Reaction Center Research Articles

Undulating Free Energy Landscapes Buffer Redox Chains from Environmental Fluctuations.

Roller-coaster or undulating free energy landscapes, with alternating high and low potential cofactors, occur frequently in biological redox chains. Yet, there is little understanding of the possible advantages created by these landscapes. We examined the tetraheme subunit associated with Blastochloris viridis reaction centers, comparing the dynamics of the native protein and of hypothetical (in silico) mutants. We computed the variation in the total number of electrons in wild type (WT) and mutant tetrahemes connected to an electron reservoir in the presence of a time-varying potential, as a model for a fluctuating redox environment. We found that roller-coaster free energy landscapes buffer the redox cofactor populations from these fluctuations. The WT roller-coaster landscape slows forward and backward electron transfer in the face of fluctuations, and may offer the advantage of sustaining the reduction of essential cofactors, such as the chlorophyll special pair in photosynthesis, even though an undulating landscape introduces thermodynamically uphill steps in multistep redox chains.

The structural basis for the collagen processing by human P3H1/CRTAP/PPIB ternary complex

Collagen posttranslational processing is crucial for its proper assembly and function. Disruption of collagen processing leads to tissue development and structure disorders like osteogenesis imperfecta (OI). OI-related collagen processing machinery includes prolyl 3-hydroxylase 1 (P3H1), peptidyl-prolyl cis-trans isomerase B (PPIB), and cartilage-associated protein (CRTAP), with their structural organization and mechanism unclear. We determine cryo-EM structures of the P3H1/CRTAP/PPIB complex. The active sites of P3H1 and PPIB form a face-to-face bifunctional reaction center, indicating a coupled modification mechanism. The structure of the P3H1/CRTAP/PPIB/collagen peptide complex reveals multiple binding sites, suggesting a substrate interacting zone. Unexpectedly, a dual-ternary complex is observed, and the balance between ternary and dual-ternary states can be altered by mutations in the P3H1/PPIB active site and the addition of PPIB inhibitors. These findings provide insights into the structural basis of collagen processing by P3H1/CRTAP/PPIB and the molecular pathology of collagen-related disorders.

Higher phosphorus and water use efficiencies and leaf stoichiometry contribute to legume success in drylands

Abstract Legumes are essential plants in dryland ecosystems worldwide because they increase nitrogen availability, so their understanding is vital for improving knowledge and modelling in the face of climate change. This work studies the differences in resource use efficiency and their relationship with photosynthetic, photochemical, bioelemental, and stoichiometric traits of coexistent legumes and non‐legumes in a Sonoran Desert ecosystem. We found that legumes had higher photosynthetic rates, intrinsic and seasonal water use efficiency (WUE), phosphorus use efficiency (PPUE), and higher light utilisation mediated by chlorophyll content and active reaction centers, which may increase their photoprotection. Legumes can increase their WUE and PPUE with no changes in nitrogen use efficiency (PNUE). Consequently, observed trait relationships between studied traits in these legumes have significant differences with the non‐legume species in the study. Stoichiometry is helpful, in some cases, as an indicator of nutrient use efficiency and enables functional group differentiation. Our results strongly relate legumes' higher resource use efficiency with their success in dryland ecosystems. Read the free Plain Language Summary for this article on the Journal blog.

The Variable Stiffness Treadmill 2: Development and Validation of a Unique Tool to Investigate Locomotion on Compliant Terrains

Abstract Understanding legged locomotion in various environments is valuable for many fields, including robotics, biomechanics, rehabilitation, and motor control. Specifically, investigating legged locomotion in compliant terrains has recently been gaining interest for the robust control of legged robots over natural environments. At the same time, the importance of ground compliance has also been highlighted in poststroke gait rehabilitation. Currently, there are not many ways to investigate walking surfaces of varying stiffness. This article introduces the variable stiffness treadmill (VST) 2, an improvement of the first version of the VST, which was the first treadmill able to vary belt stiffness. In contrast to the VST 1, the device presented in this paper (VST 2) can reduce the stiffness of both belts independently, by generating vertical deflection instead of angular, while increasing the walking surface area from 0.20m2 to 0.74m2. In addition, both treadmill belts are now driven independently, while high-spatial-resolution force sensors under each belt allow for measurement of ground reaction forces and center of pressure. Through validation experiments, the VST 2 displays high accuracy and precision. The VST 2 has a stiffness range of 13kN/m to 1.5MN/m, error of less than 1%, and standard deviations of less than 2.2kN/m, demonstrating its ability to simulate low-stiffness environments reliably. The VST 2 constitutes a drastic improvement of the VST platform, a one-of-its-kind system that can improve our understanding of human and robotic gait while creating new avenues of research on biped locomotion, athletic training, and rehabilitation of gait after injury or disease.

Antifungal mechanisms and characteristics of Pseudomonas fluorescens: Promoting peanut growth and combating Fusarium oxysporum-induced root rot

Continuous cropping of peanuts presents significant challenges to sustainable production due to soil-borne diseases like root rot caused by Fusarium species. In this study, field inoculation experiments treatments and in vitro agar plate confrontation tests were conducted, including non-inoculated controls (CK), inoculation with Pseudomonas fluorescens (PF), Fusarium oxysporum (FO), and co-inoculation with both (PF + FO). The aim was to explore the antifungal mechanisms of Pseudomonas fluorescens in mitigating root rot and enhancing peanut yield. The results indicated that PF and PF + FO significantly enhanced peanut root activity, as well as superoxide dismutase, catalase, and glutathione S-transferase activities, while simultaneously decreasing the accumulation of reactive oxygen species and malondialdehyde contents, compared to FO treatment. Additionally, PF treatment notably increased lignin content through enhanced phenylalanine ammonia lyase, cinnamate 3-hydroxylase, and peroxidase activity compared to CK and FO treatment. Moreover, PF treatment resulted in longer roots and a higher average diameter and surface area, potentially due to increased endogenous levels of auxin and zeatin riboside, coupled with decreased abscisic acid content. PF treatment significantly elevated chlorophyll content and the maximum photochemical efficiency of PSII in the light-adapted state, the actual photochemical efficiency and the proportion of PSII reaction centers open, leading to improved photosynthetic performance. Confrontation culture assays revealed PF's notable inhibitory effects on Fusarium oxysporum growth, subsequently reducing rot disease incidence in the field. Ultimately, PF treatment led to increased peanut yield by enhancing plant numbers and pod weight compared to FO treatment, indicating its potential in mitigating Fusarium oxysporum-induced root rot disease under continuous cropping systems.

Photothermal and ROS-mediated cellular apoptosis using copper-driven Prussian blue analog nanoparticles with bimetallic reaction centres

The development of chemodynamic therapy (CDT) agents derived from copper and iron is crucial due to their ability to their biological safety, biocompatibility, and bio-specificity to only kill cancer cells. This study investigates bimetallic copper/iron-Prussian blue coordination analogs nanoparticles (CuxFey-PBAs, x = 15, 11, 7, 4, 0; y = 0, 4, 8, 11, 15), which exhibit photothermally enhanced bimetallic central catalytic activity for effective cancer treatment. By adjusting the Cu2+/Fe2+ ratio, CuxFey-PBAs demonstrated remarkable photothermal properties (from 1.9 % to 39.75 %) and exceptional reactive oxygen species (ROS) activity (k: 0.077 min−1, R2: 0.97), leading to mitochondrial dysfunction and subsequent tumour cell death. Density functional theory (DFT) calculations highlighted that the most critical factors influencing photothermal properties are carrier concentration and electron transition. The electronic structure of the bimetallic centre was found to significantly correlate with the reaction pathway and ROS activity. In vitro experiments showed that CuxFey-PBAs can enter cancer cells via endocytosis, induce mitochondrial dysfunction, and cause cancer cell death through apoptosis. Compared to conventional ROS-mediated systems, CuxFey-PBAs with photothermal properties exhibit superior ROS catalytic activity, facilitating photothermally enhanced CDT. These findings represent a significant advancement in synergistic photothermal-enhanced Fenton reaction with bimetallic reaction centres, offering a novel strategy for CDT enhancement.

Anomalous Temperature Dependence of the Triplet-Triplet Energy Transfer in Cereibacter sphaeroides I(L177)H Mutant Reaction Centers.

In photosynthetic reaction centers, quenching of the primary donor triplet state by energy transfer to the carotenoid molecule provides efficient suppression of generation of singlet-excited oxygen, potent chemical oxidant. This process in the Cereibacter sphaeroides reaction centers is thermoactivated, and discontinues at temperatures below 40K. In these reaction centers, substitution of amino acid residue isoleucine at the 177position of the L-subunit with histidine results in the sharp decrease of activation energy, so that the carotenoid triplets are populated even at 10K. Activation energy of the T-T energy transfer was estimated as 7.5cm-1, which is more than 10-fold lower than activation energy in the wild type reaction centers. At certain temperatures, the energy transfer in the mutant is decelerated, which is related to the increase of effective distance of the triplet-triplet transfer. To the best of our knowledge, the described mutation presents the first reaction center modification leading to the significant decrease in activation energy of the T-T energy transfer to carotenoid molecule. TheI(L177)H mutant reaction centers present a considerable interest for further studies of the triplet state quenching mechanisms, and of other photophysical and photochemical processes in the reaction centers of bacterial photosynthesis.

Bimodal functionality of highly conductive nanostructured silver film towards improved performance of photosystem I-based graphene photocathode

We present the novel design of photosystem I (PSI)-based biosolar cell, whereby conductive transparent electrode materials, such as ITO or FTO, are replaced with glass covered with silver island film. This nanostructured metallic layer combines high electric conductance with enhancing the absorption efficiency of the PSI biocatalyst via the plasmonic effect. We demonstrate strong enhancement of the photocurrent generated in the biohybrid electrode composed of oriented layers of PSI reaction centers due to plasmonic interactions of the PSI fluorophores and redox centres with the conductive silver island film.

Chromatic acclimation in cyanobacteria renders robust photosynthesis and fitness in dynamic light environment: Recent advances and future perspectives.

Cyanobacteria are photoautotrophic organisms that use light and water as a source of energy and electrons, respectively, to fix atmospheric carbon dioxide and release oxygen as a by-product during photosynthesis. However, photosynthesis and fitness of organisms are challenged by seasonal and diurnal fluctuations in light environments. Also, the distribution of cyanobacteria in a water column is subject to changes in the light regime. The quality and quantity of light change significantly in low and bright light environments that either limit photochemistry or result in photoinhibition due to an excess amount of light reaching reaction centers. Therefore, cyanobacteria have to adjust their light-harvesting machinery and cell morphology for the optimal harvesting of light. This adjustment of light-harvesting involves remodeling of the light-harvesting complex called phycobilisome or incorporation of chlorophyll molecules such as chlorophyll d and f into their light-harvesting machinery. Thus, photoacclimation responses of cyanobacteria at the level of pigment composition and cell morphology maximize their photosynthetic ability and fitness under a dynamic light environment. Cyanobacteria exhibit different types of photoacclimation responses that are commonly known as chromatic acclimation (CA). In this work, we discuss different types of CA reported in cyanobacteria and present a molecular mechanism of well-known type 3 CA where phycoerythrin and phycocyanin of phycobilisome changes according to light signals. We also include other aspects of type 3 CA that have been recently studied at a molecular level and highlight the importance of morphogenes, cytoskeleton, and carboxysome proteins. In summary, CA gives a unique competitive benefit to cyanobacteria by increasing their resource utilization ability and fitness.

Superexchange Electron Transfer and Protein Matrix in the Charge-Separation Process of Photosynthetic Reaction Centers.

In type-II reaction centers, such as photosystem II (PSII) and reaction centers from purple bacteria (PbRC), light-induced charge separation involves electron transfer from pheophytin (PheoD1) to quinone (QA), occurring near a conserved tryptophan residue (D2-Trp253 in PSII and Trp-M252 in PbRC). This study investigates the route of the PheoD1-to-QA electron transfer, focusing on the superexchange coupling (|HPheoD1···QA|) in the PSII protein environment. |HPheoD1···QA| is significantly larger for the PheoD1-to-QA electron transfer via the unoccupied molecular orbitals of D2-Trp253 ([Trp]•--like intermediate state, 0.73 meV) compared to direct electron transfer (0.13 meV), suggesting that superexchange is the dominant mechanism in the PSII protein environment. While the overall impact of the protein environment is limited, local interactions, particularly H-bonds, enhance superexchange electron transfer by directly affecting the delocalization of molecular orbitals. The D2-W253F mutation significantly decreases the electron transfer rate. The conservation of D2-Trp253/D1-Phe255 (Trp-M252/Phe-L216 in PbRC) in the two branches appears to differentiate superexchange coupling, contributing to the branches being either active or inactive in electron transfer.

Absence of a link between stabilized charge-separated state and structural changes proposed from crystal structures of a photosynthetic reaction center

Structural differences between illuminated and unilluminated crystal structures led to the proposal that the charge-separated state was stabilized by structural changes in its membrane extrinsic protein subunit H in a bacterial photosynthetic reaction center [Katona, G. et al. Nat. Struct. Mol. Biol. 2005, 12, 630–631]. Here, we explored the proposal by titrating all titratable sites and calculating the redox potential (Em) values in these crystal structures. Contrary to the expected charge-separated states, Em for quinone, Em(QA/QA•–), is even lower in the proposed charge-separated structure than in the ground-state structure. The subunit-H residues, which were proposed to exhibit electron-density changes in the two crystal structures, contribute to an Em(QA/QA•–) difference of only <0.5 mV. Furthermore, the protonation states of the titratable residues in the entire reaction center are practically identical in the two structures. These findings indicate that the proposed structural differences are irrelevant to explaining the significant prolongation of the charge-separated-state lifetime.

Achieving Regioselectivity for Remote C-H Activation by Substructure Conformations: an Approach of Paralogous Cytochrome P450 Enzymes.

For advanced synthetic intermediates or natural products with multiple unactivated and energetically similar C(sp3)-H bonds, controlling regioselectivity for the C-H activation is particularly challenging. The use of cytochrome P450 enzymes (CYPs) is a promising solution to the 'regioelectivity' challenge in remote C-H activation. Notably, CYPs and organic catalysts share a fundamental principle: they strive to control the distance and geometry between the metal reaction center and the target C-H site. Most structural analyses of the regioselectivity of CYPs are limited to the active pocket, particularly when explaining why regioselectivity could be altered by enzyme engineering through mutagenesis. However, the substructures responsible for forming the active pocket in CYPs are well known to display complex dynamic changes and substrate-induced plasticity. In this context, we highlight a comparative study of the recently reported paralogous CYPs, IkaD and CftA, which achieve different regioselectivity towards the same substrate ikarugamycin by distinct substructure conformations. We propose that substructural conformation-controlled regioselectivity might also be present in CYPs of other natural product biosynthesis pathways, which should be considered when engineering CYPs for regioselective modifications.

STIC2 selectively binds ribosome-nascent chain complexes in the cotranslational sorting of Arabidopsis thylakoid proteins.

Chloroplast-encoded multi-span thylakoid membrane proteins are crucial for photosynthetic complexes, yet the coordination of their biogenesis remains poorly understood. To identify factors that specifically support the cotranslational biogenesis of the reaction center protein D1 of photosystem (PS) II, we generated and affinity-purified stalled ribosome-nascent chain complexes (RNCs) bearing D1 nascent chains. Stalled RNCs translating the soluble ribosomal subunit uS2c were used for comparison. Quantitative tandem-mass spectrometry of the purified RNCs identified around 140 proteins specifically associated with D1 RNCs, mainly involved in protein and cofactor biogenesis, including chlorophyll biosynthesis, and other metabolic pathways. Functional analysis of STIC2, a newly identified D1 RNC interactor, revealed its cooperation with chloroplast protein SRP54 in the de novo biogenesis and repair of D1, and potentially other cotranslationally-targeted reaction center subunits of PSII and PSI. The primary binding interface between STIC2 and the thylakoid insertase Alb3 and its homolog Alb4 was mapped to STIC2's β-sheet region, and the conserved Motif III in the C-terminal regions of Alb3/4.

The fitness of pelargonium cuttings affects the relationship between the photochemical activity of the photosynthetic apparatus and rooting ability

Pelargoniums cultivated for ornamental purposes rely on efficient vegetative propagation. This study researched applicability of chlorophyll fluorescence for validating the physiological conditions of pelargonium cuttings. Results indicated a correlation between the chlorophyll fluorescence and rooting potential. The ET0/RC values were negatively correlated with the rooting efficiency between the varieties and the duration of cold storage. A negative correlation was observed between OJIP parameters, representing energy flow in thylakoids, and chlorophyll content in cuttings with lower nutritional status. The phenomenological energy fluxes for leaf cross-sections and the number of active PSII reaction centers in the not-excited state (RC/CS0) increase with raised chlorophyll concentration. This imply the influence of rooting ability on the demand for photoassimilates in pelargonium cuttings, which can be detected early on through chlorophyll fluorescence analysis but not chlorophyll content measurements. Chlorophyll fluorescence evaluation, along with specific OJIP test parameters such as the performance indices PIABS and PItotal, prove useful for predicting rooting efficiency in relation to the nutritional status of cuttings, suggesting the effects of cuttings cold storage and discerning varietal differences in rooting. This study establishes the pragmatic application of chlorophyll fluorescence assessment for elucidating the physiological intricacies of pelargonium cuttings and factors influencing rooting efficiency.

Vacancy engineering-induced spin polarization in heterogeneous phosphides by simple iron salt infiltration for efficient overall water splitting

Optimizing electronic structure and facilitating electron transfer modulation in electrocatalyst is the key to enhancing overall water splitting (OWS) performance. In this work, the heterogeneous transition metal phosphide Fe-CoPv/Ni2P@NF, consisting of cobalt phosphide and nickel phosphide, is obtained by simple iron salt infiltration and high-temperature phosphatisation. Due to the doping of iron-atom and the formation of phosphorus vacancies, the activity of metal atoms with higher valence states and spins is induced, and then highly active Fe/Co-O-Ni channels are generated in the dynamic water-splitting process, thereby increasing the exposure of reaction center and total electron transfer rate. The catalytic mechanism is attributed to reducing the potential barrier of phase remodeling and optimizing the intermediate binding strength, thus thoroughly stimulating OER and HER activities. The Fe-CoPv/Ni2P@NF shows superior performance, requiring only total voltages of 1.626 V (OWS) to reach 100 mA·cm−2 and maintaining ultra-high stability for 500 h, suggesting promising industrial applications.

Controlled synthesis of Sn doped Cu–Ni3S2 on Ni foam as efficient electrocatalyst for urea oxidation reaction and oxygen evolution reaction

Hydrogen production technology by urea-assisted electrocatalytic water decomposition has become one of the important means to alleviate carbon emissions and water pollution. In this paper, we first doped Sn and Cu element into the Ni3S2 material by hydrothermal method on the Ni foam support. This Cu–Sn–Ni3S2 material exhibits superior urea (potential of 1.42 V at 100 mA cm−2) and water oxidation (potential of 1.63 V at 100 mA cm−2) properties, which is one of the best electrochemical performance reported up to now. Analysis of experiment demonstrate that the increase in catalytic performance is assigned to faster charge transfer, more exposure of reaction centres and smaller resistance owing to doping of Sn and Cu. Density functional theory (DFT) analysis demonstrates that introduction of Sn and Cu increases the adsorption energy of urea and improves the conductivity of the Cu–Sn–Ni3S2 material, and the co-doping of the two changes the electron state density of the active site, thereby promoting the catalytic performance. This work provides insights into the development of efficient bifunctional electrodes for urea oxidation and oxygen evolution reaction through doping strategies.

Chlorophyll Pigments and Their Synthetic Analogs.

Oxygenic phototrophs use chlorophylls (Chls) as photosynthetically active pigments. A variety of Chl molecules have been found in photosynthetic eukaryotes including green plants, algae, and cyanobacteria. Here we review their molecular structures with stereochemistry, occurrence in light-harvesting antennas and reaction centers, biosyntheses in the late stage, chemical stabilities, and visible absorption maxima in diethyl ether. The observed maxima are comparable to those of semisynthetic Chl analogs, methyl pyropheophorbides, in dichloromethane. The effects of their peripheral substituents and core π-conjugation on the maxima of the monomeric states are discussed. Notably, the oxidation along the molecular x-axis in Chl-a produces its accessory pigments, Chls-b/c, and introduction of an electron-withdrawing formyl group along the y-axis perpendicular to the x-axis affords far-red light absorbing Chls-d/f.

Co3O4 coated carbon fiber activates PMS to degrade phenolic pollutants via 1O2 dominated non-radical pathway: Role of dual reaction center

Carbon fiber (CF) with a regular fiber skeleton structure was used to prepare the Co3O4@CF catalyst. The as-prepared catalyst was then applied to activate peroxymonosulfate (PMS) for the degradation of phenolic pollutants. Furthermore, the catalytic performance and degradation mechanisms are investigated in this study. The uniform dispersion of Co3O4 on the surface of the CF, as well as the presence of Co–O–R in the Co3O4@CF structure, was confirmed. Notably, 50 mg L−1 of bisphenol A (BPA) was completely degraded in the Co3O4@CF/PMS system within 20 min, under initial conditions of catalyst mass concentration at 0.2 g L−1, the PMS concentration at 10 mmol L−1, and a pH of 6.6. The total organic carbon removal rate reached 72.33 % over 90 min, indicating that the Co3O4@CF/PMS system exhibited strong mineralization capability for BPA. Furthermore, the catalyst demonstrated high efficiency in treating various types of refractory organic pollutants, showing promise for purifying coking wastewater from 3D-EEM. X-ray photoelectron spectroscopy and solid-state electron paramagnetic resonance revealed the formation of electron-poor and electron-rich centers in the Co3O4@CF structure. Density functional theory calculations further indicated that the charge density around the CF decreased, while the charge density around Co3O4 increased, resulting in the formation of these electron-poor and electron-rich centers. Electrochemical characterization using cyclic voltammetry and electrochemical impedance spectroscopy confirmed the excellent electron transfer rate of Co3O4@CF. Additionally, the reactive oxygen species dominated in the Co3O4@CF/PMS system were 1O2 and •O2−, with possible mechanisms for the 1O2 and •O2− generation during BPA degradation elucidated. Moreover, liquid chromatography-mass spectrometry results identified degradation intermediates of BPA, proposing three possible degradation pathways.

In situ structural determination of cyanobacterial phycobilisome–PSII supercomplex by STAgSPA strategy

Photosynthesis converting solar energy to chemical energy is one of the most important chemical reactions on earth. In cyanobacteria, light energy is captured by antenna system phycobilisomes (PBSs) and transferred to photosynthetic reaction centers of photosystem II (PSII) and photosystem I (PSI). While most of the protein complexes involved in photosynthesis have been characterized by in vitro structural analyses, how these protein complexes function together in vivo is not well understood. Here we implemented STAgSPA, an in situ structural analysis strategy, to solve the native structure of PBS–PSII supercomplex from the cyanobacteria Arthrospira sp. FACHB439 at resolution of ~3.5 Å. The structure reveals coupling details among adjacent PBSs and PSII dimers, and the collaborative energy transfer mechanism mediated by multiple super-PBS in cyanobacteria. Our results provide insights into the diversity of photosynthesis-related systems between prokaryotic cyanobacteria and eukaryotic red algae but are also a methodological demonstration for high-resolution structural analysis in cellular or tissue samples.

Iron and Manganese concentrations in leaf tissues of Rhizophora mangle (Rhizophoraceae): implications for energetic metabolism

Introduction: Iron (Fe) and manganese (Mn) are bioessential micronutrients for plants but can impair the energetic metabolism when present at high levels. Objective: To assess the photosynthetic performance and oxidative damages in Rhizophora mangle L. leaf tissues at low and high concentrations of Fe (74 and 195 mg kg-1; Feleaf) and Mn (65 and 414 mg kg-1; Mnleaf). Methods: Photosynthetic pigments, chlorophyll a fluorescence, leaf CO2 assimilation and gas exchange and DPPH• radical scavenging capacity were sampled in R. mangle growing in estuarine forests in the North region of Espírito Santo State and the extreme South of Bahia State (Brazil) showing low and high Feleaf and Mnleaf. Results: Effects of high Fe and Mn were not identified on pigment levels. The increase in Feleaf and Mnleaf at the levels observed in this assessment had a positive effect on the number of reaction centers and on the efficiency of the oxygen-evolving complex, evaluated as K-band, while no changes were found in the parameters related to the excitation trapping efficiency at the active center of photosystem II. Distinct interference patterns of Fe and Mn on the functional processes of photosynthesis were identified, especially on CO2 assimilation and reactive oxygen species metabolism, with major effects on CO2 assimilation and carboxylation efficiency of Rubisco at high Mnleaf. Conclusion: These findings demonstrate the efficiency of R. mangle in positively regulating the electron transport chain in response to high Fe and Mn, at least in terms of the preservation of structure and functionality of the plant photosynthetic apparatus. Moreover, interference of high Mnleaf in R. mangle occurs at non-stomatal and biochemical levels. There is an antagonistic interference of these trace elements with the physiology of R. mangle, which is a dominant species in Brazilian mangroves.