Metal-Hydrogen-Pi-Bonded Organic Frameworks

We report the synthesis and characterization of a new series of permanently porous, three-dimensional metal-organic frameworks (MOFs), M-HAF-2 (M= Fe, Ga or In), constructed from tetratopic, hydroxamate-based, chelating linkers. The structure of M-HAF-2 was determined by three-dimensional electron diffraction (3DED), revealing a unique interpenetrated hcb-a net topology. This unusual topology is enabled by the presence of free hydroxamate groups, which lead to the formation of a diverse network of cooperative interactions comprising single metal-hydroxamate nodes, staggered π–π interactions between linkers and H-bonding interactions between metal-coordinated and free hydroxamate groups. Such extensive, multimodal interconnectivity is reminiscent of the complex noncovalent interaction networks of proteins and endows M-HAF-2 frameworks with good thermal and exceptionally high chemical stability and allows them to readily undergo post-synthetic metal exchange (PSE). We demonstrate that M-HAF-2 can serve as versatile porous materials for ionic separations, likely aided by one-dimensional channels lined by continuously π-stacked aromatic groups and H-bonding hydroxamate functionalities. As a new addition to the small group of hydroxamate-based MOFs, M-HAF-2 represents a structural merger between MOFs and hydrogen-bonded organic frameworks (HOFs).

Natural-Fibrous Lime-Based Mortar for the Rapid Retrofitting of Heritage Masonry Buildings

The present work aims to define the mechanical behavior of a new composite material for the preservation and enhancement of the vast historical and architectural heritage particularly vulnerable to environmental and seismic actions. The new composite represents a novelty in the landscape of the fibrous mortars and consists of natural hydraulic lime (NHL)-based mortar, strengthened by Sisal short fibers randomly oriented in the mortar matrix. The developed mortar ensures the chemical-physical compatibility with the original features of the historical masonry structures (especially in stone and clay) aiming to pursue the effectiveness and durability of the intervention. The use of vegetal fibers (i.e., the Sisal one) is an exciting challenge for the construction industry considering that they require a lower level of industrialization for their processing, and therefore, their costs are considerably lower, as compared to the most common synthetic/metal fibers. Samples of Sisal-composite are tested in three-point bending, aiming to estimate both their bending stress and fracture energy. Tensile and compressive tests were also performed on the composite samples, while water retention and slump test were performed on the fresh mix. At last, the tensile tests on the Sisal strand were performed to evaluate the tensile stress of both strand and wire. An original mechanical interpretation is proposed to explain two interesting phenomena that arose from the analysis of experimental data. The comparison among the performances of unreinforced and reinforced mortar suggests that the use of short fibers is recommendable as coating in the retrofitting interventions alternatively to the long uni or bi-directional fiber strands adopted in the classic fibrous reinforcement (i.e., FRCM). The proposed composite also ensures mix-independent great workability, excellent ductility, and strength, and it can be considered a promising alternative to the classic fiber-reinforcing systems. As final remarks, the use of fiber F1 (length of 24 mm) with respect to fiber F2 (length of 13 mm) is more recommendable in the retrofitting interventions of historical buildings, ensuring higher strength and/or ductility for the composite.

Thermodynamic and kinetic models for the removal of copper and cadmium using industrial effluents by mixed adsorbent

The potential of Activated Charcoal and bone Charcoal as a low cost material for the removal of copper and cadmium from synthetic metal solution was studied. A number of experiments were performed in order to determine the potential capacity of the adsorbent in terms of thermo Dynamic equilibrium from the batch data. The Positive values of change in Enthalpy show that the process is endothermic in nature for Cd (II) and the negative values of Change in Enthalpy shows that the process is exothermic in nature for Cu (II). The standard Gibb’s free energy values are positive which means that the process is not spontaneous in nature. The negative values of ΔS show that there is decrease in randomness at the solid/solution interface during the adsorption of copper. The study revealed that mixed adsorbent prepared by blending the activated charcoal and bone charcoal in 1: 1 ratio has more potential to act as an adsorbent for the removal of Cu and Cd from aqueous solution. The optimum temperature was found to be 40°C for both the metals. The higher correlation coefficient R2(0.9824) value shown that cadmium ions were well fitted the thermodynamic model comparing copper ions. The batch adsorption studies have been carried out for 2 hrs considering all the 6 parameters by optimizing each of them. The data obtained for optimized parameters were studied through fitting of kinetic models such as Pseudo-first order and Pseudo second order models for both Copper and Cadmium along with Correlation or regression coefficient (R2) values.

Semiempirical method for examining asynchronicity in metal–oxido-mediated C–H bond activation

The oxidation of substrates via the cleavage of thermodynamically strong C–H bonds is an essential part of mammalian metabolism. These reactions are predominantly carried out by enzymes that produce high-valent metal–oxido species, which are directly responsible for cleaving the C–H bonds. While much is known about the identity of these transient intermediates, the mechanistic factors that enable metal–oxido species to accomplish such difficult reactions are still incomplete. For synthetic metal–oxido species, C–H bond cleavage is often mechanistically described as synchronous, proton-coupled electron transfer (PCET). However, data have emerged that suggest that the basicity of the M–oxido unit is the key determinant in achieving enzymatic function, thus requiring alternative mechanisms whereby proton transfer (PT) has a more dominant role than electron transfer (ET). To bridge this knowledge gap, the reactivity of a monomeric MnIV–oxido complex with a series of external substrates was studied, resulting in a spread of over 104 in their second-order rate constants that tracked with the acidity of the C–H bonds. Mechanisms that included either synchronous PCET or rate-limiting PT, followed by ET, did not explain our results, which led to a proposed PCET mechanism with asynchronous transition states that are dominated by PT. To support this premise, we report a semiempirical free energy analysis that can predict the relative contributions of PT and ET for a given set of substrates. These findings underscore why the basicity of M–oxido units needs to be considered in C–H functionalization.

Metal-Based Nanomaterials: Work as Drugs and Carriers against Viral Infections

Virus infection is one of the threats to the health of organisms, and finding suitable antiviral agents is one of the main tasks of current researchers. Metal ions participate in multiple key reaction stages of organisms and maintain the important homeostasis of organisms. The application of synthetic metal-based nanomaterials as an antiviral therapy is a promising new research direction. Based on the application of synthetic metal-based nanomaterials in antiviral therapy, we summarize the research progress of metal-based nanomaterials in recent years. This review analyzes the three inhibition pathways of metal nanomaterials as antiviral therapeutic materials against viral infections, including direct inactivation, inhibition of virus adsorption and entry, and intracellular virus suppression; it further classifies and summarizes them according to their inhibition mechanisms. In addition, the use of metal nanomaterials as antiviral drug carriers and vaccine adjuvants is summarized. The analysis clarifies the antiviral mechanism of metal nanomaterials and broadens the application in the field of antiviral therapy.

The zinc transporter ZnuABC is critical for the virulence of Chromobacterium violaceum and contributes to diverse zinc-dependent physiological processes

Chromobacterium violaceum is a ubiquitous environmental bacterium that causes sporadic life-threatening infections in humans. How C. violaceum acquires zinc to colonize environmental and host niches is unknown. In this work, we demonstrated that C. violaceum employs the zinc uptake system ZnuABC to overcome zinc limitation in the host, ensuring the zinc supply for several physiological demands. Our data indicated that the C. violaceum ZnuABC transporter is encoded in a zur -CV_RS15045-CV_RS15040- znuCBA operon. This operon was repressed by the zinc uptake regulator Zur and derepressed in the presence of the host protein calprotectin (CP) and the synthetic metal chelator EDTA. A Δ znuCBA mutant strain showed impaired growth under these zinc-chelated conditions. Moreover, the deletion of znuCBA provoked a reduction in violacein production, swimming motility, biofilm formation, and bacterial competition. Remarkably, the Δ znuCBA mutant strain was highly attenuated for virulence in an in vivo mouse infection model and showed a low capacity to colonize the liver, grow in the presence of CP, and resist neutrophil killing. Overall, our findings demonstrate that ZnuABC is essential for C. violaceum virulence, contributing to subvert the zinc-based host nutritional immunity.

Natural-Fibrous Lime-Based Mortar for the Rapid Retrofitting of Masonry Heritage

The present work aims to characterize the mechanical behavior of a new composite material for the conservation and development of the vast historical and architectural heritage that is particularly vulnerable to environmental and seismic actions. The new composite consists of natural hydraulic lime (NHL) -based mortar, reinforced by sisal short fibers randomly oriented in the mortar matrix. The NHL-based mortar ensures the chemical-physical compatibility with the original feature of the historical masonry structures (mostly in stone and clay) aiming to pursue both the effectiveness and durability of the intervention. The use of vegetable fibers (i.e. the sisal one) is an exciting challenge for the construction industry since they require a lower degree of industrialization for their processing, and therefore, their costs are also low, as compared to the most common synthetic/metal fibers. Beams of sisal-composite sizing 160x40x40 mm3 with a central notch are tested in three-point bending, aiming to evaluate both their bending strength and fracture energy. Also, tensile tests and compressive tests were performed on the composite samples, while water retention test and slump test were performed on the fresh mix. Finally, the tensile tests on the Sisal strand were carried out to evaluate the tensile strength of both strand and wire. A final comparison with unreinforced mortar specimens shows that the proposed composite ensures great workability and good performances in term of ductility and strength and it can be considered a promising alternative to the classic fiber-reinforcing systems.

The zinc transporter ZnuABC is critical for the virulence of Chromobacterium violaceum and contributes to diverse zinc-dependent physiological processes

Chromobacterium violaceum is a ubiquitous environmental bacterium that causes sporadic life-threatening infections in humans. How C. violaceum acquires zinc to colonize environmental and host niches is unknown. In this work, we demonstrated that C. violaceum employs the zinc uptake system ZnuABC to overcome zinc limitation in the host, ensuring the zinc supply for several physiological demands. Our data indicated that the C. violaceum ZnuABC transporter is encoded in a zur-CV_RS15045-CV_RS15040-znuCBA operon. This operon was repressed by the zinc uptake regulator Zur and derepressed in the presence of the host protein calprotectin (CP) and the synthetic metal chelator EDTA. A ΔznuCBA mutant strain showed impaired growth under these zinc-chelated conditions. Moreover, the deletion of znuCBA provoked a reduction in violacein production, swimming motility, biofilm formation, and bacterial competition. Remarkably, the ΔznuCBA mutant strain was highly attenuated for virulence in an in vivo mouse infection model and showed a low capacity to colonize the liver, grow in the presence of CP, and resist neutrophil killing. Overall, our findings demonstrate that ZnuABC is essential for C. violaceum virulence, contributing to subvert the zinc-based host nutritional immunity.

Polypyrrole-Based Metal Nanocomposite Electrode Materials for High-Performance Supercapacitors

Metallic nanostructures (MNs) and metal-organic frameworks (MOFs) play a pivotal role by articulating their significance in high-performance supercapacitors along with conducting polymers (CPs). The interaction and synergistic pseudocapacitive effect of MNs with CPs have contributed to enhance the specific capacitance and cyclic stability. Among various conjugated heterocyclic CPs, polypyrrole (PPy) (prevalently knows as “synthetic metal”) is exclusively studied because of its excellent physicochemical properties, ease of preparation, flexibility in surface modifications, and unique molecular structure–property relationships. Numerous researchers attempted to improve the low electronic conductivity of MNs and MOFs, by incorporating conducting PPy and/or used decoration strategy. This was succeeded by fine-tuning this objective, which managed to get outstanding supercapacitive performances. This brief technical note epitomizes various PPy-based metallic hybrid materials with different nano-architectures, emphasizing its technical implications in fabricating high-performance electrode material for supercapacitor applications.