Toxoplasma acyl-CoA synthetase TgACS3 is crucial to channel host fatty acids in lipid droplets and for parasite propagation.

Apicomplexa comprise important pathogenic parasitic protists that heavily depend on lipid acquisition to survive within their human host cells. Lipid synthesis relies on the incorporation of an essential combination of fatty acids (FAs) either generated by a metabolically adaptable de novo synthesis in the parasite or by scavenging from the host cell. The incorporation of FAs into membrane lipids depends on their obligate metabolic activation by specific enzyme groups, acyl-CoA synthetases (ACSs). Each ACS has its own specificity, so it can fulfill specific metabolic functions. Whilst such functionalities have been well studied in other eukaryotic models, their roles and importance in Apicomplexa are currently very limited, especially for Toxoplasma gondii. Here, we report the identification of seven putative ACSs encoded by the genome of T. gondii (TgACS), which localize to different sub-cellular compartments of the parasite, suggesting exclusive functions. We show that the perinuclear/cytoplasmic TgACS3 regulates the replication and growth of Toxoplasma tachyzoites. Conditional disruption of TgACS3 shows that the enzyme is required for parasite propagation and survival, especially under high host nutrient content. Lipidomic analysis of parasites lacking TgACS3 reveals its role in the activation of host-derived FAs that are used for i) parasite membrane phospholipid and ii) storage triacylglycerol (TAG) syntheses, allowing proper membrane biogenesis of parasite progenies. Altogether, our results reveal the role of TgACS3 as the bulk FA activator for membrane biogenesis allowing intracellular division and survival in T. gondii tachyzoites, further pointing to the importance of ACS and FA metabolism for the parasite.

Prehydrated Electrons Activated by Continuous Electron Transfer Stemmed from Peracetic Acid Homolysis Mediated by Diamond Surface Defects for Enhanced PFOA Destruction.

Research on the use of peracetic acid (PAA) activated by nonmetal solid catalysts for the removal of dissolved refractory organic compounds has gained attention recently due to its improved efficiency and suitability for advanced water treatment (AWT). Among these catalysts, nanocarbon (NC) stands out as an exceptional example. In the NC-based peroxide AWT studies, the focus on the mechanism involving multimedia coordination on the NC surface (reactive species (RS) path, electron reduction non-RS pathway, and singlet oxygen non-RS path) has been confined to the one-step electron reaction, leaving the mechanisms of multichannel or continuous electron transfer paths unexplored. Moreover, there are very few studies that have identified the nonfree radical pathway initiated by electron transfer within PAA AWT. In this study, the complete decomposition (kobs = 0.1995) and significant defluorination of perfluorooctanoic acid (PFOA, deF% = 72%) through PAA/NC has been confirmed. Through the use of multiple electrochemical monitors and the exploration of current diffusion effects, the process of electron reception and conduction stimulated by PAA activation was examined, leading to the discovery of the dynamic process from the PAA molecule → NC solid surface → target object. The vital role of prehydrated electrons (epre-) before the entry of resolvable electrons into the aqueous phase was also detailed. To the best of our knowledge, this is the first instance of identifying the nonradical mechanism of continuous electron transfer in PAA-based AWT, which deviates from the previously identified mechanisms of singlet oxygen, single-electron, or double-electron single-path transfer. The pathway, along with the strong reducibility of epre- initiated by this pathway, has been proven to be essential in reducing the need for catalysts and chemicals in AWT.

Coconut shell carbon via phosphoric acid activation for rhodamine B, malachite green, and methylene blue adsorption - equilibrium and kinetics.

This study was aimed at evaluating the removal of different cationic dyes onto phosphoric acid-activated coconut shell carbon. The activated carbon was characterized for surface functional groups, thermal decomposition profiles, surface morphology, and textural properties. The specific area was recorded as 1,221 m2/g with 100% mesoporosity. On molecular basis, the activated carbon adsorbs malachite green, methylene blue, and rhodamine B at maximum capacities of 1.52 mmol/g, 0.80 mmol/g, and 0.58 mmol/g, respectively. It indirectly implies the selectivity of activated carbon toward malachite green, and behaves differently due to steric hindrance of dye molecules. All equilibrium data obeyed Langmuir model, while the kinetic data are closely fitted to pseudo-second order model as concentration increases. To conclude, coconut shell activated carbon is more effective to remove malachite green compared to methylene blue and rhodamine B.

This paper is expected to give a further insight into the valorization of coconut shell into activated carbon, and its re-purpose for the remediation of dye-contaminated streams, for which methylene blue, malachite green and rhodamine B were used as model pollutants. This study aims to contribute to the growing body of research on the selective removal of malachite green over the other two dyes onto coconut shell activated carbon, which to the best of our knowledge is still absent in the open literature.

Facet-dependent activation of oxalic acid over hematite nanocrystals under the irradiation of visible light for efficient degradation of pollutants.

Naturally occurring hematite has been widely studied in the Fenton-like system for water pollutant remediation due to its abundance and non-toxicity. However, its inadequate catalytic activity results in difficulty in effectively degrading pollutants in the catalytic degradation system that it constitutes. Thus, we constructed a photochemical system composed of hematite with {001} facet of high activity facet and low-cost and non-toxic oxalic acid (OA) for the removal of various types of pollutants. The removal rate for the degradation of metronidazole, tetracycline hydrochloride, Rhodamine B, and hexavalent chromium by hematite nanoplate with the exposed {001} facet activating OA under visible light irradiation was 4.75, 2.25, 2.33, and 2.74 times than that by the exposed {110} facet, respectively. Density functional theory (DFT) calculation proved that the OA molecule was more easily adsorbed on the {001} facet of hematite than that on the {110} facet, which would favor the formation of the more Fe(III)-OA complex and reactive species. In addition, the reactive site of metronidazole for the attraction of radicals was identified on the basis of the DFT calculation on the molecular occupied orbitals, and the possible degradation pathway for metronidazole included carbon chain fracture, hydroxyethyl-cleavage, denitrogenation, and hydroxylation. Thus, this finding may offer a valuable direction in designing an efficient iron-based catalyst based on facet engineering for the improved activity of Fenton-like systems such as OA activation.

Ultrahigh Performance H2 O2 Generation by Single-Atom Fe Catalysts with N/O Bidentate Ligand via Oxalic Acid and Oxygen Molecules Activation.

Single-atom catalysts (SACs) for photocatalytic hydrogen peroxide (H2 O2 ) generation are researched but it is still challenging to obtain high H2 O2 yields. Herein, graphite carbon nitride (FeSA /CN) confined single Fe atoms with N/O coordination is prepared, and FeSA /CN shows high H2 O2 production via oxalic acid and O2 activation. Under visible light illumination, the concentration of H2 O2 generated by FeSA /CN can achieve 40.19 mM g-1 h-1 , which is 10.44 times higher than that of g-C3 N4 . The enhanced H2 O2 generation can be attributed to the formation of metal-organic complexes and rapid electron transfer. Moreover, the O2 activation of photocatalysts is revealed by 3,3',5,5'-tetramethylbenzidine oxidation. The results display that the O2 activation capacity of FeSA /CN is higher than that of g-C3 N4 , which facilitates the formation of H2 O2 . Finally, density functional theory calculation demonstrates that O2 is chemically adsorbed on Fe atomic sites. The adsorption energy of O2 is enhanced from -0.555 to -1.497 eV, and the bond length of OO is extended from 1.235 to 1.292 Å. These results exhibit that the confinement of single Fe atoms can promote O2 adsorption and activation. Finally, the photocatalytic mechanism is elaborated, which provides a deep understanding for SACs-catalyzed H2 O2 generation.

Whose Oxygen Atom Is Transferred to the Products? A Case Study of Peracetic Acid Activation via Complexed MnII for Organic Contaminant Degradation.

Identifying reactive species in advanced oxidation process (AOP) is an essential and intriguing topic that is also challenging and requires continuous efforts. In this study, we exploited a novel AOP technology involving peracetic acid (PAA) activation mediated by a MnII-nitrilotriacetic acid (NTA) complex, which outperformed iron- and cobalt-based PAA activation processes for rapidly degrading phenolic and aniline contaminants from water. The proposed MnII/NTA/PAA system exhibited non-radical oxidation features and could stoichiometrically oxidize sulfoxide probes to the corresponding sulfone products. More importantly, we traced the origin of O atoms from the sulfone products by 18O isotope-tracing experiments and found that PAA was the only oxygen-donor, which is different from the oxidation process mediated by high-valence manganese-oxo intermediates. According to the results of theoretical calculations, we proposed that NTA could tune the coordination circumstance of the MnII center to elongate the O-O bond of the complexed PAA. Additionally, the NTA-MnII-PAA* molecular cluster presented a lower energy gap than the MnII-PAA complex, indicating that the MnII-peroxy complex was more reactive in the presence of NTA. Thus, the NTA-MnII-PAA* complex exhibited a stronger oxidation potential than PAA, which could rapidly oxidize organic contaminants from water. Further, we generalized our findings to the CoII/PAA oxidation process and highlighted that the CoII-PAA* complex might be the overlooked reactive cobalt species. The significance of this work lies in discovering that sometimes the metal-peroxy complex could directly oxidize the contaminants without the further generation of high-valence metal-oxo intermediates and/or radical species through interspecies oxygen and/or electron transfer.

Carbonized polyaniline-activated peracetic acid advanced oxidation process for organic removal: Efficiency and mechanisms.

Recently, advanced oxidation processes (AOPs) based upon peracetic acid (PAA) with high efficiency for degrading aqueous organic contaminants have attracted extensive attention. Herein, a novel metal-free N-doped carbonaceous catalyst, namely, carbonized polyaniline (CPANI), was applied to activate PAA to degrade phenolic and pharmaceutical pollutants. The results showed that the CPANI/PAA system could effectively degrade 10 µM phenol in 60 min with low concentrations of PAA (0.1 mM) and catalyst (25 mg L-1). This system also performed well within a wide pH range of 5-9 and displayed high tolerance to Cl-, HCO3- and humic acid. The nonradical pathway [singlet oxygen (1O2)] was found to be the dominant pathway for degrading organic contaminants in the CPNAI/PAA system. Systematic characterization revealed that the graphitic N, pyridinic N, carbonyl groups (CO) and defects played the role of active sites on CPANI during the activation of PAA. The catalytic capacity of spent CPANI could be conveniently recovered by thermal treatment. The findings will be helpful for the application of metal-free carbonaceous catalyst/PAA processes in decontaminating water.

Potential of magnetic quinoa biosorbent composite and HNO3 treated biosorbent for effective sequestration of chromium (VI) from contaminated water.

The present study aims to prepare novel quinoa biosorbent (QB), acid activated QB (QB/Acid) and its nanocomposite with magnetic nanoparticles (QB/MNPs) for batch scale Cr removal from contaminated water. The Cr adsorption was systematically studied at different pH (2-9), adsorbent dosage (1-3 g/L), initial concentration (25-200 mg/L), contact time (180 min) and competing ions in water. Maximum Cr adsorption was observed onto QB/MNPs (57.4 mg/L), followed by QB/Acid (46.35 mg/g) and QB (39.9 mg/g). The Cr removal by QB/MNPs was higher than QB/Acid and QB. Results revealed that the highest Cr removal was obtained at optimum pH 4, 25 mg/L, and 2 g/L dosage. The FTIR spectra displayed various functional groups on adsorbents surface serving as a potential scaffold to remove Cr from contaminated water. The equilibrium and kinetic Cr adsorption data best fitted with Freundlich and pseudo-second order models, respectively (R2 ≥ 0.96). The QB/MNPs showed excellent reusability in five adsorption/desorption cycles (4.7% decline) with minor leaching of Fe (below threshold level). The coexisting ions in groundwater showed an inhibitory effect on Cr sequestration (5%) from water. The comparison of Cr adsorption by QB/MNPs and QB/Acid showed better potential for Cr sequestration than various previously explored adsorbents in the literature.

Quinoa is a cereal crop and after harvesting quinoa straws are either burnt or thrown away which can cause several environmental problems. It would be beneficial to utilize quinoa straws and its modified forms as adsorbents for the water remediation. Therefore, current study aims to estimate the adsorption capacity of quinoa biomass as biosorbent (QB) and its modifications (QB/Acid and QB/MNPs) to treat Cr (VI) contaminated water. The influence of various parameters governing the Cr removal from water has been evaluated. The reusability of QB/MNPs has also been evaluated for its economical use without losing effectiveness for Cr removal from water. The comparison of Cr adsorption by QB/MNPs and QB/Acid showed better adsorption potential for Cr sequestration than various previously explored adsorbents in the literature.

N-(Morpholine-4-dithio)phthalimide: A Shelf-Stable, Bilateral Platform Molecule Enabling Access to Diverse Unsymmetrical Disulfides.

Synthetic methods for unsymmetrical disulfides are greatly needed owing to their applications in drug discovery, linker chemistry, and materials sciences. In this study, a new shelf-stable and easy-to-prepare bilateral disulfurating platform molecule, N-(morpholine-4-dithio)phthalimide, has been developed for the divergent synthesis of unsymmetrical disulfides. The amino and imide leaving groups of this reagent can be orthogonally transformed. Under acidic conditions, the amino moiety undergoes selective protonation and thus can be displaced by various carbon nucleophiles, such as allyl trimethylsilanes, alkynyl silanes, and electron-rich arenes, leaving the phthalimide moiety untouched. Meanwhile, the phthalimide leaving group is amenable to substitution under basic or neutral conditions. The combination of these transformations provides rapid access to diverse unsymmetrical disulfides through two C-S bond-forming reactions.

Dicarboxylic Acid Monoesters in ß- and δ-Lactam Synthesis.

A N-(2-methoxy-2-oxoethyl)-N-(phenylsulfonyl)glycine monomethyl ester of the respective dicarboxylic acid was involved in a reaction with imines promoted by acetic anhydride at an elevated temperature. Instead of the initially expected δ-lactam products of the Castagnoli-Cushman-type reaction, medicinally important 3-amino-2-azetidinones were obtained as the result of cyclization, involving a methylene group adjacent to an acid moiety. In contrast, replacing alcohol residue with hexafluoroisopropyl in the same substrate made another methylene group (adjacent to the ester moiety) more reactive to furnishing the desired δ-lactam in the Castagnoli-Cushman fashion.

Characteristics of Raw and Acid-Activated Bentonite and Its Application for Improving Electrical Conductivity of Tap Water.

This study aimed to investigate the characteristics of acid-activated bentonite by focusing on its capability of improving the quality of tap water used during wire electrical discharge machining. Raw bentonite (RB) was activated using sulfuric acid, nitric acid, and phosphoric acid solutions with concentrations of 1, 5, and 10 mol/L, respectively. Scanning electron microscopy images, specific surface area, pore volume, cation exchange capacity, X-ray diffraction patterns, and binding energy of RB and acid-activated bentonites were also evaluated. The specific surface area and pore volume of acid-activated bentonites exceeded those of RB. Conversely, the cation exchange capacity of acid-activated bentonites exhibited an opposite trend. The electrical conductivity of tap water was decreased significantly due to bentonite activated with sulfuric acid, nitric acid, and phosphoric acid solution (removal percentage of approximately 31-39%), as compared to that due to RB. Therefore, the relationship between electrical conductivity and the removed concentration of anion/cation ions was evaluated; the correlation coefficient was -0.950 for the experimental condition in this study. Additionally, the amount of magnesium, calcium, potassium, and sodium ions were decreased after the treatment. These results indicated that acid-activated bentonite can be produced from RB via acid activation and that it can be used to decrease electrical conductivity of tap water.

Activation of Aryl Carboxylic Acids by Diboron Reagents towards Nickel-Catalyzed Direct Decarbonylative Borylation.

The Ni-catalyzed decarbonylative borylation of (hetero)aryl carboxylic acids with B2 cat2 has been achieved without recourse to any additives. This Ni-catalyzed method exhibits a broad substrate scope covering poorly reactive non-ortho-substituted (hetero)aryl carboxylic acids, and tolerates diverse functional groups including some of the groups active to Ni0 catalysts. The key to achieve this decarbonylative borylation reaction is the choice of B2 cat2 as a coupling partner that not only acts as a borylating reagent, but also chemoselectively activates aryl carboxylic acids towards oxidative addition of their C(acyl)-O bond to Ni0 catalyst via the formation of acyloxyboron compounds. A combination of experimental and computational studies reveals a detailed plausible mechanism for this reaction system, which involves a hitherto unknown concerted decarbonylation and reductive elimination step that generates the aryl boronic ester product. This mode of boron-promoted carboxylic acid activation is also applicable to other types of reactions.

Batch interaction of emerging tetracycline contaminant with novel phosphoric acid activated corn straw porous carbon: Adsorption rate and nature of mechanism.

In this work, corn straw (CS) based porous carbon was prepared by one-step phosphoric acid (H3PO4) low temperature activation. The impregnation ratios (H3PO4/CS, g/g) played an important role in the pore development. ACS300-1 engineered at 300 °C and the impregnation ratio of 1.0 showed the maximal specific surface area of 463.89 m2/g with total pore volume of 0.387 cm3/g, attaining a high tetracycline (TC) uptake of 227.3 mg/g. The adsorption of TC onto ACS300-1 was found tolerant with wide pH (2.0-10.0) and high ionic strength (0 - 0.5 M). The adsorption data can be fitted well by the pseudo-second order kinetic model and Langmuir isotherm model. The endothermic and spontaneous properties of the adsorption system was implied by Thermodynamic study. The findings of the current work conclude that one-step H3PO4 activation is a green and promising method for corn straw based porous carbon that may be found with great potentials in antibiotic containing wastewater treatment.

Removal of sulfadiazine from aqueous solution by in-situ activated biochar derived from cotton shell.

Phosphoric acid is used to in-situ activate biochar pyrolyzed by cotton shells to enhance the adsorption ability of sulfadiazine (SDZ). To confirm the optimum condition, different impregnation ratios and impregnation times were investigated. It was found that the biochar (BC) pyrolyzed under the condition of an impregnation ratio of 2.5 and an impregnation time of 6 h showed the highest performance for the removal of SDZ. The maximum adsorption ability was 86.89 mg/g at a temperature of 298 K. The pseudo-second-order model was used to disclose the adsorption process of SDZ by BCs. The experimental data were described by the Langmuir and Temkin isotherms at different temperatures. It was found that the sorption of SDZ was an exothermic process according to the thermomechanical analysis. The activated BC could be recycled for at least five times with a high removal rate of SDZ. Thus, activated BCs are regarded as promising adsorbents for SDZ removal.

The High Efficiency of Anionic Dye Removal Using Ce-Al13/Pillared Clay from Darbandikhan Natural Clay.

Natural clay from Darbandikhan (DC) was evaluated in its natural form, after acid activation (ADC), and after pillaring (PILDC) as a potential adsorbent for the adsorption of methyl orange (MO) as a model anionic dye adsorbate. The effect of different clay treatments was investigated using X-Ray Diffraction (XRD), X-Ray Fluorescence (XRF), Scanning Electron Microscope (SEM) and Fourier-Transform Infrared Spectroscopy (FT-IR), and N2 physisorption analysis. Both acid activation and pillaring resulted in a significant increase in adsorption affinity, respectively. The adsorption favored acidic pH for the anionic dye (MO). The adsorption process was found to follow pseudo-second-order kinetics with activation energies of 5.9 and 40.1 kJ·mol-1 for the adsorption of MO on ADC and PILDC, respectively, which are characteristic of physical adsorption. The adsorption isotherms (Langmuir, Redlich-Peterson and Freundlich) were fitted well to the experimental data. The specific surface area of the natural clay was very low (22.4 m2·g-1) compared to high-class adsorbent materials. This value was increased to 53.2 m2·g-1 by the pillaring process. Nevertheless, because of its local availability, the activated materials may be useful for the cleaning of local industrial wastewaters.

Yarrowia lipolytica AAL genes are involved in peroxisomal fatty acid activation.

In yeast, ß-oxidation of fatty acids (FAs) essentially takes place in peroxisomes, and FA activation must precede FA oxidation. In Saccharomyces cerevisiae, a single fatty-acyl­CoA-synthetase, ScFaa2p, mediates peroxisomal FA activation. We have previously shown that this reaction also exists in the oleaginous yeast Yarrowia lipolytica; however, the protein involved in this process remains unknown. Here, we found that proteins, named Aal proteins (Acyl/Aryl-CoA-ligases), resembling the 4-coumarate­CoA-ligase-like enzymes found in plants are involved in peroxisomal FA activation in Y. lipolytica; Y. lipolytica has 10 AAL genes, eight of which are upregulated by oleate. All the Aal proteins contain a PTS1-type peroxisomal targeting sequence (A/SKL), suggesting a peroxisomal localization. The function of the Aal proteins was analyzed using the faa1Δant1Δ mutant strain, which demonstrates neither cytoplasmic FA activation (direct result of FAA1 deletion) nor peroxisomal FA activation (indirect result of ANT1 deletion, a gene coding an ATP transporter). This strain is thus highly sensitive to external FA levels and unable to store external FAs in lipid bodies (LBs). Whereas the overexpression of (cytoplasmic) AAL1ΔPTS1 was able to partially complement the growth defect observed in the faa1Δant1Δ mutant on short-, medium- and long-chain FA media, the presence of Aal2p to Aal10p only allowed growth on the short-chain FA medium. Additionally, partial LB formation was observed in the oleate medium for strains overexpressing Aal1ΔPTS1p, Aal4ΔPTS1p, Aal7ΔPTS1p, and Aal8ΔPTS1p. Finally, an analysis of the FA content of cells grown in the oleate medium suggested that Aal4p and Aal6p present substrate specificity for C16:1 and/or C18:0.

Dynamic regulation of fatty acid pools for improved production of fatty alcohols in Saccharomyces cerevisiae.

BACKGROUND: In vivo production of fatty acid-derived chemicals in Saccharomyces cerevisiae requires strategies to increase the intracellular supply of either acyl-CoA or free fatty acids (FFAs), since their cytosolic concentrations are quite low in a natural state for this organism. Deletion of the fatty acyl-CoA synthetase genes FAA1 and FAA4 is an effective and straightforward way to disable re-activation of fatty acids and drastically increase FFA levels. However, this strategy causes FFA over-accumulation and consequential release to the extracellular medium, which results in a significant loss of precursors that compromises the process yield. In the present study, we aimed for dynamic expression of the fatty acyl-CoA synthetase gene FAA1 to regulate FFA and acyl-CoA pools in order to improve fatty alcohol production yields. RESULTS: We analyzed the metabolite dynamics of a faa1Δ faa4Δ strain constitutively expressing a carboxylic acid reductase from Mycobacterium marinum (MmCAR) and an endogenous alcohol dehydrogenase (Adh5) for in vivo production of fatty alcohols from FFAs. We observed production of fatty acids and fatty alcohols with different rates leading to high levels of FFAs not being converted to the final product. To address the issue, we expressed the MmCAR + Adh5 pathway together with a fatty acyl-CoA reductase from Marinobacter aquaeolei to enable fatty alcohol production simultaneously from FFA and acyl-CoA, respectively. Then, we expressed FAA1 under the control of different promoters in order to balance FFA and acyl-CoA interconversion rates and to achieve optimal levels for conversion to fatty alcohols. Expressing FAA1 under control of the HXT1 promoter led to an increased accumulation of fatty alcohols per OD600 up to 41% while FFA levels were decreased by 63% compared with the control strain. CONCLUSIONS: Fine-tuning and dynamic regulation of key metabolic steps can be used to improve cell factories when the rates of downstream reactions are limiting. This avoids loss of precursors to the extracellular medium or to competing reactions, hereby potentially improving the process yield. The study also provides knowledge of a key point of fatty acid regulation and homeostasis, which can be used for future design of cells factories for fatty acid-derived chemicals.

Biosorption of chromium(VI) in aqueous solutions by chemically modified Strychnine tree fruit shell.

Chromium(VI) was removed from aqueous solution using sulfuric- and phosphoric-acid-activated Strychnine tree fruit shells (SSTFS and PSTFS) as biosorbents. Effects of various parameters such as adsorbent dose (0.02-0.1 g/L), temperature (303-333 K), agitation speed, solution pH (2-9), contact time, and initial Cr(VI) concentration (50-250 mg/L) were studied for a batch adsorption system. The optimum pH range for Cr(VI) adsorption was determined as 2. Equilibrium adsorption data were analyzed with isotherm models and the Langmuir and Freundlich models got best fitted values for SSTFS (R2 value - 0.994) and PSTFS (R2 value - 0.996), respectively. The maximum adsorption capacities of SSTFS and PSTFS were 100 and 142.85 mg/g, respectively. The biosorption process was well explained by pseudo-second-order kinetic model with higher R2 value (SSTFS - 0.996, PSTFS - 0.990) for both biosorbents. Characterization of biosorbents was done using Fourier transform infrared spectroscopy, scanning electron microscopy, elemental analysis, energy-dispersive X-ray analysis, and thermogravimetric analysis. Thermodynamic studies revealed the spontaneous, endothermic, and randomness in nature of the Cr(VI) adsorption process. Different concentrations of NaOH solutions were used to perform the desorption studies. The results demonstrated that both SSTFS and PSTFS can be used as an effective and low-cost biosorbent for removal of Cr(VI) from aqueous solutions.

Functional Class I and II Amino Acid-activating Enzymes Can Be Coded by Opposite Strands of the Same Gene.

Aminoacyl-tRNA synthetases (aaRS) catalyze both chemical steps that translate the universal genetic code. Rodin and Ohno offered an explanation for the existence of two aaRS classes, observing that codons for the most highly conserved Class I active-site residues are anticodons for corresponding Class II active-site residues. They proposed that the two classes arose simultaneously, by translation of opposite strands from the same gene. We have characterized wild-type 46-residue peptides containing ATP-binding sites of Class I and II synthetases and those coded by a gene designed by Rosetta to encode the corresponding peptides on opposite strands. Catalysis by WT and designed peptides is saturable, and the designed peptides are sensitive to active-site residue mutation. All have comparable apparent second-order rate constants 2.9-7.0E-3 M(-1) s(-1) or ∼750,000-1,300,000 times the uncatalyzed rate. The activities of the two complementary peptides demonstrate that the unique information in a gene can have two functional interpretations, one from each complementary strand. The peptides contain phylogenetic signatures of longer, more sophisticated catalysts we call Urzymes and are short enough to bridge the gap between them and simpler uncoded peptides. Thus, they directly substantiate the sense/antisense coding ancestry of Class I and II aaRS. Furthermore, designed 46-mers achieve similar catalytic proficiency to wild-type 46-mers by significant increases in both kcat and Km values, supporting suggestions that the earliest peptide catalysts activated ATP for biosynthetic purposes.

A bridge between the aminoacylation and editing domains of leucyl-tRNA synthetase is crucial for its synthetic activity.

Leucyl-tRNA synthetases (LeuRSs) catalyze the linkage of leucine with tRNA(Leu). LeuRS contains a catalysis domain (aminoacylation) and a CP1 domain (editing). CP1 is inserted 35 Å from the aminoacylation domain. Aminoacylation and editing require CP1 to swing to the coordinated conformation. The neck between the CP1 domain and the aminoacylation domain is defined as the CP1 hairpin. The location of the CP1 hairpin suggests a crucial role in the CP1 swing and domain-domain interaction. Here, the CP1 hairpin of Homo sapiens cytoplasmic LeuRS (hcLeuRS) was deleted or substituted by those from other representative species. Lack of a CP1 hairpin led to complete loss of aminoacylation, amino acid activation, and tRNA binding; however, the mutants retained post-transfer editing. Only the CP1 hairpin from Saccharomyces cerevisiae LeuRS (ScLeuRS) could partly rescue the hcLeuRS functions. Further site-directed mutagenesis indicated that the flexibility of small residues and the charge of polar residues in the CP1 hairpin are crucial for the function of LeuRS.