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The response of plant species to the variation in abiotic factors affects the regeneration capacity and, consequently, the structure of the forest community. This study aims to describe the structure of the regenerating stratum in a Brazilian montane rainforest and investigate its relationship with environmental and spatial variables along an altitudinal gradient. Data on the height and diameter at soil height of regenerating individuals and environmental variables were collected from 28 sample units, distributed in seven altitudinal sites. To understand the spatial influence on species distribution, spatial variables (MEMs - Moran’s Eigenvector Maps) were created based on geographic coordinates. Phytosociological parameters were calculated by species. Floristic similarity between the altitudinal quota was determined by the Bray-Curtis index (UPGMA), and the species that characterize each group were determined by the Indicator Species Analysis. Redundancy Analysis (RDA) was performed, and generalized linear models were adjusted to verify the influence of environmental and spatial factors on regenerating vegetation. The species Palicourea sessilis had the highest Importance Value in the regenerating community. Two floristic groups were formed: the highest sites (1420 to 1550 m a.s.l.) were floristically more similar to each other (Group 1) than to the sites in the 1112 to 1391 m elevation range (Group 2). Overall, 11 species were indicators of Group 1 and only one of Group 2. Finally, a pattern of species substitution was verified as a function of abiotic factors. The first two axes of the RDA explained 51.02% of the variation in the floristic composition of the regenerating community. Natural regeneration demonstrated environmental preferences, being influenced by luminosity, abundance in adult components, calcium and sodium contents, plant litter accumulation, altitude, and the spatial structure of the environment. Altitude did not seem to influence the pattern of abundance or richness of regenerating species.

Environmental changes caused by edge effects and matrix land use can interfere with plant community resilience and, consequently, alter forest succession. Here, we aimed to (i) investigate whether species composition, density and richness in a forest’s regeneration layer vary in its edge-to-interior gradient and (ii) analyze the relationship between regeneration and local abiotic variables. We conducted the study in the lowland rainforest of the Atlantic Forest biodiversity hotspot at the Córrego Grande Biological Reserve, Espírito Santo state, Brazil. We sampled the regeneration layer in two edge environments with different matrices (forest and road) and the fragmented interior to link vegetation structure with environmental variables. In each environment, we set up 12 plots of 5 × 10 m size and recorded, in each plot, the height and stem base diameter of all living individuals above 50 cm of height and below 2.5 cm of diameter at breast height (1.30 m height). We applied different multivariate analyses to assess the influence of environmental data, such as canopy openness and physical-chemical soil variables. The three environments shared 22 out of the 174 morphospecies recorded, and the forest-side edge had the lowest species richness among all environments. The environmental variables that better explained the distribution of species across the three environments were: canopy openness, soil penetration resistance, zinc, and calcium content. Our results revealed significant environmental differences among the forest edges and the forest interior of the study site, highlighting the relevant role of the forest surrounding matrix for the maintenance of protected remnants.

A chemical reagent to access methyl sulfones has been developed. Its reaction with various bis-nucleophiles leads to the rapid formation of previously unknown heteroaromatic methyl sulfones. Analogous strategy can also be used to construct alkyl-, CHF2-, CF3- and even bicyclo[1.1.1]pentane-containing derivatives. These compounds have been demonstrated to have a high potential for use in medicinal chemistry and coordination chemistry. Methyl sulfone is a standard polar substituent used in chemistry and can be found in different agro chemicals or drugs but due to lack of convenient and efficient chemical approaches to them, heteroaromatic methyl sulfones are less investigated. Here the authors report a reagent to access previously unknown heteroaromatic methyl sulfones. [ABSTRACT FROM AUTHOR]

Fluorescent organotin compounds are useful in sensing, optoelectronic devices, and in vitro bioimaging. Although in vitro fluorescence bioimaging shows low resolution at room temperature, a better resolution is possible at cryotemperatures. Therefore, the search for new cryoluminescent materials with potential application in high-resolution fluorescence bioimaging remains a great challenge. Herein, we report the cryoluminescence properties of two fluorescent bis-organotin compounds, namely, BisNTHySnBu2 (5) and BisNTHySnPh2 (6), synthesized via microwave irradiation. All compounds were fully characterized using 1H, 13C, and 119Sn NMR spectroscopy, Raman spectroscopy, IR spectroscopy, and HR-MS. The 119Sn δ and 3J(1H,119Sn) of 5 and 6 indicate that two Sn-ligands are chemically and electronically equivalent, as confirmed by cyclic voltammetry. The crystal structure of 6 showed pentacoordinate tin atoms with skeleton ligands. The study of self-assembled monolayers of both Sn-complexes via STM microscopy revealed a similar supramolecular packing in lamella-like patterns, adopting a face-on arrangement, where molecules stay flat lying on HOPG in accordance with the height profile of closely packed monolayers on graphite of about 0.33 nm thickness. However, only the Sn complex 6, which bears phenyls, covers large surface areas. The photophysical properties of bis-organotin compounds were also investigated in solution (room and low temperatures) and in the solid state. Good luminescence properties in solutions with fluorescence quantum yields (Φ) of approximately 35% and 50% were found. Despite this, Φ is quenched in the solid state because of aggregation, as supported by solvent/non solvent fluorescence studies, which is in agreement with STM and AFM investigation. [ABSTRACT FROM AUTHOR]

Sterically loaded, anionic pyridine has been synthesized and utilized successfully in the stabilization of a isoleptic series of coinage metal complexes. The treatment of [4‐(Ph3B)‐2,6‐Trip2Py]K (Trip=2,4,6‐iPr3C6H2) with CuBr(PPh3), AgCl(PPh3) or AuCl(PPh3) (Py=pyridine) afforded the corresponding [4‐(Ph3B)‐2,6‐Trip2Py]M(PPh3) (M=Au, Ag, Cu) complexes, via salt metathesis, as isolable, crystalline solids. Notably, these reactions avoid the facile single electron transfer chemistry reported with the less bulky ligand systems. The X‐ray structures revealed that they are two‐coordinate metal adducts. The M−N and M−P bond distances are longest in the silver and shortest in the copper adduct among the three group 11 family members. Computational analysis revealed an interesting stability dependence on steric bulk of the anionic pyridine (i. e., pyridyl borate) ligand. A comparison of structures and bonding of [4‐(Ph3B)‐2,6‐Trip2Py]Au(PPh3) to pyridine and m‐terphenyl complexes, {[2,6‐Trip2Py]Au(PPh3)}[SbF6] and [2,6‐Trip2Ph]Au(PPh3) are also provided. The Au(I) isocyanide complex, [4‐(Ph3B)‐2,6‐Trip2Py]Au(CNBut) has been stabilized using the same anionic pyridylborate illustrating that it can support other gold‐ligand moieties as well. [ABSTRACT FROM AUTHOR]

Phenanthroline-based ligands with bulky aryl groups flanking the metal binding pocket enabled the synthesis and detailed investigation of ethylene complexes of copper(I), silver(I), and gold(I), including structural data of [{2,9-bis(2,4,6-triisopropylphenyl)-1,10-phenanthroline}M(C2H4)][SbF6] (M = Cu, Ag, Au), Additionally, a related copper(I)-ethylene complex with a highly fluorinated ligand is also reported. Gold(I) affects the ethylene moiety significantly as evident from the notable upfield coordination shifts of ethylene carbon signals in the NMR and lengthening of the ethylene C＝C bond length. Silver(I) forms the weakest bond with ethylene in this series of isoleptic, group 11 metal-ethylene complexes. Preliminary catalytic investigations underscore the potential of copper complexes, particularly those with weakly coordinating supporting ligands, as effective catalysts for C(sp3)–H functionalization through trifluoromethyl carbene insertion. [ABSTRACT FROM AUTHOR]

Gold coordination chemistry and catalysis involving unsaturated hydrocarbons such as olefins have experienced a remarkable growth during the last few decades. Despite the importance, isolable and well-characterized molecules with ethylene, the simplest and the most widely produced olefin, on gold are still limited. This review aims to cover features of, and strategies utilized to stabilize, gold–ethylene complexes and their diverse use in chemical transformations and homogeneous catalytic processes. Isolable and well-authenticated gold–ethylene complexes are important not only for structural, spectroscopic, and bonding studies but also as models for likely intermediates in gold mediated reactions of alkenes and gold–alkene species observed in the gas phase. There has also been development on AuI/III catalytic cycles. Nitrogen based ligands have been the most widely utilized ligand supports thus far for the successful stabilization of gold–ethylene adducts. Gold has a bright future in olefin chemistry and with ethylene. [ABSTRACT FROM AUTHOR]

In the course of studying Diels–Alder reactions of 4-vinylimidazoles with N-phenylmaleimide, it was discovered that they engage in cycloaddition at room temperature to give high yields of the initial cycloadduct as a single stereoisomer. In certain cases, the product precipitated out of the reaction mixture and could be isolated by simple filtration, thereby avoiding issues with aromatization observed during chromatographic purification. Given these results, intramolecular variants using doubly activated dienophiles were also investigated at room temperature. Amides underwent cycloaddition at room temperature in modest yields, but the initial adducts were not isolable with Nimid-benzyl-protected systems. Attempts to extend these results to the corresponding esters and hydroxamate were less successful with these substrates only undergoing cycloaddition at elevated temperatures in lower yields. Density functional theory calculations were performed to evaluate the putative transition states for both the inter- and intramolecular variants to rationalize experimental observations. [ABSTRACT FROM AUTHOR]

The 3d transition metal (Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II)) complexes, supported by anions of sterically demanding β-diketones, 1,3-dimesitylpropane-1,3-dione (HLMes) and 1,3-bis(3,5-bis(trifluoromethyl)phenyl)-3-hydroxyprop-2-en-1-one (HLCF3), were synthesized and evaluated for their antitumor activity. To assess the biological effects of substituents on phenyl moieties, we also synthesized and investigated the analogous metal(II) complexes of the anion of the less bulky 1,3-diphenylpropane-1,3-dione (HLPh) ligand. The compounds [Cu(LCF3)2], [Cu(LMes)2] and ([Zn(LMes)2]) were characterized by X-ray crystallography. The [Cu(LCF3)2] crystallizes with an apical molecule of solvent (THF) and features a rare square pyramidal geometry at the Cu(II) center. The copper(II) and zinc(II) complexes of diketonate ligands, derived from the deprotonated 1,3-dimesitylpropane-1,3-dione (HLMes), adopt a square planar or a tetrahedral geometry at the metal, respectively. We evaluated the antitumor properties of the newly synthesized (Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II)) complexes against a series of human tumor cell lines derived from different solid tumors. Except for iron derivatives, cellular studies revealed noteworthy antitumor properties, even towards cancer cells endowed with poor sensitivity to the reference drug cisplatin. [ABSTRACT FROM AUTHOR]

A unique four‐coordinate, classical gold(I)‐carbonyl complex with substantial backdonation from gold has been isolated by using a B‐methylated and fluorinated tris(pyridyl)borate chelator. Its lighter silver(I) and copper(I) analogs enabled a study of trends in the coinage‐metal family. The B‐arylated ligand version also afforded a gold–carbon monoxide complex that displays a notably low C−O stretch value, but with trigonal planar geometry at the gold. A computational analysis shows that the AuI−CO bonds of these tris(pyridyl)borate ligand‐supported molecules consist of electrostatic attraction, OC→Au σ‐donation, and very significant Au→CO π‐back‐bonding components. The latter is responsible for the observed C−O stretching frequencies, which are lower than in free CO. [ABSTRACT FROM AUTHOR]

Copyright of Brazilian Journal of Biology is the property of Instituto Internacional de Ecologia and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Copyright of Brazilian Journal of Biology is the property of Instituto Internacional de Ecologia and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Successful synthesis has been reported of 4-Mes2B-3,5-(CF3)2PzH and 4-Mes2B-3,5-(CF3)2PzH bearing sterically demanding diarylboron moieties at the pyrazole ring 4-position, and their corresponding copper(I) pyrazolate complexes. They show visible blue photoluminescence in solution. The X-ray crystal structures revealed that the fluorinated {[4-BMes2-3,5-(CF3)2Pz]Cu}3 crystallizes as discrete trinuclear molecules whereas as the non-fluorinated {[4-BMes2-3,5-(CH3)2Pz]Cu}3 forms dimers of trimers with two close inter-trimer Cu⋯Cu separations. The solid {[4-BMes2-3,5-(CF3)2Pz]Cu}3 featuring a sterically confined Cu3N6 core displays bright blue phosphorescence while {[4-BMes2-3,5-(CH3)2Pz]Cu}3, which is a dimer of a trimer, is a red phosphor at room temperature. This work illustrates the modulation of photo-physical properties of metal pyrazolates by adjusting the supporting ligand steric features and introducing secondary diarylboron luminophores. Computational analysis of the structures and photophysical properties of copper complexes are also presented. [ABSTRACT FROM AUTHOR]

Design, synthesis, and in vitro antitumor properties of Cu(I) and Ag(I) phosphane complexes supported by the anions of sterically hindered β-diketone ligands, 1,3-dimesitylpropane-1,3-dione (HLMes) and 1,3-bis(3,5-bis(trifluoromethyl)phenyl)-3-hydroxyprop-2-en-1-one (HLCF3) featuring trifluoromethyl or methyl groups on the phenyl moieties have been reported. In order to compare the biological effects of substituents on the phenyl moieties, the analogous copper(I) and silver(I) complexes of the anion of the parent 1,3-diphenylpropane-1,3-dione (HLPh) ligand were also synthesized and included in the study. In the syntheses of the Cu(I) and Ag(I) complexes, the phosphane coligands triphenylphosphine (PPh3) and 1,3,5-triaza-7-phosphaadamantane (PTA) were used to stabilize silver and copper in the +1 oxidation state, preventing the metal ion reduction to Ag(0) or oxidation to Cu(II), respectively. X-ray crystal structures of HLCF3 and the metal adducts [Cu(LCF3)(PPh3)2] and [Ag(LPh)(PPh3)2] are also presented. The antitumor properties of both classes of metal complexes were evaluated against a series of human tumor cell lines derived from different solid tumors, by means of both 2D and 3D cell viability studies. They display noteworthy antitumor properties and are more potent than cisplatin in inhibiting cancer cell growth. [ABSTRACT FROM AUTHOR]

Background: The World Health Organisation (WHO) calls on stakeholders to give Higher Education a key educational importance for the future of Europe. Within the content of the training programmes at university, sexuality emerges as a relevant topic in the nursing degree, to promote integral health from a holistic perspective. However, research on the presence of sexuality at the curricular level in Higher Education suggests that it is incomplete and underdeveloped. Methods: This is a protocol for a long-term, multi-centre, exploratory, descriptive, and cross-sectional study with a quantitative and qualitative approach lasting two years. The research will be carried out in the educational community, including, on the one hand, students, and professors and health professionals of nursing programmes from five universities in different parts of the world (Portugal, Spain, Italy, and the United States), and on the other hand, women, young people, and immigrants from these communities. The study will have several target populations. Firstly, the target is nursing students, with whom the aim is to define their perspective on the sexuality content taught at the university, and their level of knowledge. Secondly university professors and health professionals, with whom we will check their perspective on sexuality in the classroom, as well as their level of knowledge in this field. And finally, we will work with the community (women, young people, and immigrants) to whom we will try to bring sexuality from a useful and enjoyable perspective. In order to measure these variables in the protocol, instruments such as questionnaires and semi-structured interviews will be used. During data collection, ethical principles will be guaranteed and informed consent will be requested from the participants. Discussion: The results of the research will have a high curricular impact on the educational community, and will last over time, since the tools generated in the project will be included as part of nursing training programmes. In addition, participation in the project will improve health education for health professionals and at the community level on sexuality in both urban and rural populations. [ABSTRACT FROM AUTHOR]

The fluorescence imaging technique is becoming a useful tool in the natural and life sciences. Commercial biomarkers are available; however, some disadvantages exist like high isolation cost, low-temperature storage, photodegradation, and low yields. Here two new fluorescent molecular rotors (SB-B 2 and SB-B2 3) derived from Boron Schiff bases (BOSCHIBAs) were synthesized and characterized by NMR (1H and 13C), UV/Vis, and fluorescence spectroscopy. The crystal structure of SB-B2 3 by X-ray diffraction showed a binuclear complex and C2 symmetry. Both compounds showed viscochromic and thermochromic properties. The binuclear rotor 3 showed a greater luminescence intensity increase than the mononuclear one at the highest level of viscosity (90%). From the remarkable findings and to our best knowledge this is the first time low cytotoxicity BOSCHIBAs exhibit selective fluorescent staining of endoplasmic reticulum in HeLa cells and HUVECs. [ABSTRACT FROM AUTHOR]

Described herein are the synthesis, structure, and photophysics of the iodo-substituted cyclic trinuclear copper(I) complex, Cu3[4-I-3,5-(CF3)2Pz]3 supported by a highly-fluorinated pyrazolate in comparison with its previously reported 4-Br/4-Cl analogues. The crystal structure is stabilised by multiple supramolecular interactions of Cu3⋯I and hydrogen/halogen bonding. The photophysical properties and supramolecular interactions are investigated experimentally/computationally for all three 4-halo complexes vis-à-vis relativistic effects. [ABSTRACT FROM AUTHOR]

The π‐complexes of cationic coinage metal ions (Cu(I), Ag(I), Au(I)) provide useful experimental support for understanding fundamental characteristics of bonding and 13C‐NMR patterns of the group 11 triad. Here, we account for the role of relativistic effects on olefin‐coinage metal ion interaction for cationic, homoleptic tris‐ethylene, and tris‐norbornene complexes, [M(η2‐C2H4)3]+ and [M(η2‐C7H10)3]+ (M = Cu, Ag, Au), as representative case of studies. The M‐(CC) bond strength in the cationic, tris‐ethylene complexes is affected sizably for Au and to a lesser extent for Ag and Cu (48.6%, 16.7%, and 4.3%, respectively), owing to the influence on the different stabilizing terms accounting for the interaction energy in the formation of coinage metal cation‐π complexes. The bonding elements provided by olefin → M σ‐donation and olefin ← M π‐backbonding are consequently affected, leading to a lesser covalent interaction going down in the triad if the relativistic effects are ignored. Analysis of the 13C‐NMR tensors provides further understanding of the observed experimental values, where the degree of backbonding charge donation to π2*‐olefin orbital is the main influence on the observed high‐field shifts in comparison to the free olefin. This donation is larger for ethylene complexes and lower for norbornene counterparts. However, the bonding energy in the later complexes is slightly stabilized given by the enhancement in the electrostatic character of the interaction. Thus, the theoretical evaluation of metal‐alkene bonds, and other metal‐bonding situations, benefits from the incorporation of relativistic effects even in lighter counterparts, which have an increasing role going down in the group. [ABSTRACT FROM AUTHOR]

The bonding situation of Ag(I)CO complexes having a Scorpionate ligand directly attached to the transition metal has been analyzed in detail by means of relativistic density functional theory calculations. To this end, different experimentally characterized complexes together with other representative species have been considered to rationalize the observed shift of the corresponding ν(CO) stretching frequencies and the influence of the substituents in the Scorpionate ligand. With the help of the energy decomposition analysis method combined with the natural orbital for chemical valence it is found that the main contribution to the bonding comes from the electrostatic attractions between the LAg(I) and CO fragments. Despite that, the LAg → CO π‐backdonation is also significant in these species as well as in related LCu(I)CO complexes. [ABSTRACT FROM AUTHOR]

A series of DOSY experiments have been carried out to determine the solution stoichiometry of silver(I) 3,5‐bis (trifluoromethyl)pyrazolate species. This compound exists as a trimer in the solid state (n = 3) but in solutions of chlorinated solvents, the DOSY data suggest the presence of a mixture of solvent stabilized monomer (n = 1) and dimer (n = 2) in equilibrium. Different approximations have been used including the Stokes–Einstein and the Stokes–Einstein–Gierer–Wirtz equations. Some methodological problems are discussed. [ABSTRACT FROM AUTHOR]

Fluorinated tris(pyrazolyl)borate supporting ligands enable the stabilization of silver(I) bonded to a neutral, organometallic Fe(CO)5 ligand. The Ag–Fe interaction in these molecules is mainly electrostatic in nature, but σ-donor and backbonding contributions between the two metal fragments also play notable roles, which can be modulated by the scorpionate substituents. [ABSTRACT FROM AUTHOR]

The copper(I), silver(I), and gold(I) metals bind π‐ligands by σ‐bonding and π‐back bonding interactions. These interactions were investigated using bidentate ancillary ligands with electron donating and withdrawing substituents. The π‐ligands span from ethylene to larger terminal and internal alkenes and alkynes. Results of X‐ray crystallography, NMR, and IR spectroscopy and gas phase experiments show that the binding energies increase in the order Ag

A useful ligand involving three pyridyl donor arms and fluorocarbon substituents surrounding the coordination pocket has been assembled and utilized in coinage metal chemistry. This tris(pyridyl)borate serves as an excellent ligand support for the stabilization of ethylene complexes of copper, silver and gold. [ABSTRACT FROM AUTHOR]

Homoleptic, tetranuclear copper(I) pyrazolates {[3,5-(t-Bu)2Pz]Cu}4, {[3-(CF3)-5-(t-Bu)Pz]Cu}4, and {[4-Br-3,5-(i-Pr)2Pz]Cu}4 are excellent stand-alone catalysts for azide–alkyne cycloaddition reactions (CuAAC). This work demonstrates that a range of pyrazolates, including those with electron donating and electron-withdrawing groups to sterically demanding substituents on the pyrazolyl backbones, can serve as effective ligand supports on tetranuclear copper catalysts. However, in contrast to the tetramers and also highly fluorinated {[3,5-(CF3)2Pz]Cu}3, trinuclear copper(I) complexes such as {[3,5-(i-Pr)2Pz]Cu}3 and {[3-(CF3)-5-(CH3)Pz]Cu}3 supported by relatively electron rich pyrazolates display poor catalytic activity in CuAAC. The behavior and degree of aggregation of several of these copper(I) pyrazolates in solution were examined using vapor pressure osmometry. Copper(I) complexes such as {[3,5-(CF3)2Pz]Cu}3 and {[3-(CF3)-5-(t-Bu)Pz]Cu}4 with electron withdrawing pyrazolates were found to break up in solution to different degrees producing smaller aggregates while those such as {[3,5-(i-Pr)2Pz]Cu}3 and {[3,5-(t-Bu)2Pz]Cu}4 with electron rich pyrazolates remain intact. In addition, kinetic experiments were performed to understand the unusual activity of tetranuclear copper(I) pyrazolate systems. [ABSTRACT FROM AUTHOR]

Copyright of Brazilian Journal of Biology is the property of Instituto Internacional de Ecologia and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Purification of C2H4 from an C2H4 /C2H6 mixture is one of the most challenging separation processes, which is achieved mainly through energy‐intensive, cryogenic distillation in industry. Sustainable, non‐distillation methods are highly desired as alternatives. We discovered that the fluorinated bis(pyrazolyl)borate ligand supported copper(I) complex {[(CF3)2Bp]Cu}3 has features very desirable in an olefin–paraffin separation material. It binds ethylene exclusively over ethane generating [(CF3)2Bp]Cu(C2H4). This molecular compound exhibits extremely high and record ideal adsorbed solution theory (IAST) C2H4 /C2H6 gas separation selectivity, affording high purity (>99.5 %) ethylene that can be readily desorbed from separation columns. In‐situ PXRD provides a "live" picture of the reversible conversion between [(CF3)2Bp]Cu(C2H4) and the ethylene‐free sorbent in the solid‐state, driven by the presence or removal of C2H4. Molecular structures of trinuclear {[(CF3)2Bp]Cu}3 and mononuclear [(CF3)2Bp]Cu(C2H4) are also presented. [ABSTRACT FROM AUTHOR]