Metal-binding Functional Groups Research Articles

АДАПТАЦИЯ МИКРООРГАНИЗМОВ К ТЯЖЕЛЫМ МЕТАЛЛАМ

Many heavy metals (HM) (Zn, Cu, Mn, Co, etc.) take an active part in the most important processes of vital activity of microorganisms as microelements. However, at high concentrations they become toxic, and a number of metals (Pb, Hg, Cd, etc.) are highly toxic even at low concentrations. Microorganisms are able to resist the toxic effects of HMs due to the presence of various resistance mechanisms that are aimed at converting cations to a less toxic form or oxidation state, which makes them less mobile and bioavailable. The very first reaction of microorganisms to the toxic effects of metals is a change in cell morphology, their agglomeration, which leads to a decrease in the availability of binding sites for toxic metals. The mechanisms used by bacteria can be divided into biochemical and molecular. Bacterial cells have the ability to sorb metal cations with the help of metal-binding functional groups (carboxylic, sulfhydryl, hydroxyl, sulfate, phosphate, and amino groups) of the cell membrane,preventing their penetration into the cell. Bacteria have a variety of efflux systems for HM outflow from cells with the help of carrier proteins belonging to different families, which maintain a low concentration of HM inside the cell, protecting cellular components. Polysaccharides, biosurfactants, inorganic anions (phosphate, carbonate, and sulfide ions) and other metabolic products of microorganisms participate in extracellular detoxification, and gluta- thione, metal-binding proteins, intracellular polyphosphate granules, which bind HM cations into poorly soluble compounds, participate in intracellular sequestration. The reduction of HM ions with the help of enzymes leads to the formation of their less toxic forms. The genes responsible for bacterial resistance to toxic metals are localized on chromosomes or plasmids and can be transferred to closely related bacterial species, which plays an important role in the spread of HM resistance in nature. Microorganisms also demonstrate indirect mechanisms of HM tolerance aimed at maintaining cell integrity by protecting them from oxidative stress.

Uncovering strong π-metal interactions on Ag and Au nanosurfaces under ambient conditions via in-situ surface-enhanced Raman spectroscopy

Uncovering strong π-metal interactions on Ag and Au nanosurfaces under ambient conditions via in-situ surface-enhanced Raman spectroscopy

Insights into potassium permanganate reducing H2S generation from anaerobic fermentation of sludge

• Pretreatment with 0.1 g/g TSS KMnO 4 reduced H 2 S yield from WAS to 67%. • KMnO 4 inhibited sulfur containing organics hydrolysis and sulfate reduction. • KMnO 4 addition changed the chemical equilibrium of sulfide species. • KMnO 4 decreased the related abundances of S 2− producers and functional genes. Potassium permanganate, a versatile strong oxidant, has been applied as a highly effective additive to degrade pollutants and recover resources from Waste activated sludge (WAS). In addition to these benefits, it was observed in this study that KMnO 4 largely reduced H 2 S production from WAS anaerobic fermentation. With an increase of KMnO 4 dosage from 0 to 0.1 g/g TSS, the maximal H 2 S production reduced from 292.3 × 10 −4 to 96.4 × 10 −4 mg/g VSS while the maximal short-chain fatty acids production increased from 23 to 251 mg COD/g VSS. Model-based analysis showed that KMnO 4 decreased the maximal H 2 S yield potential and H 2 S production rate. The mechanism explorations revealed that several oxidative substances (e.g., •O 2 − and •OH), Mn 2+ , and O H - were substantially generated after KMnO 4 being added into the fermenters. The generated oxidative substances resulted in intracellular substance release even cell apoptosis. This inhibited the activities of two main S 2 - (H 2 S precursor) producers, i.e., Sulfate reducing bacteria (SRBs) and anaerobes responsible for hydrolysis of sulfur-containing organics, especially that of SRBs. Experimental results showed that 0.1 g/g TSS KMnO 4 inhibited sulfur-containing organics hydrolysis, amino acids degradation, and sulfate reducing process by 12.5%, 27.2%, and 61.2%, respectively. The Mn 2+ released from KMnO 4 and other metal ions (e.g., Fe 2+ ) originated from metal-binding functional groups owing to KMnO 4 addition caused substantial S-based precipitations, which also decreased S 2 - in the fermentation liquor. Besides, the generated O H - increased fermentation pH, which benefited the chemical equilibrium of sulfide species from H 2 S to H S - and S 2 - . Microbial community and PICRUSt2 analyses further revealed that KMnO 4 significantly decreased the abundances of S 2 - producers and functional genes responsible for sulfate reducing process.

Mechanistic investigation of the mass transfer stages involved during the adsorption of aqueous lead onto Scopulariopsis brevicompactum fungal biomass

The Scopulariopsis brevicompactum fungal biomass (SFB) was applied as an adsorbent for the uptake of aqueous lead species via the dynamic sorption process. The adsorption capacity dependence on the solution pH, contact time, initial adsorbate concentration and adsorbent concentration was investigated via batch mode. According to the experimental findings, the adsorption capacity was favoured by an increase in all the aforementioned process variables except adsorbent concentration. The optimum adsorption capacity was recorded at pH 6.0, 120 min, and 0.2 g/L adsorbent concentration. The process isotherm was explained by the D-R model, with predominated physisorption (E = 0.069 kJ/mol), while the pseudo-second-order model explained the process kinetics. The characterization results confirmed the presence of several metal-binding functional groups on SFB. Furthermore, by applying the mass transfer factor model, the dependence of the lead ions adsorptive mass transfer on the film diffusion regime was established. Thus, the adsorptive performance of the SFB was demonstrated in the study.

Cellular and physiological approaches to evaluate the chelating effect of Chlorella on metal ion stressed lymphocytes.

Chlorella is a green alga consumed as dietary food supplement in pulverized form. In addition to its high nutritional value, it is reported as an excellent detoxifying agent. The pulverized Chlorella is partially soluble in water and insoluble portion has been reported for removal of mercury, cadmium and radioactive strontium from body. Chlorella contains a variety of metal-binding functional groups such as carboxyl, amino, phosphoryl, hydroxyl and carbonyl groups, which has high affinity towards various metal ions. The present study was envisaged to evaluate the chelating effect of water soluble fraction of Chlorella powder (AqCH) on metal ions. Fura-2 fluorescence ratio (F340/F380) was measured by fluorescence spectrometer (FS) after the exposure of chloride salt of metals viz., strontium, cobalt, barium, cesium, thallium and mercury to lymphocytes. Pretreatment of AqCH (0.1-20mg mL-1) was given to evaluate the attenuating effect on fura-2 fluorescence ratio induced by metal ions. The intracellular levels of these metal ions were analyzed by atomic absorption spectrophotometer (AAS) and fluorescence microscopy (FM). Pretreatment with AqCH significantly attenuated the metal induced fluorescence ratio in dose-dependent manner. The results of AAS and FM were found in coherence with fura-2 fluorescence ratio which emphasized that AqCH significantly prevented the metal ions internalization. The present study suggests AqCH chelates with these metal ions and prevents its interaction with cells thereby reducing the intracellular mobilization of Ca2+.

Computer-Assisted Design of Macrocyclic Chelators for Actinium-225 Radiotherapeutics.

Actinium-225 (225Ac) is an excellent candidate for targeted radiotherapeutic applications for treating cancer, because of its 10-day half-life and emission of four high-energy α2+ particles. To harness and direct the energetic potential of actinium, strongly binding chelators that remain stable in vivo during biological targeting must be developed. Unfortunately, controlling chelation for actinium remains challenging. Actinium is the largest +3 cation on the periodic table and has a 6d05f0 electronic configuration, and its chemistry is relatively unexplored. Herein, we present theoretical work focused on improving the understanding of actinium bonding with macrocyclic chelating agents as a function of (1) macrocycle ring size, (2) the number and identity of metal binding functional groups, and (3) the length of the tether linking the metal binding functional group to the macrocyclic backbone. Actinium binding by these chelators is presented within the context of complexation with DOTA4-, the most relevant Ac3+ binding agent for contemporary radiopharmaceutical applications. The results enabled us to develop a new strategy for actinium chelator design. The approach is rooted in our identification that Ac3+-chelation chemistry is dominated by ionic bonding interactions and relies on (1) maximizing electrostatic interactions between the metal binding functional group and the Ac3+ cation and (2) minimizing electronic repulsion between negatively charged actinium binding functional groups. This insight will provide a foundation for future innovation in developing the next generation of multifunctional actinium chelators.

Preparation of Carboxymethyl Cellulose-g- Poly(acrylamide)/Attapulgite Porous Monolith With an Eco-Friendly Pickering-MIPE Template for Ce(III) and Gd(III) Adsorption.

Due to their high specific surface and metal-binding functional groups in their crosslinked polymeric networks, monolithic materials incorporating a porous structure have been considered one of the most efficient kinds of adsorbents for rare earth element recovery. Herein, a facile and novel monolithic multi-porous carboxymethyl cellulose-g-poly(acrylamide)/attapulgite was synthesized by free radical polymerization via green vegetable oil-in-water Pickering medium internal phase emulsion (O/W Pickering-MIPEs), which was synergically stabilized by attapulgite and tween-20. The homogenizer rotation speed and time were investigated to form stable Pickering-MIPEs. The effects of different types of oil phase on the formation of Pickering-MIPEs were investigated with stability tests and rheological characterization. The structure and composition of the porous material when prepared with eight kinds of vegetable oil were characterized by FTIR and SEM. The results indicate that the obtained materials, which have abundant interconnected porosity, are comparable to those fabricated with Pickering-HIPE templates. The adsorption experiment demonstrated that the prepared materials have a fast capture rate and high adsorption capacities for Ce(III) and Gd(III), respectively. The saturation adsorption capacities for Ce(III) and Gd(III) are 205.48 and 216.73 mg/g, respectively, which can be reached within 30 min. Moreover, the monolithic materials exhibit excellent regeneration ability and reusability. This work provides a feasible and eco-friendly pathway for the construction of a multi-porous adsorbent for adsorption and separation applications.

Adsorptive Removal of Cr(VI) by Sargassum horneri–Based Activated Carbon Coated with Chitosan

A novel polymer/activated carbon composite was prepared in this study by one-step chemical activation of Sargassum horneri, followed by surface modification with chitosan, a widely abundant biopolymer. The prepared composite was used as adsorbent to remove one of the most toxic metal ions, Cr(VI), from aqueous solution. Surface characterization tests revealed the material to be predominantly mesoporous with the specific surface area of 293.4 m2·g−1 and the average pore diameter of 6.27 nm. Enhanced uptake capacity of Cr(VI) by the prepared composite was obtained due to the presence of more metal-binding functional (amino and hydroxyl) groups on its surface. Extremely fast adsorption rate of Cr(VI) was also achieved due to the porous structure of the prepared composite. This study has clearly shown that Sargassum horneri can be a potential alternative precursor for carbon-based adsorbents and the proper designed polymer/AC composites can be tailor-made adsorbents for heavy metal removal.

Electrochemical Pretreatment for Sludge Sulfide Control without Chemical Dosing: A Mechanistic Study.

Sulfide is a toxic and corrosive odorant generated in various sludge treatment and disposal systems. We developed an electrochemical pretreatment (EPT) approach to eliminate sludge sulfide production without adding chemicals. Biochemical sulfide potential (BSP) test was used to evaluate the effectiveness of EPT on sludge sulfide production. The sulfide control was effective with EPT, and we determined the underlying mechanism of EPT. EPT which was operated at 12 V for 720 s eliminated 99% of dissolved sulfide and 100% of gaseous H2S(g). In comparison, the dissolved sulfide reached 104 ± 1 mg S/L in the control BSP test. A sulfur mass balance analysis in the BSP test showed that 90% of the produced sulfide was removed via metal precipitation. Metal distribution results confirmed that metals (i.e., Fe, Mn, and Ni) in the sludge became soluble after EPT and were released from their residual and organically bound fractions. EPT which was operated at 15 V solubilized around 73, 92, and 72% of Fe, Mn, and Ni, and these metals precipitated the sulfide that was produced from biological sulfate reduction. Sludge analysis revealed that EPT disintegrated sludge flocs and disrupted metal-binding functional groups. Specifically, reduction of 17% C═O functional groups in the sludge was found, which could be associated with metal release. The impact of oxidants (e.g., chlorine) generated from EPT on sulfide oxidation was minimal. The findings of this study broadened up our understanding of the electrochemical process for sulfide control during saline sludge digestion.

Metal-Binding Isosteres as New Scaffolds for Metalloenzyme Inhibitors.

The principle of isosteres or bioisosteres in medicinal chemistry is a central and essential concept in modern drug discovery. For example, carboxylic acids are often replaced by bioisosteres to mitigate issues related to lipophilicity or acidity while retaining acidic characteristics in addition to hydrogen bond donor/acceptor abilities. Separately, the development of metal-binding pharmacophores (MBPs) for binding to the active site metal ion in metalloenzymes of therapeutic interest is an emerging area in the realm of fragment-based drug discovery (FBDD). The direct application of the bioisostere concept to MBPs has not been well-described or systematically investigated. Herein, the picolinic acid MBP is used as a case study for the development of MBP isosteres (so-called MBIs). Many of these isosteres are novel compounds, and data on their physicochemical properties, metal binding capacity, and metalloenzyme inhibition characteristics are presented. The results show that MBIs of picolinic acid generally retain metal coordinating properties and exhibit predictable metalloenzyme inhibitory activity while possessing a broad range of physicochemical properties (e.g., p Ka, log P). These findings demonstrate the use of bioisosteres results in an untapped source of metal binding functional groups suitable for metalloenzyme FBDD. These MBIs provide a previously unexplored route for modulating the physicochemical properties of metalloenzyme inhibitors and improving their drug-likeness.

Direct growth of high crystallinity graphene from water-soluble polymer powders

The use of solid-state carbon sources is effective to produce graphene by safe and low-cost chemical vapor deposition (CVD) process. Water-soluble polymers are generally environmentally friendly and have great potential on large-scale green production of graphene. Here, we systematically study the growth of graphene from water-soluble polymers on copper foils. Two different conversion ways are adopted to investigate the growth mechanism of graphene from water-soluble polymers. We find that the metal-binding functional group hydroxyl strongly influences the vaporization of water-soluble polymers on Cu foils, which hinders the formation of graphene films by rapid thermal treatment. In direct CVD process using water-soluble polymer powders as precursors, oxygenated functional groups in polymers can enhance the crystallinity of as-grown graphene in contrast to solid hydrocarbons without containing oxygen (e.g. polyethylene). Large and continuous graphene films of high quality are synthesized from polyvinyl alcohol and polyethylene glycol. Nitrogen doping in graphene can be easily realized by using nitrogen-containing water-soluble polymers (e.g. polyvinyl pyrrolidone).

The identification of inhibitory compounds of Rickettsia prowazekii methionine aminopeptidase for antibacterial applications

Methionine aminopeptidase (MetAP) is a dinuclear metalloprotease responsible for the cleavage of methionine initiator residues from nascent proteins. MetAP activity is necessary for bacterial proliferation and is therefore a projected novel antibacterial target. A compound library consisting of 294 members containing metal-binding functional groups was screened against Rickettsia prowazekii MetAP to determine potential inhibitory motifs. The compounds were first screened against the target at a concentration of 10 µM and potential hits were determined to be those exhibiting greater than 50% inhibition of enzymatic activity. These hit compounds were then rescreened against the target in 8-point dose–response curves and 11 compounds were found to inhibit enzymatic activity with IC50 values of less than 10 µM. Finally, compounds (1–5) were docked against RpMetAP with AutoDock to determine potential binding mechanisms and the results were compared with crystal structures deposited within the PDB.

Captopril/enalapril inhibit promiscuous esterase activity of carbonic anhydrase at micromolar concentrations: An in vitro study

The inhibitory activity of captopril, a thiol-containing competitive inhibitor of the angiotensin-converting enzyme, ACE, against esterase activity of carbonic anhydrase, CA was investigated. This small molecule, as well as enalapril, was selected in order to represents both thiol and carboxylate, as two well-known metal binding functional groups of metalloprotein inhibitors. Since captopril, has also been observed to inhibit other metalloenzymes such as tyrosinase and metallo-beta lactamase through binding to the catalytic metal ions and regarding CA as a zinc-containing metallo-enzyme, in the current study, we set out to determine whether captopril/enalapril inhibit CA esterase activity of the purified human CA II or not? Then, we revealed the inhibitors' potencies (IC50, Ki and Kdiss values) and also mode of inhibition. Our results also showed that enalapril is more potent CA inhibitor than captopril. Since enalapril represents no sulfhydryl moiety, thus carboxylate group may have a determinant role in inhibiting of CA esterase activity, the conclusion confirmed by molecular docking studies. Additionally, since CA inhibitory potencies of captopril/enalapril were much lower than those of classic sulfonamide drugs, the findings of the current study may explain why these drugs exhibit no effective CA inhibition at the concentrations reached in vivo and also may shed light on the way of generating new class of inhibitors that will discriminately inhibit various CA isoforms.

Effect of Chemical Structure on Polymer-Templated Growth of Graphitic Nanoribbons.

Graphene nanoribbon (GNR) is an important candidate for future nanoelectronics due to its high carrier mobility and dimension-controlled band gap. Polymer-templated growth is a promising method toward high quality and massive production of GNRs. However, the obtained GNRs so far are still quite defective. In order to rationally control the crystallinity of the synthesized GNRs, herein we systematically investigate the effect of polymer chemical structure on their templated growth of GNRs. We studied the morphology/dimensions, composition, graphitization degree, and electrical conductivity of GNRs derived from four different types of electrospun polymers. The four polymers polystyrene (PS), poly(vinyl alcohol) (PVA), polyvinylphenol (PVP), and Novolac (a phenolic resin) are chosen to investigate the effect of metal binding and the effect of aromatic moieties. We found that metal-binding functional groups are crucial for obtaining uniform and continuous GNRs. On the other hand, a polymer with aromatic moieties leads to a higher sp(2) percentage in the resulting GNRs, showing a higher graphitization degree and electrical conductivity.

Biosorption of metals (Cd, Cu and Zn) by the freshwater diatom Planothidium lanceolatum: a laboratory study

Biosorption, the naturally occurring physiochemical process which passively concentrates and binds contaminants to cellular structures, can be used in biological systems for the removal of metal ions from polluted waters. It also has the potential to achieve better performance at lower cost than conventional wastewater treatment technologies. The aim of this study was to characterize the ability of the freshwater diatom Planothidium lanceolatum (Brébisson) Lange-Bertalot to biosorb cadmium (Cd), copper (Cu) and zinc (Zn) from aqueous solutions. This diatom is one of the most dominant microalgae in the Tensift River, Marrakech region, Morocco, into which industrial wastewaters are often discharged directly, without pretreatment. As the water from this river is used for irrigation, it represents a potential risk to the environment and human health. The choice of these three heavy metals is based on their high concentrations in mining waste and industrial wastewaters. Our results indicate that the biosorption of metals by P. lanceolatum increased with the initial concentration of metal ions in the medium up to 100–130 mg L−1. The maximum biosorbed metal ion concentrations were 104, 81 and 41 mg per 16×108 diatom cells L−1 for Zn, Cu and Cd, respectively. The maximum uptake of metals was obtained at pH 6.0 for Cu and at pH 8.0 for Cd and Zn. An increase in the biosorption of P. lanceolatum was observed with an increase in temperature from 15 to 25†C. The biosorption of all three metal ions followed the Langmuir isotherm. Competitive biosorption of Cd, Cu and Zn ions was also achieved. Fourier transform infrared spectroscopy revealed the different metal-binding functional groups on the diatom surface that are able to react with metals in the medium. The results suggest that P. lanceolatum can be used as a biosorbent for the efficient removal of heavy metals from aqueous solutions at temperature and pH values close to average values in the Tensift River.

Cobalt binding in the photosynthetic bacterium R. sphaeroides by X-ray absorption spectroscopy

Cobalt is an important oligoelement required for bacteria; if present in high concentration, exhibits toxic effects that, depending on the microorganism under investigation, may even result in growth inhibition. The photosynthetic bacterium Rhodobacter (R.) sphaeroides tolerates high cobalt concentration and bioaccumulates Co(2+) ion, mostly on the cellular surface. Very little is known on the chemical fate of the bioaccumulated cobalt, thus an X-ray absorption spectroscopy investigation was conducted on R. sphaeroides cells to gain structural insights into the Co(2+) binding to cellular components. X-ray absorption near-edge spectroscopy and extended X-ray absorption fine structure measurements were performed on R. sphaeroides samples containing whole cells and cell-free fractions obtained from cultures exposed to 5 mM Co(2+). An octahedral coordination geometry was found for the cobalt ion, with six oxygen-ligand atoms in the first shell. In the soluble portion of the cell, cobalt was found bound to carboxylate groups, while a mixed pattern containing equivalent amount of two sulfur and two carbon atoms was found in the cell envelope fraction, suggesting the presence of carboxylate and sulfonate metal-binding functional groups, the latter arising from sulfolipids of the cell envelope.

Functional Cavitands: Chemical Reactivity in Structured Environments

AbstractFor Abstract see ChemInform Abstract in Full Text.

Functional cavitands: Chemical reactivity in structured environments

Container-shaped molecules provide structured environments that impart geometric bounds on the motions and conformations of smaller molecular occupants. Moreover, they provide "solvation" that is constrained in time and space. When inwardly directed functional groups are present, they can interact chemically with the occupants. Additionally, the potential for reactivity and catalysis is greatly enhanced. Deep cavitands, derived from resorcinarenes, nearly surround smaller molecules and have been one of the most successful platforms for elaboration with functional groups. Derivatives bearing organic and metal-binding functional groups have been shown to affect recognition properties and selectively accelerate diverse reactions. In this review, we examine recent examples of these systems with an emphasis on how and why ordered nanoenvironments impart changes in the properties and reactivity of their occupants.

Neptunium(IV) complexation by humic substances studied by X-ray absorption fine structure spectroscopy

SummaryWe studied the coordination environment of neptunium(IV) in complexes with various natural and synthetic humic and fulvic acids at pH 1 by X-ray absorption fine structure (XAFS) spectroscopy. The results were compared to those obtained for the interaction of neptunium(IV) with Bio-Rex70, a cation exchange resin having solely carboxylic groups as metal binding functional groups. In both neptunium humate complexes and neptunium Bio-Rex70 sorbates, Np4+is surrounded by about 10 oxygen atoms at an average distance of 2.36±0.02 Å. This verifies that the carboxylic groups are the main complexing sites of the humic substances responsible for binding neptunium(IV) in the acidic pH range. The data suggest a predominant monodentate coordination of the carboxylate groups to neptunium(IV) ions.

Inhibition of the antibacterial target UDP-(3-O-acyl)-N-acetylglucosamine deacetylase (LpxC): isoxazoline zinc amidase inhibitors bearing diverse metal binding groups.

UDP-3-O-[R-3-hydroxymyristoyl]-GlcNAc deacetylase (LpxC) is a zinc amidase that catalyzes the second step of lipid A biosynthesis in Gram negative bacteria. Known inhibitors of this enzyme are oxazolines incorporating a hydroxamic acid at the 4-position, which is believed to coordinate to the single essential zinc ion. A new structural class of inhibitors was designed to incorporate a more stable and more synthetically versatile isoxazoline core. The synthetic versatility of the isoxazoline allowed for a broad study of metal binding groups. Nine of 17 isoxazolines, each incorporating a different potential metal binding functional group, were found to exhibit enzyme inhibitory activity, including one that is more active than the corresponding hydroxamic acid. Additionally, a designed affinity label inhibits LpxC in a time-dependent manner.