The influence of thioether-substituted ligands in dicopper(II) complexes: Enhancing oxidation and biological activities.

This paper describes the synthesis, structural analysis, as well as the magnetic and spectroscopic characterizations of three new dicopper(II) complexes with dinucleating phenol-based ligands containing different thioether donor substituents: aromatic (1), aliphatic (2) or thiophene (3). Temperature-dependent magnetometry reveals the presence of antiferromagnetic coupling for 1 and 3 (J = -2.27 cm-1 and -5.01 cm-1, respectively, H = -2JS1S2) and ferromagnetic coupling for 2 (J = 5.72 cm-1). Broken symmetry DFT calculations attribute this behavior to a major contribution from the dz2 orbitals for 1 and 3, and from the dx2-y2 orbitals for 2, along with the p orbitals of the oxygens. The bioinspired catalytic activities of these complexes related to catechol oxidase were studied using 3,5-di-tert-butylcatechol as substrate. The order of catalytic rates for the substrate oxidation follows the trend 1 > 2 > 3 with kcat of (90.79 ± 2.90) × 10-3 for 1, (64.21 ± 0.99) × 10-3 for 2 and (14.20 ± 0.32) × 10-3 s-1 for 3. The complexes also cleave DNA through an oxidative mechanism with minor-groove preference, as indicated by experimental and molecular docking assays. Antimicrobial potential of these highly active complexes has shown that 3 inhibits both Staphylococcus aureus bacterium and Epidermophyton floccosum fungus. Notably, the complexes were found to be nontoxic to normal cells but exhibited cytotoxicity against epidermoid carcinoma cells, surpassing the activity of the metallodrug cisplatin. This research shows the multifaceted properties of these complexes, making them promising candidates for various applications in catalysis, nucleic acids research, and antimicrobial activities.

Improving Enzymatic Saccharification of Peach Palm (Bactris gasipaes) Wastes via Biological Pretreatment with Pleurotus ostreatus.

The white-rot fungus Pleurotus ostreatus was used for biological pretreatment of peach palm (Bactris gasipaes) lignocellulosic wastes. Non-treated and treated B. gasipaes inner sheaths and peel were submitted to hydrolysis using a commercial cellulase preparation from T. reesei. The amounts of total reducing sugars and glucose obtained from the 30 d-pretreated inner sheaths were seven and five times higher, respectively, than those obtained from the inner sheaths without pretreatment. No such improvement was found, however, in the pretreated B. gasipaes peels. Scanning electronic microscopy of the lignocellulosic fibers was performed to verify the structural changes caused by the biological pretreatments. Upon the biological pretreatment, the lignocellulosic structures of the inner sheaths were substantially modified, making them less ordered. The main features of the modifications were the detachment of the fibers, cell wall collapse and, in several cases, the formation of pores in the cell wall surfaces. The peel lignocellulosic fibers showed more ordered fibrils and no modification was observed after pre-treatment. In conclusion, a seven-fold increase in the enzymatic saccharification of the Bactris gasipaes inner sheath was observed after pre-treatment, while no improvement in enzymatic saccharification was observed in the B. gasipaes peel.

Magnetic mining waste based-geopolymers applied to catalytic reactions with ozone.

The demand for sustainable and low-cost materials for wastewater treatment is increasing considerably. In this scenario, geopolymers have gained great interest, due to their good mechanical properties, their ability to be produced from industrial waste and their adsorbent or catalytic properties. In this study, novel magnetic mining waste based-geopolymers were produced by incorporating a residue from phosphate waste rocks, which were extensively characterized (XRD, TGA/DTA, SEM, BET, XRF, FTIR, Mössbauer, ss-NMR and XPS). The materials produced showed formation of a dense framework, even with 75% incorporation of the residue. The iron oxides and their magnetic properties remained unchanged, and their application in advanced oxidation reactions were evaluated, in particular, as catalysts in ozonation reactions. All of the geopolymers presented catalytic activity in the ozonation reaction, with catalytic ozone decomposition values of up to 2.98 min-1, which is 99 times greater than non-catalyzed reactions. Moreover, the reuse (performed in three cycles) and hot filtration-like experiments demonstrated, respectively, the regenerability and heterogeneous catalytic properties of the produced materials, showcasing the potential of these waste materials for catalytic geopolymer production. demonstrating the potential of this waste to produce catalytic geopolymers.

Spectroscopical and Molecular Studies of Four Manganese(I) PhotoCORMs with Bioinspired Ligands Containing Non-Coordinated Phenol Groups.

Carbonyl compounds are widely explored in medicinal inorganic chemistry and have drawn attention due to their signaling functions in homeostasis. Carbon-monoxide-releasing molecules (CORMs) were developed with the purpose of keeping the CO inactive until its release in the intracellular environment, considering its biological relevance. However, for therapeutic applications, the mechanisms of photorelease and which electronic and structural variations influence its rates must be fully understood. In this work, four ligands containing a pyridine, a secondary amine, and a phenolic group with different substituents were used to prepare new Mn(I) carbonyl compounds. Structural and physicochemical characterization of these complexes was carried out and confirmed the proposed structures. X-ray diffractometry structures obtained for the four organometallic compounds revealed that the substituents in the phenolic ring promote only negligible distortions in their geometry. Furthermore, UV-Vis and IR kinetics showed the direct dependence of the electron-withdrawing or donating ability of the substituent group, indicating an influence of the phenol ring on the CO release mechanism. These differences in properties were also supported by theoretical studies at the DFT, TD-DFT, and bonding situation analyses (EDA-NOCV). Two methods were used to determine the CO release constants (kCO,old and kCO,new), where Mn-HbpaBr (1) had the greatest kCO by both methods (Kco,old = 2.36 × 10-3 s-1 and kCO,new = 2.37 × 10-3 s-1). Carbon monoxide release was also evaluated using the myoglobin assay, indicating the release of 1.248 to 1.827 carbon monoxides upon light irradiation.

High-performance hydrophobic magnetic hydrotalcite for selective treatment of oily wastewater.

Oil emulsified in water is one of the most difficult mixtures to treat due to the good stability of emulsions, so there is a growing demand for more efficient methods for separating immiscible oil/water mixtures. In this context, the focus of this study was to obtain an adsorbent for the selective treatment of a simulated oily wastewater. To this aim, a modified hydrotalcite sample with hydrophobic and magnetic characteristics was prepared and characterized. Initially, the effect of sodium dodecyl sulfate (SDS) amount on the adsorbent characteristics was evaluated (266-800 mgSDS g-1LDH). The hydrophobic hydrotalcite (LDH-SDS) containing 533 mgSDS g-1LDH (LDH-SDS2) presented a higher interlayer space where the surfactant molecules were arranged perpendicular to the lamellae, allowing better access to the hydrotalcite pores and facilitating the selective adsorption of oil compounds. Moreover, the synergistic association of hydrophobic properties with super-wetting and effective adhesion oil to Fe3O4 favoured the selective adsorption of the simulated oily wastewater onto the hydrophobic and magnetic hydrotalcite (LDH-MSDS), facilitating the post-treatment separation. The kinetic analysis demonstrated that the adsorption equilibrium was attained in 120 min and the pseudo-second order model was the most suitable for predicting the removal of total organic carbon (TOC) from the simulated oily wastewater. The Langmuir model described very well the equilibrium experimental data, with a maximum adsorption capacity for TOC removal using LDH-MSDS of 659.9 mg g-1. Therefore, the modified hydrotalcite prepared in this study showed intrinsic characteristics that make it a promising adsorbent for the selective treatment of oily wastewaters.

Bioinspired oxidation of benzyl alcohol: The role of environment and nuclearity of the catalyst evaluated by multivariate analysis.

Inspired by copper-containing enzymes such as galactose oxidase and catechol oxidase, in which distinct coordination environments and nuclearities lead to specific catalytic activities, we summarize here the catalytic properties of dinuclear and mononuclear copper species towards benzyl alcohol oxidation using a multivariate statistical approach. The new dinuclear [Cu2(µ-L1)(µ-pz)]2+ (1) is compared against the mononuclear [CuL2Cl] (2), where (L1)- and (L2)- are the respective deprotonated forms of 2,6-bis((bis(pyridin-2-ylmethyl)amino)methyl)-4-methylphenol, and 3-((bis(pyridin-2-ylmethyl)amino)methyl)-2-hydroxy-5-methylbenzaldehyde and (pz)- is a pyrazolato bridge. Copper(II) perchlorate (CP) is used as control. The catalytic oxidation of benzyl alcohol is pursued, aiming to assess the role of the ligand environment and nuclearity. The multivariate statistical approach allows for the search of optimal catalytic conditions, considering variables such as catalyst load, hydrogen peroxide load, and time. Species 1, 2 and CP promoted selective production of benzaldehyde at different yields, with only negligible amounts of benzoic acid. Under normalized conditions, 2 showed superior catalytic activity. This species is 3.5-fold more active than the monometallic control CP, and points out to the need for an efficient ligand framework. Species 2 is 6-fold more active than the dinuclear 1, and indicates the favored nuclearity for the conversion of alcohols into aldehydes.

Biomimetics for purple acid phosphatases: A historical perspective.

Biomimetics hold potential for varied applications in biotechnology and medicine but have also attracted particular interest as benchmarks for the functional study of their more complex biological counterparts, e.g. metalloenzymes. While many of the synthetic systems adequately mimic some structural and functional aspects of their biological counterparts the catalytic efficiencies displayed are mostly far inferior due to the smaller size and the associated lower complexity. Nonetheless they play an important role in bioinorganic chemistry. Numerous examples of biologically inspired and informed artificial catalysts have been reported, designed to mimic a plethora of chemical transformations, and relevant examples are highlighted in reviews and scientific reports. Herein, we discuss biomimetics of the metallohydrolase purple acid phosphatase (PAP), examples of which have been used to showcase synergistic research advances for both the biological and synthetic systems. In particular, we focus on the seminal contribution of our colleague Prof. Ademir Neves, and his group, pioneers in the design and optimization of suitable ligands that mimic the active site of PAP.

Full Exploitation of Peach Palm (Bactris gasipaes Kunth): State of the Art and Perspectives.

The peach palm (Bactris gasipaes Kunth) is a palm tree native to the Amazon region, with plantations expanding to the Brazilian Southwest and South regions. This work is a critical review of historical, botanical, social, environmental, and nutritional aspects of edible and nonedible parts of the plant. In Brazil, the importance of the cultivation of B. gasipaes to produce palm heart has grown considerably, due to its advantages in relation to other palm species, such as precocity, rusticity and tillering. The last one is especially important, as it makes the exploitation of peach palm hearts, contrary to what happens with other palm tree species, a non-predatory practice. Of special interest are the recent efforts aiming at the valorization of the fruit as a source of carotenoids and starch. Further developments indicate that the B. gasipaes lignocellulosic wastes hold great potential for being upcycled into valuable biotechnological products such as prebiotics, enzymes, cellulose nanofibrils and high fiber flours. Clean technologies are protagonists of the recovery processes, ensuring the closure of the product's life cycle in a "green" way. Future research should focus on expanding and making the recovery processes economically viable, which would be of great importance for stimulating the peach palm production chain.

Hydrolytic activity of new bioinspired MnIIIMnII and FeIIIMnII complexes as mimetics of PAPs: Biological and environmental interest.

Coordination compounds that mimic Purple Acid Phosphatases (PAPs) have drawn attention in the bioinorganic field due to their capacity to cleave phosphodiester bonds. However, their catalytic activity upon phosphate triesters is still unexplored. Thus, we report the synthesis and characterization of two binuclear complexes, [MnIIMnIII(L1)(OAc)2]BF4 (1) and [MnIIFeIII(L1)(OAc)2]BF4 (2) (H2L1 = 2-[N,N-bis-(2- pyridilmethyl)aminomethyl]-4-methyl-6-[N-(2-hydroxy-3-formyl-5-methylbenzyl)-N-(2-pyridylmethyl)aminomethyl]phenol), their hydrolytic activity and antioxidant potential. The complexes were fully characterized, including the X-Ray diffraction (XRD) of 1. Density functional theory (DFT) calculations were performed to better understand their electronic and structural properties and phosphate conjugates. The catalytic activity was analyzed for two model substrates, a diester (BDNPP) and a triester phosphate (DEDNPP). The results suggest enhancement of the hydrolysis reaction by 170 to 1500 times, depending on the substrate and complex. It was possible to accompany the catalytic reaction of DEDNPP hydrolysis by phosphorus nuclear magnetic resonance (31P NMR), showing that both 1 and 2 are efficient catalysts. Moreover, we also addressed that 1 and 2 present a relevant antioxidant potential, protecting the yeast Saccharomyces cerevisiae, used as eukaryotic model of study, against the exposure of cells to acute oxidative stress.

Hydrogen-atom and oxygen-atom transfer reactivities of iron(IV)-oxo complexes of quinoline-substituted pentadentate ligands.

A series of iron(II) complexes with the general formula [FeII(L2-Qn)(L)]n+ (n = 1, L = F-, Cl-; n = 2, L = NCMe, H2O) have been isolated and characterized. The X-ray crystallographic data reveals that metal-ligand bond distances vary with varying ligand field strengths of the sixth ligand. While the complexes with fluoride, chloride and water as axial ligand are high spin, the acetonitrile-coordinated complex is in a mixed spin state. The steric bulk of the quinoline moieties forces the axial ligands to deviate from the Fe-Naxial axis. A higher deviation/tilt is noted for the high spin complexes, while the acetonitrile coordinated complex displays least deviation. This deviation from linearity is slightly less in the analogous low-spin iron(II) complex [FeII(L1-Qn)(NCMe)]2+ of the related asymmetric ligand L1-Qn due to the presence of only one sterically demanding quinoline moiety. The two iron(II)-acetonitrile complexes [FeII(L2-Qn)(NCMe)]2+ and [FeII(L1-Qn)(NCMe)]2+ generate the corresponding iron(IV)-oxo species with higher thermal stability of the species supported by the L1-Qn ligand. The crystallographic and spectroscopic data for [FeIV(O)(L1-Qn)](ClO4)2 bear resemblance to other crystallographically characterized S = 1 iron(IV)-oxo complexes. The hydrogen atom transfer (HAT) and oxygen atom transfer (OAT) reactivities of both the iron(IV)-oxo complexes were investigated, and a Box-Behnken multivariate optimization of the parameters for catalytic oxidation of cyclohexane by [FeII(L2-Qn)(NCMe)]2+ using hydrogen peroxide as the terminal oxidant is presented. An increase in the average Fe-N bond length in [FeII(L1-Qn)(NCMe)]2+ is also manifested in higher HAT and OAT rates relative to the other reported complexes of ligands based on the N4Py framework. The results reported here confirm that the steric influence of the ligand environment is of critical importance for the reactivity of iron(IV)-oxo complexes, but additional electronic factors must influence the reactivity of iron-oxo complexes of N4Py derivatives.

New AlIIIZnII and AlIIICuII dinuclear complexes: Phosphatase-like activity and cytotoxicity.

Herein, we report the synthesis and characterization of the first two AlIII(µ-OH)MII (M = Zn (1) and Cu (2)) complexes with the unsymmetrical ligand H2L{2-[[(2-hydroxybenzyl)(2-pyridylmethyl)]aminomethyl]-6-bis(pyridylmethyl)aminomethyl}-4-methylphenol. The complexes were characterized through elemental analysis, X-ray crystallography, IR spectroscopy, mass spectrometry and potentiometric titration. In addition, complex 2 was characterized by electronic spectroscopy. Kinetics studies on the hydrolysis of the model substrate bis(2,4-dinitrophenyl)phosphate by 1 and 2 show Michaelis-Menten behavior, with 1 being slightly more active (8.31%) than 2 (at pH 7.0). The antimicrobial effect of the compounds was studied using four bacterial strains (Staphylococcus aureus, Pseudomonas aeuruginosa, Shigella sonnei and Shigella dysenteriae) and for both complexes the inhibition of bacterial growth was superior to that caused by sulfapyridine, but inferior to that of tetracycline. The dark cytotoxicity and photocytotoxicity (under UV-A light) of the complexes in a chronic myelogenous leukemia cell line were investigated. Complexes 1 and 2 exhibited significant cytotoxic activity against K562 cells, which undergoes a 2-fold increase on applying 5 min of irradiation with UV-A light. Complex 2 was more effective and a good correlation between cytotoxicity and intracellular concentration was observed, the intracellular copper concentration required to inhibit 50% of cell growth being 3.5 × 10-15 mol cell-1.

Chitosan functionalized with heptadentate dinucleating ligand applied to removal of nickel, copper and zinc.

The preconcentration of metal ions present at low concentration levels in aqueous systems and the selective removal of potentially toxic metals are important applications of adsorption processes. In this study, a heptadentate dinucleating ligand was anchored to chitosan for use in adsorption studies on Zn(II), Cu(II) and Ni(II) ions. The novel adsorbent was characterized by 13C NMR and FT-IR spectroscopy, TGA and BET surface area analysis. The degree of substitution of the ligand in chitosan, obtained from CHN analysis, was 0.73. The adsorption kinetics followed a pseudo-second-order model. The rate constants and the adsorption capacities for multicomponent systems decreased in the order Cu(II) >> Ni(II) ∼ Zn(II), indicating the preferential adsorption of Cu(II). For Cu(II) ions, the Langmuir model provided the best fitting to the experimental data, and the monolayer Cu(II) adsorption capacity was 0.404 mmol g-1, while the linear isotherm described Zn(II) and Ni(II) ion adsorption.

Plastic optical fibres applied on the photocatalytic degradation of phenol with Ag2MoO4 and ß-Ag2MoO4/Ag3PO4 under visible light.

In this study, plastic optical fibre (POF) was considered as a light-transmitting medium and substrate for use in a photocatalytic environmental purification system, using Ag2MoO4 and ß-Ag2MoO4/Ag3PO4 as photocatalysts. Pure Ag2MoO4 and a ß-Ag2MoO4/Ag3PO4 composite were synthesized using a facile precipitation method. The composition, structures and optical properties of as-prepared catalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), field-emission scanning electron microscopy (FESEM), UV/Vis diffuse reflectance spectroscopy (UV/Vis DRS), BET surface area and TGA/DTG. The catalysts were immobilized on POF and on the glass reactor surface and their efficiency in the phenol degradation was evaluated in a batch reactor under visible light. The use of POF offers advantages such as ease of handling and good adherence characteristics to support Ag2MoO4. The photoactivity follows the order ß-Ag2MoO4/Ag3PO4 ≅ Ag2MoO4 > TiO2 P25, for photocatalysts immobilized on the glass reactor surface or in aqueous suspension. The immobilization of Ag2MoO4 on POF revealed that thinner Ag2MoO4 coatings achieved faster pollutant removal rates from solution, and the optimal catalyst deposition is 0.64 mg/cm2, causing maximum the light penetration and electron-hole generation close to the solid-liquid interface.

Dinuclear copper(II) complexes with derivative triazine ligands as biomimetic models for catechol oxidases and nucleases.

The research reported herein focuses on the synthesis of two new Cu(II) complexes {[Cu2(2-X-4,6-bis(di-2-picolylamino)-1,3,5-triazine], with X = butane-1,4-diamine (2) or N-methylpyrenylbutane-1,4-diamine (3)}, the latter with a pyrene group as a possible DNA intercalating agent. The structure of complex (3) was determined by X-ray crystallography and shows the dinuclear {CuII(µ-OCH3)2CuII} unit in which the CuII···CuII distance of 3.040 Å is similar to that of 2.97 Å previously found for 1, which contains a {CuII(µ-OH)2CuII} structural unit. Complexes (2) and (3) were also characterized in spectroscopic and electrochemical studies, and catecholase-like activity were performed for both complexes. The kinetic parameters obtained for the oxidation of the model substrate 3,5-di-tert-butylcatechol revealed that the insertion of the spacer butane-1,4-diamine and the pyrene group strongly contributes to increasing the catalytic efficiency of these systems. In fact, Kass becomes significantly higher, indicating that these groups influence the interaction between the complex and the substrate. These complexes also show DNA cleavage under mild conditions with moderate reaction times. The rate of cleavage (kcat) indicated that the presence of butane-1,4-diamine and pyrene increased the activity of both complexes. The reaction mechanism seems to have oxidative and hydrolytic features and the effect of DNA groove binding compounds and circular dichroism indicate that all complexes interact with plasmid DNA through the minor groove. High-resolution DNA cleavage assays provide information on the interaction mechanism and for complex (2) a specificity for the unpaired hairpin region containing thymine bases was observed, in contrast to (3).

Synthetic dyes biodegradation by fungal ligninolytic enzymes: Process optimization, metabolites evaluation and toxicity assessment.

This work aimed to provide information that contributes to establishing environmental-friendly methods for synthetic dyes' degradation. The potential decolorization capacity of the crude enzymatic extract produced by Phanerochaete chrysosporium CDBB 686 using corncob as a substrate was evaluated on seven different dyes. Critical variables affecting the in-vitro decolorization process were further evaluated and results were compared with an in-vivo decolorization system. Decolorization with enzymatic extracts presented advantages over the in-vivo system (higher or similar decolorization within a shorter period). Under improved in-vitro process conditions, the dyes with higher decolorization were: Congo red (41.84 %), Poly R-478 (56.86 %), Methyl green (69.79 %). Attempts were made to confirm the transformation of the dyes after the in-vitro process as well as to establish a molecular basis for interpreting changes in toxicity along with the degradation process. In-vitro degradation products of Methyl green presented a toxicity reduction compared with the original dye; however, increased toxicity was found for Congo red degradation products when compared with the original dyes. Thus, for future applications, it is crucial to evaluate the mechanisms of biodegradation of each target synthetic dye as well as the toxicity of the products obtained after enzymatic oxidation.

Luminescent PhotoCORMs: Enabling/Disabling CO Delivery upon Blue Light Irradiation.

The new luminescent carbonyl compounds [Mn(Oxa-H)(CO)3Br] (1) and [Mn(Oxa-NMe2)(CO)3Br] (2) were synthesized and fully characterized. Complexes 1 and 2 showed CO release under blue light (λ453). Spectroscopic techniques and TD-DFT and SOC-TD-DFT calculations indicated that 1 and 2 release the Oxa-H and Oxa-NMe2 coligands in addition to the carbonyl ligands, increasing the luminescence during photoinduction.

Advanced oxidative processes in the degradation of 17ß-estradiol present on surface waters: kinetics, byproducts and ecotoxicity.

Endocrine disruptors represent risks to aquatic ecosystem and humans, and are commonly detected in surface water. Photochemical treatments can be used to remove 17ß-estradiol (E2), but few studies have analyzed the kinetics, intermediates, and 17ß-estradiol degradation pathways in natural matrices. In this study, the photochemical behavior of E2 under ultraviolet irradiation (UVC, 254 nm) associated with oxidants (H2O2 or O3) or photocatalyst (TiO2) was investigated to evaluate the degradation potential and the transformation pathway in a natural surface water matrix. Additionally, computational modeling analyses with Ecological Structure Activity Relationships (ECOSAR) software were performed to predict the toxicity from the E2 and its transformation byproducts. E2 degradation kinetics showed adjusted to the pseudo-first-order kinetic model, being kUV/O3 > kUV/TiO2 > kUV/H2O2 > kUV. Eight transformation byproducts were identified by liquid chromatography with time-of-flight mass spectrometry (HPLC/TOF-MS) in natural surface water samples. These byproducts formed as the result of opening the aromatic ring and adding the hydroxyl radical. The E2 degradation pathway was proposed based on the byproducts identified in this study and in previous studies, suggesting the formation of aliphatic and hydroxylated byproducts. E2 treatment presented both very toxic and not harmful byproducts.

An Overview of Structural Aspects and Health Beneficial Effects of Antioxidant Oligosaccharides.

BACKGROUND: Non-digestible oligosaccharides are versatile sources of chemical diversity, well known for their prebiotic actions, found naturally in plants or produced by chemical or enzymatic synthesis or by hydrolysis of polysaccharides. Compared to polyphenols or even polysaccharides, the antioxidant potential of oligosaccharides is still unexplored. The aim of the present work was to provide an up-to-date, broad and critical contribution on the topic of antioxidant oligosaccharides. METHODS: The search was performed by crossing the words oligosaccharides and antioxidant. Whenever possible, attempts at establishing correlations between chemical structure and antioxidant activity were undertaken. RESULTS: The most representative in vitro and in vivo studies were compiled in two tables. Chitooligosaccharides and xylooligosaccharides and their derivatives were the most studied up to now. The antioxidant activities of oligosaccharides depend on the degree of polymerization and the method used for depolymerization. Other factors influencing the antioxidant strength are solubility, monosaccharide composition, the type of glycosidic linkages of the side chains, molecular weight, reducing sugar content, the presence of phenolic groups such as ferulic acid, and the presence of uronic acid, among others. Modification of the antioxidant capacity of oligosaccharides has been achieved by adding diverse organic groups to their structures, thus increasing also the spectrum of potentially useful molecules. CONCLUSION: A great amount of high-quality evidence has been accumulating during the last decade in support of a meaningful antioxidant activity of oligosaccharides and derivatives. Ingestion of antioxidant oligosaccharides can be visualized as beneficial to human and animal health.

Guanidine- and purine-functionalized ligands of FeIIIZnII complexes: effects on the hydrolysis of DNA.

In this paper, the catalytic effects of aminoguanidine and aminopurine groups in the second sphere of a FeIIIZnII complex that mimics the active site of the metallohydrolase purple acid phosphatase (PAP) are investigated, with a particular view on DNA as substrate. The ligand 3-(((3-((bis(2-(pyridin-2-yl)ethyl)amino)methyl)-2-hydroxy-5-methylbenzyl)(pyridin-2-ylmethyl)amino)meth-yl)-2 hydroxy-5-methylbenzaldehyde-(H2L1bpea) was synthesized and its complex [(OH)FeIII(µ-OH)ZnII(H2O)(L1bpea)](ClO4) was used as a base for comparison with similar complexes previously published in the literature. Subsequent modifications were conducted in the aldehyde group, where aminoguanidine (amig) and aminopurine (apur) were used as side chain derivatives. The complexes [(OH)FeIII(µ-OH)ZnII(H2O)(L1bpea)](ClO4) (1), [(OH)FeIII(µ-OH)ZnII(H2O)(L1bpea-amig)](ClO4) (2) and [(OH)FeIII(µ-OH)ZnII(H2O)(L1bpea-apur)](ClO4) (3) were characterized by spectroscopic methods (infrared, UV-Vis) and ESI-MS spectrometry. Density functional theory (DFT) was also used to better understand the structure of the complexes. The hydrolytic activity of complexes 1, 2 and 3 was analyzed using both the model substrate 2,4-BDNPP (bis-(2,4-dinitrophenyl)phosphate) and DNA. Complexes 2 and 3, containing the derivatized ligands, have a significantly higher association constant (Kassoc≅ 1/KM) for the activated substrate 2,4-BDNPP compared to complex 1. The catalytic efficiency (kcat/KM) is also higher due to hydrogen bonds and/or π-stacking interactions between the substrate and the aminoguanidine or aminopurine groups present in 2 and 3, respectively. In the DNA cleavage assays, all complexes were able to cleave DNA, with 1 and 2 having higher catalytic activity than 3. In addition, when compared to previously analyzed complexes, complex 2 is one of the most active, having a kcat of 0.21 h-1.