectral region, employing organic tetracationic cyclophanes, we have inserted two 9,10-divinylanthracene units between two of the pyridinium units in cyclobis(paraquat-p-phenylene). Steady-state absorption, fluorescence, and transient-absorption spectroscopies reveal the deep-red and NIR photoluminescence of this cyclophane. This tetracationic cyclophane is highly soluble in water and has been employed successfully as a probe for live-cell imaging in a breast cancer cell line (MCF-7).

Porous structured cotton-based ACF for the adsorption of benzen.

Fibrous activated carbon has attracted emerging research interests due to its remarkable adsorption performance for volatile organic compounds (VOCs). Though this adsorption behavior for VOCs is closely related to the pore structure on the surface of activated carbon fiber (ACF), few researchers paid attentions to the influence of textural properties of this adsorption process. Especially, cotton-based activated carbon fiber (CACF) for adsorbing benzene pollutant is rarely reported. Herein, in order to develop a high-performance adsorbent for the removal of VOCs pollutants, this work studied the influence of textural properties of CACF on the adsorption of benzene. The results showed that the increase of carbonization temperature would lead to the reduction of mesopores but the increase of micropores for CACF; the embedment of phosphoric acid and its derivatives into the carbon layers contributed to the formation of pore structure for CACF; furthermore, specific surface area of CACF can also be enlarged by increasing the concentration of phosphoric acid. More importantly, it was found that the adsorption capacity of CACF for benzene was strongly dependent on the specific surface area and volume of micropores within CACF because micropores can provide more favorable binding sites. This adsorption process preferred to occur on the wall of micropores, then the accumulated benzene would slowly fill the pores. Interestingly, the decrease of pore size of micropores can unexpectedly improve the affinity of CACF to benzene on the contrary. This work provides a new strategy to develop porous structured ACF materials for the high-performance adsorption of VOCs.

A comprehensive bibliometric overview: antibiotic resistance and Escherichia coli in natural water.

The environment is the most important reservoir for both resistance mechanisms and gene transfer in biological science studies. This study gives a bibliometric overview of studies of "antibiotic resistance" and "Escherichia coli" in the field of "Agricultural and Biological Sciences" from 2015 to 2019 to assess both research trends and scholarly networks in diverse research disciplines. The two keywords of "antibiotic resistance" and "Escherichia coli" were selected to search in the Scopus database. Each review article was categorized into materials, natural waters (i.e., seawater, freshwater) and wastewater, journal name, and quartile in category of the journal, the year of publication, and the country. Bibliometric indicators and visualization maps were utilized to analyse the retrieved data quantitatively and qualitatively. A total of 1376 publications in the field of agricultural and biological sciences over the last 5 years were obtained using the keywords of antibiotic resistance and Escherichia coli. With additional keywords of freshwater and wastewater, 4 and 24 studies were obtained, respectively. Wastewater was found to be the most common working environment for the keywords of antibiotic resistance and Escherichia coli. It is also found that the studies of antibiotic resistance are mainly conducted in wastewater environments, focusing on human and food health. Working under "One Health" consisting of human, animal and agriculture, and environmental health could be the only permanent and effective approach to solving antibiotic resistance-related issues.

An alternative material for an effective treatment technique proposal in the light of bibliometric profile of global scientific research on antibiotic resistance and Escherichia coli.

Antibiotic resistance is considered by the countries to be a global health issue and a huge threat to public health. The reduction of resistant microorganisms from water/wastewater is of importance in environmental sciences since they are resistant in the aquatic environment. In this study, a bibliometric analysis of literature from the field of environmental science in water ecosystems from 2015 to 2019 was carried out using the keywords "Antibiotic Resistance (AR)" and "Escherichia coli". Furthermore, using the keywords of "Fresh Water," "Sea Water," and "Waste Water," 155, 52, and 57 studies were discovered, respectively. It is found that 217 studies of the total 2115 studies investigated on AR are mostly performed in the "Waste Water" by considering human health. Given the studies, an up-to-date solution should be proposed since the release of antibiotic-resistant bacteria (ARB) and antibiotic resistance genes (ARGs) from wastewater treatment plants needs to be mitigated. For this reason, it is obvious that working on micro and macro ecosystems will increase the probability of solutions in antibiotic resistance. A discussion of removal techniques for coliform bacteria, particularly antibiotic resistant Escherichia coli, was presented. One of the unique values of this study is to offer an innovative solution that removing them by metal-organic frameworks (MOFs) are emerging crystalline hybrid materials. MOFs are used for environmental, biological, and food antimicrobial substances efficiently. Therefore, we can give inspiration to the future studies of antimicrobial resistance removal via adsorption using MOFs as adsorbents. Graphical Abstract.

Zirconium-Based Metal-Organic Frameworks for the Removal of Protein-Bound Uremic Toxin from Human Serum Albumin.

Uremic toxins often accumulate in patients with compromised kidney function, like those with chronic kidney disease (CKD), leading to major clinical complications including serious illness and death. Sufficient removal of these toxins from the blood increases the efficacy of hemodialysis, as well as the survival rate, in CKD patients. Understanding the interactions between an adsorbent and the uremic toxins is critical for designing effective materials to remove these toxic compounds. Herein, we study the adsorption behavior of the uremic toxins, p-cresyl sulfate, indoxyl sulfate, and hippuric acid, in a series of zirconium-based metal-organic frameworks (MOFs). The pyrene-based MOF, NU-1000, offers the highest toxin removal efficiency of all the MOFs in this study. Other Zr-based MOFs possessing comparable surface areas and pore sizes to NU-1000 while lacking an extended aromatic system have much lower toxin removal efficiency. From single-crystal X-ray diffraction analyses assisted by density functional theory calculations, we determined that the high adsorption capacity of NU-1000 can be attributed to the highly hydrophobic adsorption sites sandwiched by two pyrene linkers and the hydroxyls and water molecules on the Zr6 nodes, which are capable of hydrogen bonding with polar functional groups of guest molecules. Further, NU-1000 almost completely removes p-cresyl sulfate from human serum albumin, a protein that these uremic toxins bind to in the body. These results offer design principles for potential MOFs candidates for uremic toxin removal.

Exploiting π-π Interactions to Design an Efficient Sorbent for Atrazine Removal from Water.

The United States Environmental Protection Agency (EPA) recognizes atrazine, a commonly used herbicide, as an endocrine disrupting compound. Excessive use of this agrochemical results in contamination of surface and ground water supplies via agricultural runoff. Efficient removal of atrazine from contaminated water supplies is paramount. Here, the mechanism governing atrazine adsorption in Zr6-based metal-organic frameworks (MOFs) has been thoroughly investigated by studying the effects of MOF linkers and topology on atrazine uptake capacity and uptake kinetics. We found that the mesopores of NU-1000 facilitated rapid atrazine uptake saturating in <5 min and that the pyrene-based linkers offered sufficient sites for π-π interactions with atrazine as demonstrated by the near 100% uptake. Without the presence of a pyrene-based linker, NU-1008, a MOF similar to NU-1000 with respect to surface area and pore size, removed <20% of the exposed atrazine. These results suggest that the atrazine uptake capacity demonstrated by NU-1000 stems from the presence of a pyrene core in the MOF linker, affirming that π-π stacking is responsible for driving atrazine adsorption. Furthermore, NU-1000 displays an exceptional atrazine removal capacity through three cycles of adsorption-desorption. Powder X-ray diffraction and Brunauer-Emmett-Teller surface area analysis confirmed the retention of MOF crystallinity and porosity throughout the adsorption-desorption cycles.

From Transition Metals to Lanthanides to Actinides: Metal-Mediated Tuning of Electronic Properties of Isostructural Metal-Organic Frameworks.

Isostructural metal-organic frameworks (MOFs) have been prepared from a variety of metal-oxide clusters, including transition metals, lanthanides, and actinides. Experimental and calculated shifts in O-H stretching frequencies for hydroxyl groups associated with the metal-oxide nodes reveal varying electronic properties for these units, thereby offering opportunities to tune support effects for other materials deposited onto these nodes.

The investigation and assessment of characteristics of waste activated sludge after ultrasound pretreatment.

In this study, the characteristics of sonicated waste activated sludge (WAS) originating from a nutrient-removal wastewater treatment plant were investigated and evaluated. Different combinations of power inputs, sonication durations and volumes were used for optimization of the sonication conditions. Ultrasound density levels ranged between 0.32 and 3.2 W/mL. Optimal conditions based on soluble COD concentrations (SCOD) after sonication at different ultrasound density levels and sonication durations (1, 5, 10 and 30 min) were determined. An ultrasonic density of 1.6 W/mL and a sonication time of 30 min were identified as optimal sonication conditions in terms of SCOD concentration. The sludge sonicated under these optimal conditions was further investigated to determine the effect of ultrasound treatment on solubilization of organic matter and volatile solids, particle size and biodegradability. Disruption of the sludge structure was confirmed by the increase in the SCOD by 35.5%, reduction in volatile suspended solids by 26% and reduction in particle size by 85%. The availability of COD fractions of sonicated sludge was also tested with oxygen uptake rate and phosphate release data indicating that using sonicated sludge for both subsequent biological treatment and sludge treatment is promising.