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1.
Molecules ; 29(8)2024 Apr 17.
Artigo em Inglês | MEDLINE | ID: mdl-38675647

RESUMO

This study aimed to develop multifunctional nanoplatforms for both cancer imaging and therapy using superparamagnetic iron oxide nanoparticles (SPIONs). Two distinct synthetic methods, reduction-precipitation (MR/P) and co-precipitation at controlled pH (MpH), were explored, including the assessment of the coating's influence, namely dextran and gold, on their magnetic properties. These SPIONs were further functionalized with gadolinium to act as dual T1/T2 contrast agents for magnetic resonance imaging (MRI). Parameters such as size, stability, morphology, and magnetic behavior were evaluated by a detailed characterization analysis. To assess their efficacy in imaging and therapy, relaxivity and hyperthermia experiments were performed, respectively. The results revealed that both synthetic methods lead to SPIONs with similar average size, 9 nm. Mössbauer spectroscopy indicated that samples obtained from MR/P consist of approximately 11-13% of Fe present in magnetite, while samples obtained from MpH have higher contents of 33-45%. Despite coating and functionalization, all samples exhibited superparamagnetic behavior at room temperature. Hyperthermia experiments showed increased SAR values with higher magnetic field intensity and frequency. Moreover, the relaxivity studies suggested potential dual T1/T2 contrast agent capabilities for the coated SPpH-Dx-Au-Gd sample, thus demonstrating its potential in cancer diagnosis.


Assuntos
Meios de Contraste , Nanopartículas Magnéticas de Óxido de Ferro , Imageamento por Ressonância Magnética , Nanopartículas de Magnetita , Nanomedicina Teranóstica , Nanopartículas Magnéticas de Óxido de Ferro/química , Imageamento por Ressonância Magnética/métodos , Meios de Contraste/química , Nanopartículas de Magnetita/química , Nanopartículas de Magnetita/uso terapêutico , Humanos , Ouro/química , Dextranos/química , Gadolínio/química , Propriedades de Superfície , Hipertermia Induzida/métodos , Tamanho da Partícula
2.
Inorg Chem ; 62(5): 1988-1999, 2023 Feb 06.
Artigo em Inglês | MEDLINE | ID: mdl-36662518

RESUMO

The complete structure revision of the RE2PdGe3 (RE = rare-earth metal) series revealed that Yb2PdGe3 is the only AlB2 ordered superstructure. Good-quality single crystals of this compound were successfully grown from molten indium flux, enabling accurate single-crystal investigations. Yb2PdGe3 crystallizes with the Ce2CoSi3-type structure in the hexagonal space group P6/mmm (no. 191) with lattice parameters a = 8.468(1) Å and c = 4.0747(7) Å. This structure is a four-order derivative of AlB2, composed of planar ∞2[PdGe3] honeycomb layers spaced by Yb species, located at the center of Ge6 and Ge4Pd2 hexagons. A superconducting transition is observed below the critical temperature of 4 K. A divalent state of Yb is deduced from magnetic susceptibility measurements below room temperature, which indicate an almost nonmagnetic behavior. A charge transfer from Yb to Pd and Ge was evidenced by the Quantum Theory of Atoms in Molecules (QTAIM) effective charges; polar four-atomic Ge-Pd/Yb and two-atomic Pd-Yb bonds were observed from the ELI-D (electron localizability indicator), partial ELI-D, and ELI-D/QTAIM intersections. The bonding interactions between Ge atoms within regular Ge6 hexagons are found to be intermediate between single bonds, as in elemental Ge, and higher-order bonds in the hypothetic Ge6H6 and Ge66- aromatic molecules.

3.
Inorg Chem ; 62(34): 14044-14054, 2023 Aug 28.
Artigo em Inglês | MEDLINE | ID: mdl-37594252

RESUMO

Three mixed-valence barium iron fluorides, Ba7Fe7F34, Ba2Fe2F9, and BaFe2F7, were prepared through hydrothermal redox reactions. The characteristic structures of these compounds feature diverse distributions of FeIIF6 octahedra and FeIIIF6 groups. Ba7Fe7F34 contained one-dimensional infinite ∞[FeIIFeIII6F34]14- double chains, comprising cis corner-sharing octahedra along the b direction; Ba2Fe2F9 contained one-dimensional ∞[Fe2F9]4- double chains, consisting of cis corner-sharing octahedra along the chain (a-axis direction) and trans corner-sharing octahedra vertical to the chain, while BaFe2F7 revealed three-dimensional (3D) frameworks that consist of isolated edge-sharing dinuclear FeII2F10 units linked via corners by FeIIIF6 octahedra. Magnetization and Mössbauer spectroscopy measurements revealed that Ba7Fe7F34 exhibits an antiferromagnetic phase transition at ∼11 K, where ferrimagnetic ∞[FeIIFeIII6F34]14- double chains are arranged in a paralleling manner, while Ba2Fe2F9 shows canted antiferromagnetic ordering at ∼32.5 K, leading to noncollinear spin ordering.

4.
Bioscience ; 72(11): 1062-1073, 2022 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-36506699

RESUMO

Global biodiversity and ecosystem service models typically operate independently. Ecosystem service projections may therefore be overly optimistic because they do not always account for the role of biodiversity in maintaining ecological functions. We review models used in recent global model intercomparison projects and develop a novel model integration framework to more fully account for the role of biodiversity in ecosystem function, a key gap for linking biodiversity changes to ecosystem services. We propose two integration pathways. The first uses empirical data on biodiversity-ecosystem function relationships to bridge biodiversity and ecosystem function models and could currently be implemented globally for systems and taxa with sufficient data. We also propose a trait-based approach involving greater incorporation of biodiversity into ecosystem function models. Pursuing both approaches will provide greater insight into biodiversity and ecosystem services projections. Integrating biodiversity, ecosystem function, and ecosystem service modeling will enhance policy development to meet global sustainability goals.

5.
Horm Behav ; 144: 105217, 2022 08.
Artigo em Inglês | MEDLINE | ID: mdl-35785711

RESUMO

Prolactin, a hormone involved in vertebrate parental care, is hypothesized to inhibit reproductive hypothalamic-pituitary-gonadal (HPG) axis activity during parenting, thus maintaining investment in the current brood as opposed to new reproductive efforts. While prolactin underlies many parental behaviors in birds, its effects on other reproductive behaviors, such as courtship, remain unstudied. How prolactin affects neuropeptide and hormone receptor expression across the avian HPG axis also remains unknown. To address these questions, we administered ovine prolactin (oPRL) or a vehicle control to both sexes in experienced pairs of the biparental rock dove (Columba livia), after nest removal at the end of incubation. We found that oPRL promoted parental responses to novel chicks and stimulated crop growth compared to controls, consistent with other studies. However, we found that neither courtship behaviors, copulation rates nor pair maintenance differed with oPRL treatment. Across the HPG, we found oPRL had little effect on gene expression in hypothalamic nuclei, but increased expression of FSHB and hypothalamic hormone receptor genes in the pituitary. In the gonads, oPRL increased testes size and gonadotropin receptor expression, but did not affect ovarian state or small white follicle gene expression. However, the oviducts of oPRL-treated females were smaller and had lower estrogen receptor expression compared with controls. Our results highlight that some species, especially those that show multiple brooding, may continue to express mating behavior despite elevated prolactin. Thus, mechanisms may exist for prolactin to promote investment in parental care without concurrent inhibition of reproductive function or HPG axis activity.


Assuntos
Columbidae , Prolactina , Animais , Columbidae/metabolismo , Feminino , Expressão Gênica , Gônadas/metabolismo , Masculino , Prolactina/metabolismo , Prolactina/farmacologia , Reprodução/fisiologia , Ovinos
6.
Inorg Chem ; 59(13): 9261-9269, 2020 Jul 06.
Artigo em Inglês | MEDLINE | ID: mdl-32543836

RESUMO

Tetraphenylphosphonium salts of Co and Fe complexes with alkyl-substituted, tert-butyl (tb), and isopropyl (dp) 2,3-thiophenedithiolate (α-tpdt) ligands, namely, TPP[Co(α-tb-tpdt)2] (3), TPP2[Fe(α-tb-tpdt)2]2 (4a-b), TPP[Co(α-dp-tpdt)2] (5), and TPP[Fe(α-dp-tpdt)2] (6) were prepared and characterized by cyclic voltammetry, single crystal X-ray diffraction, magnetic susceptibility measurements, and 57Fe Mössbauer spectroscopy. Compound 3 and 5 are isostructural with their Au and Ni analogues with a square-planar coordination geometry. Compound 4 presents two polymorphs (4a-b) both showing a Fe(III) bisdithiolene dimerization. The magnetic susceptibility of 3 and 5 exhibits behavior dominated by antiferromagnetic interactions, with room-temperature magnetic moments of 3.40 and 3.36 µB, respectively, indicating that these square-planar Co(III) complexes assume an intermediate spin electronic configuration (S = 1) as supported by multiconfigurational and DFT calculations.

7.
PLoS Genet ; 13(10): e1007032, 2017 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-28968387

RESUMO

The NALCN/NCA ion channel is a cation channel related to voltage-gated sodium and calcium channels. NALCN has been reported to be a sodium leak channel with a conserved role in establishing neuronal resting membrane potential, but its precise cellular role and regulation are unclear. The Caenorhabditis elegans orthologs of NALCN, NCA-1 and NCA-2, act in premotor interneurons to regulate motor circuit activity that sustains locomotion. Recently we found that NCA-1 and NCA-2 are activated by a signal transduction pathway acting downstream of the heterotrimeric G protein Gq and the small GTPase Rho. Through a forward genetic screen, here we identify the GPCR kinase GRK-2 as a new player affecting signaling through the Gq-Rho-NCA pathway. Using structure-function analysis, we find that the GPCR phosphorylation and membrane association domains of GRK-2 are required for its function. Genetic epistasis experiments suggest that GRK-2 acts on the D2-like dopamine receptor DOP-3 to inhibit Go signaling and positively modulate NCA-1 and NCA-2 activity. Through cell-specific rescuing experiments, we find that GRK-2 and DOP-3 act in premotor interneurons to modulate NCA channel function. Finally, we demonstrate that dopamine, through DOP-3, negatively regulates NCA activity. Thus, this study identifies a pathway by which dopamine modulates the activity of the NCA channels.


Assuntos
Proteínas de Caenorhabditis elegans/metabolismo , Caenorhabditis elegans/efeitos dos fármacos , Caenorhabditis elegans/genética , Dopamina/farmacologia , Quinases de Receptores Acoplados a Proteína G/metabolismo , Canais Iônicos/metabolismo , Acetilcolina/metabolismo , Animais , Proteínas de Caenorhabditis elegans/genética , Epistasia Genética , Quinases de Receptores Acoplados a Proteína G/genética , Subunidades alfa Gi-Go de Proteínas de Ligação ao GTP/genética , Subunidades alfa Gi-Go de Proteínas de Ligação ao GTP/metabolismo , Regulação da Expressão Gênica , Estudo de Associação Genômica Ampla , Interneurônios/efeitos dos fármacos , Interneurônios/metabolismo , Canais Iônicos/genética , Oxigenases de Função Mista/genética , Oxigenases de Função Mista/metabolismo , Regiões Promotoras Genéticas , Receptores de Dopamina D2/genética , Receptores de Dopamina D2/metabolismo , Transdução de Sinais
8.
Chemistry ; 25(7): 1758-1766, 2019 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-30403293

RESUMO

Early actinide ions have large spin-orbit couplings and crystal field interactions, leading to large anisotropies. The success in using actinides as single-molecule magnets has so far been modest, underlining the need for rational strategies. Indeed, the electronic structure of actinide single-molecule magnets and its relation to their magnetic properties remains largely unexplored. A uranium(III) single-molecule magnet, [UIII {SiMe2 NPh}3 -tacn)(OPPh3 )] (tacn=1,4,7-triazacyclononane), has been investigated by means of a combination of magnetic, spectroscopic and theoretical methods to elucidate the origin of its static and dynamic magnetic properties.

9.
Food Control ; 104: 333-342, 2019 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-39015434

RESUMO

Background: The recent listeriosis outbreak in South Africa brought food safety concerns to the fore in terms of both policy and practice. These concerns encompass both health and nutrition aspects, as well as the economy, because the food system in South Africa contributes significantly to economic growth and food security. However, the food sector is challenged with food safety risks, such as foodborne diseases, food fraud and a general lack of effective enforcement of regulation. The inability of government to effectively regulate the food sector is a contributing factor to increased food safety risks. Focusing on the formal sector, which is subject to regulation, this review provides an overview of the current state of food safety policies and regulations, food safety challenges, and food safety practices in the food system, after the listeriosis crisis of 2017 and 2018. Method: This study used a systematic process to review three sets of data in South Africa: food safety related public policies and regulations, company reports (2013-2018) and media articles (May 2017-May 2018). Food safety policies were selected from a food system policy database created by the research team. The company reports were retrieved from their websites. Factivia was used to search for the media articles. The data were thematically analyzed. The analysis framework was informed by the Food and Agriculture Organization's (FAO) food safety risk analysis. Activities related to food safety risk analysis: risk assessment, risk management, and risk communication were searched for in each material included in the study. Results: Seventy-four documents made up of 13 policies, 47 media articles and 15 company reports were reviewed. Food safety is regulated by three governments departments: Department of Health (DOH), Department of Agriculture, Forestry and Fisheries (DAFF), and Department of Trade and Industry (DTI) through bylaws and regulations. The departments are directly (DAFF) or indirectly (DOH through municipal or metro Environmental Health Professional) involved in food safety enforcement, surveillance, and education. The enforcement of different regulatory processes is often poorly coordinated. Responding to this regulatory environment, food safety activities of the food retail industry include a self-regulatory system reliant on internal and third-party food audits, worker training, external testing, and consumer education. Given this fragmented framework and the lack of interaction, it is clear that the governance of the South African food safety system is not "fit for purpose" in that there is a gap in the effectiveness of government regulation and the self-regulation of the formal sector, and a growing risk from an inability to regulate the large informal sector. Food safety challenges identified in our analysis included disease outbreaks, concerns over mislabeling, and lack of regulation for food handling and distribution. Conclusion: The findings suggest that there should be a combination of responsibility from all levels of stake-holders in the food retail sector in order to improve food safety and prevent food safety breaches. In addition, strong governance of the food safety system is required to enable effective legislation and enforcement.

10.
J Lipid Res ; 59(2): 237-249, 2018 02.
Artigo em Inglês | MEDLINE | ID: mdl-29167413

RESUMO

Recent studies have highlighted the role of palmitoleic acid [16:1n-7 (cis-9-hexadecenoic acid)] as a lipid hormone that coordinates cross-talk between liver and adipose tissue and exerts anti-inflammatory protective effects on hepatic steatosis and insulin signaling in murine models of metabolic disease. More recently, a 16:1n-7 isomer, cis-7-hexadecenoic acid (16:1n-9), that also possesses marked anti-inflammatory effects, has been described in human circulating monocytes and monocyte-derived macrophages. By using gas chromatographic/mass spectrometric analyses of dimethyl disulfide derivatives of fatty acyl methyl esters, we describe in this study the presence of a third 16:1 isomer, sapienic acid [16:1n-10 (6-cis-hexadecenoic acid)], in phagocytic cells. Cellular levels of 16:1n-10 appear to depend not only on the cellular content of linoleic acid, but also on the expression level of fatty acid desaturase 2, thus revealing a complex regulation both at the enzyme level, via fatty acid substrate competition, and directly at the gene level. However, unlike 16:1n-7 and 16:1n-9, 16:1n-10 levels are not regulated by the activation state of the cell. Moreover, while 16:1n-7 and 16:1n-9 manifest strong anti-inflammatory activity when added to the cells at low concentrations (10 µM), notably higher concentrations of 16:1n-10 are required to observe a comparable effect. Collectively, these results suggest the presence in phagocytic cells of an unexpected variety of 16:1 isomers, which can be distinguished on the basis of their biological activity and cellular regulation.


Assuntos
Ácidos Graxos Monoinsaturados/farmacologia , Fagócitos/efeitos dos fármacos , Animais , Células Cultivadas , Ácidos Graxos Monoinsaturados/química , Voluntários Saudáveis , Humanos , Lipopolissacarídeos/farmacologia , Camundongos , Estrutura Molecular , Fagócitos/metabolismo , Células RAW 264.7 , Estereoisomerismo
11.
J Lipid Res ; 59(12): 2308-2320, 2018 12.
Artigo em Inglês | MEDLINE | ID: mdl-30352954

RESUMO

Tyrosine hydroxylase (TH) catalyzes the first step in catecholamines synthesis. We studied the impact of reduced TH in brown adipose tissue (BAT) activation. In adult heterozygous (Th+/- ) mice, dopamine and noradrenaline (NA) content in BAT decreased after cold exposure. This reduced catecholaminergic response did not impair cold adaptation, because these mice induced uncoupling protein 1 (UCP-1) and maintained BAT temperature to a similar extent than controls (Th+/+ ). Possible compensatory mechanisms implicated were studied. Prdm16 and Fgf21 expression, key genes in BAT activation, were elevated in Th+/- mice at thermoneutrality from day 18.5 of embryonic life. Likewise, plasma FGF21 and liver Fgf21 mRNA were increased. Analysis of endoplasmic reticulum (ER) stress, a process that triggers elevations in FGF21, showed higher phospho-IRE1, phospho-JNK, and CHOP in BAT of Th+/- mice at thermoneutrality. Also, increased lipolysis in BAT of cold-exposure Th+/- mice was demonstrated by increased phosphorylation of hormone-sensitive lipase (HSL), as well as diacylglycerol (DAG) and FFA content. Overall, these results indicate that the mild effects of Th haploinsufficiency on BAT function are likely due to compensatory mechanisms involving elevations in Fgf21 and Prdm16 and through adaptive changes in the lipid profile.


Assuntos
Tecido Adiposo Marrom/metabolismo , Fatores de Crescimento de Fibroblastos/metabolismo , Tirosina 3-Mono-Oxigenase/metabolismo , Animais , Western Blotting , Calorimetria Indireta , Catecolaminas/sangue , Temperatura Baixa , Proteínas de Ligação a DNA/metabolismo , Dopamina/metabolismo , Ácidos Graxos não Esterificados/sangue , Imuno-Histoquímica , Fígado/metabolismo , Camundongos , Camundongos Endogâmicos C57BL , Camundongos Mutantes , Norepinefrina/sangue , Reação em Cadeia da Polimerase em Tempo Real , Fatores de Transcrição/metabolismo , Triglicerídeos/sangue
12.
Inorg Chem ; 57(14): 8146-8159, 2018 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-29953212

RESUMO

The 5-substituted 2-aryliminopyrrolyl ligand precursors of the type 5-R-2-[ N-(2,6-diisopropylphenyl)formimino]-1 H-pyrrole (R = 2,6-Me2-C6H3 (1a), 2,4,6-iPr3-C6H2 (1b), 2,4,6-Ph3-C6H3 (1c; reported in this work), anthracen-9-yl (1d), CPh3 (1e; reported in this work)) were treated with K[N(SiMe3)2] in toluene to yield the respective 5-R-2-[ N-(2,6-diisopropylphenyl)formimino]pyrrolyl potassium salts 2a-e in high yields. The paramagnetic 15-electron Co(II) complexes of the type [Co{κ2 N,N'-5-R-NC4H2-2-C(H)═N(2,6-iPr2-C6H3)}(Py)Cl] (3a-e; Py = pyridine) were prepared by salt metathesis of CoCl2(Py)4 with the respective potassium salts 2a-e in moderate to good yields. When the CoCl2(THF)1.5 precursor was combined with the in situ prepared sodium salt of ligand precursor 1b, the trinuclear complex [Co{κ2 N, N'-5-(2,4,6-iPr3-C6H2)-NC4H2-2-C(H)═N(2,6-iPr2-C6H3)}(µ-Cl)]2[(µ-Cl)2Co(THF)2] (4) was obtained in high yields. Complexes 3a-e have high-spin electronic configurations both in solution and in the solid state. X-ray diffraction studies of complexes 3a,e confirmed distorted tetrahedral coordination geometries. Complex 4, on the other hand, is a linear trinuclear Co(II)-Co(II)-Co(II) complex with two terminal distorted tetrahedral four-coordinate sites and a central octahedral six-coordinate site, all in the high-spin state, S = 3/2, as confirmed by the magnetization measurements and DFT calculations. Solid-state magnetic measurements in both complexes 3a and 4 point to paramagnetic behavior with a significant contribution of spin-orbit coupling. Additionally, intramolecular antiferromagnetic coupling of the adjacent cobalt atoms is observed in 4. The Co(II) family 3a-d, on activation with K(HBEt3), catalyzed the hydroboration of several α-olefins with pinacolborane, in good to high yields (50-80%). This system almost exclusively yielded the anti-Markovnikov (a-Mk) addition product, except when styrene was used, where the selectivity in the Markovnikov (Mk) product increased with increasing steric bulkiness of the 5-R-2-iminopyrrolyl substituent, with the a-Mk:Mk molar ratio varying from 2.33:1 (3a, R = 2,6-Me2-C6H3) to 0.75:1 (3c, R = 2,4,6-Ph3-C6H3). Preliminary mechanistic studies indicate that the activation by K(HBEt3) gave rise to a Co(I) species, the catalyst system likely following an oxidative addition pathway.

13.
Molecules ; 23(2)2018 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-29443956

RESUMO

Gold and nickel bisdithiolene complexes with methyl and tert-butyl substituted thiophenetetrathiafulavalenedithiolate ligands (α-mtdt and α-tbtdt) were prepared and characterized. These complexes were obtained, under anaerobic conditions, as tetrabutylammonium salts. The diamagnetic gold monoanion (n-Bu4N)[Au(α-mtdt)2] (3) and nickel dianionic species (n-Bu4N)x[Ni(α-mtdt)2] (x = 1,2) (4) were similar to the related non-substituted extended thiophenic-TTF (TTF = tetrathiafulvalene) bisdithiolenes. However the introduction of the large, bulky substituent tert-butyl, led to the formation of a Au (I) dinuclear complex, (n-Bu4N)2[Au2(α-tbtdt)2] (5). The neutral methyl substituted gold and nickel complexes were easily obtained through air or iodine exposure as polycrystalline or amorphous fine powder. [Au(α-mtdt)2] (6) and [Ni(α-mtdt)2] (7) polycrystalline samples display properties of a metallic system with a room temperature electrical conductivity of 0.32 S/cm and ≈4 S/cm and a thermoelectric power of ≈5 µV/K and ≈32 µV/K, respectively. While [Au(α-mtdt)2] (6) presented a Pauli-like magnetic susceptibility typical of conducting systems, in [Ni(α-mtdt)2] (7) large magnetic susceptibilities indicative of high spin states were observed. Both electric transport properties and magnetic properties for gold and nickel [M(α-mtdt)2] are indicative that these compounds are single component molecular conductors.


Assuntos
Complexos de Coordenação/química , Ouro/química , Níquel/química , Tiofenos/química , Cristalografia por Raios X , Ligantes , Modelos Moleculares , Compostos Organometálicos/química
14.
Chemistry ; 21(49): 17817-26, 2015 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-26536849

RESUMO

A tetravalent uranium compound with a radical azobenzene ligand, namely, [{(SiMe2 NPh)3 -tacn}U(IV) (η(2) -N2 Ph2 (.) )] (2), was obtained by one-electron reduction of azobenzene by the trivalent uranium compound [U(III) {(SiMe2 NPh)3 -tacn}] (1). Compound 2 was characterized by single-crystal X-ray diffraction and (1) H NMR, IR, and UV/Vis/NIR spectroscopy. The magnetic properties of 2 and precursor 1 were studied by static magnetization and ac susceptibility measurements, which for the former revealed single-molecule magnet behaviour for the first time in a mononuclear U(IV) compound, whereas trivalent uranium compound 1 does not exhibit slow relaxation of the magnetization at low temperatures. A first approximation to the magnetic behaviour of these compounds was attempted by combining an effective electrostatic model with a phenomenological approach using the full single-ion Hamiltonian.

15.
Inorg Chem ; 54(4): 1354-62, 2015 Feb 16.
Artigo em Inglês | MEDLINE | ID: mdl-25634799

RESUMO

The Fe(III) complexes Fe(5-Br-qsal)2Ni(dmit)2·solv with solv = CH2Cl2 (1) and (CH3)2CO (2) were synthesized, and their structural and magnetic properties were studied. While magnetization and Mössbauer spectroscopy data of 1 showed a gradual spin transition, compound 2 evidenced an abrupt transition with a thermal hysteresis of 13 K close to room temperature (T1/2 ↓ ∼273 K and T1/2 ↑ ∼286 K). A similar packing arrangement of segregated layers of cations and anions was found for 1 and 2. In both low-spin, LS, structures there are a large number of short intra- and interchain contacts. This number is lower in the high-spin, HS, phases, particularly in the case of 1. The significant loss of strong π-π interactions in the cationic chains and short contacts in the anionic chains in the HS structure of 1 leads to alternating strong and weak bonds between cations along the cationic chains and the formation of unconnected dimers along the anionic chains. This is consistent with a significant weakening of the extended interactions in 1. On the other hand, in the HS phase of 2 the 3D dimensionality of the short contacts observed in the LS phases is preserved. The effect of distinct solvent molecules on the intermolecular spacings explains the different spin crossover behaviors of the title compounds.

16.
Inorg Chem ; 54(4): 1949-57, 2015 Feb 16.
Artigo em Inglês | MEDLINE | ID: mdl-25651301

RESUMO

The magnetic properties of layered dysprosium hydroxides, both diluted in the diamagnetic yttrium analogous matrix (LYH:0.04Dy), and intercalated with 2,6-naphthalene dicarboxylate anions (LDyH-2,6-NDC), were studied and compared with the recently reported undiluted compound (LDyH = Dy8(OH)20Cl4·6H2O). The Y diluted compound reveals a single-molecule magnet (SMM) behavior of single Dy ions, with two distinct slow relaxation processes of the magnetization at low temperatures associated with the two main types of Dy sites, 8- and 9-fold coordinated. Only one relaxation process is observed in both undiluted LDyH and intercalated compounds as a consequence of dominant ferromagnetic Dy-Dy interactions, both intra- and interlayer. Semiempirical calculations using a radial effect charge (REC) model for the crystal field splitting of the Dy levels are used to explain data in terms of contributions from the different Dy sites. The dominant ferromagnetic interactions are explained in terms of orientations of easy magnetization axes obtained by REC calculations together with the sign of the superexchange expected from the Dy-O-Dy angles.

17.
Inorg Chem ; 54(14): 7000-6, 2015 Jul 20.
Artigo em Inglês | MEDLINE | ID: mdl-26158196

RESUMO

(α-DT-TTF)2[Au(i-mnt)2] and (α-DT-TTF)2[Co(mnt)2] are two new salts of the donor α-dithiophene-tetrathiafulvalene with stable diamagnetic anions, both presenting a ladder structure of the donors organized in paired segregated stacks. The first one is isostructural with previously reported closely related compounds and presents a magnetic spin-ladder behavior with J∥= 83.5 K and J⊥ = 110.3 K as estimated from spin susceptibility data in single crystals. (α-DT-TTF)2[Co(mnt)2] presents a new structural type with a different arrangement of pairs of donor stacks, alternating with stacks of dimerized [Co(mnt)2] anions which are however arranged in an uncorrelated fashion perpendicular to the stacking axis. Due to the strong coupling between the disordered anion chains and the donor chains, this compound does not present a magnetic spin-ladder behavior. The low temperature superstructure of (DT-TTF)2[Cu(mnt)2] below the transition at 235 K, previously known to be associated with a lattice doubling along the stacking axis, was solved by synchrotron radiation diffraction in small single crystals. It is found that this dimerization is due to donor charge localization with the spin carriers being associated with fully oxidized donor species alternating with neutral donors.

18.
Nanotechnology ; 26(42): 425704, 2015 Oct 23.
Artigo em Inglês | MEDLINE | ID: mdl-26421876

RESUMO

Iron oxide nanoparticles (NPs) have been extensively studied in the last few decades for several biomedical applications such as magnetic resonance imaging, magnetic drug delivery and hyperthermia. Hyperthermia is a technique used for cancer treatment which consists in inducing a temperature of about 41-45 °C in cancerous cells through magnetic NPs and an external magnetic field. Chemical precipitation was used to produce iron oxide NPs 9 nm in size coated with oleic acid and trisodium citrate. The influence of both stabilizers on the heating ability and in vitro cytotoxicity of the produced iron oxide NPs was assessed. Physicochemical characterization of the samples confirmed that the used surfactants do not change the particles' average size and that the presence of the surfactants has a strong effect on both the magnetic properties and the heating ability. The heating ability of Fe3O4 NPs shows a proportional increase with the increase of iron concentration, although when coated with trisodium citrate or oleic acid the heating ability decreases. Cytotoxicity assays demonstrated that both pristine and trisodium citrate Fe3O4 samples do not reduce cell viability. However, oleic acid Fe3O4 strongly reduces cell viability, more drastically in the SaOs-2 cell line. The produced iron oxide NPs are suitable for cancer hyperthermia treatment and the use of a surfactant brings great advantages concerning the dispersion of NPs, also allowing better control of the hyperthermia temperature.


Assuntos
Coloides/química , Nanopartículas de Magnetita/química , Tensoativos/química , Animais , Sobrevivência Celular/efeitos dos fármacos , Chlorocebus aethiops , Coloides/toxicidade , Temperatura Alta , Nanopartículas de Magnetita/toxicidade , Células Vero
19.
Inorg Chem ; 53(22): 11809-11, 2014 Nov 17.
Artigo em Inglês | MEDLINE | ID: mdl-25354258

RESUMO

The magnetic properties of the two uranium coordination compounds, [K(18c6)][U(OSi(O(t)Bu)3)4] and [K(18c6)][U(N(SiMe3)2)4], both presenting the U(III) ion in similar pseudotetrahedral coordination environments but with different O- or N-donor ligands, have been measured. The static magnetic susceptibility measurements and density functional theory studies suggest the presence of different ligand fields in the two compounds. Alternating-current susceptibility studies conducted at frequencies ranging from 95 to 9995 Hz and at temperatures in the 1.7-10 K range revealed for both compounds slow magnetic relaxation already at zero static magnetic field with similar energy barriers U ∼24 K.

20.
Nanomedicine ; 10(8): 1757-66, 2014 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-24941462

RESUMO

Surface chemistry plays an important role in gold nanoparticles (AuNPs) stability and biocompatibility, which are crucial for their implementation into the clinical setting. We evaluated short- (30 min) and long-term (28 days) biodistribution and toxicity of ~20 nm citrate- and pentapeptide CALNN-coated AuNPs after a single intravenous injection in rats. The pattern of AuNPs distribution in Cit- and CALNN-AuNPs-injected rats was very similar in the assessed time-points. Both AuNPs were quickly removed from the bloodstream and preferentially accumulated in the liver. At 28 days liver remained the main accumulation site but at significantly lower levels compared to those found at 30 min. Spleen atrophy and hematological findings compatible with mild anemia were observed in CALNN-AuNPs-administered rats. Under our experimental conditions, surface coating had more impact on toxicity rather than on biodistribution of the AuNPs. Improvements in the design of capping peptides need to be done to increase biomedical applicability of peptide-coated AuNPs. FROM THE CLINICAL EDITOR: The biodistribution and toxicity of ~ 20 nm citrate- and pentapeptide CALNN-coated gold nanoparticles was investigated after a single intravenous injection in rats. Rapid clearance and hepatic accumulation was found at 30-minutes, whereas mild anemia and spleen atrophy was seen 28 days post injection. The authors also concluded that the toxicity was related to the capping proteins as opposed to the biodistribution of the particles, providing important suggestion for future design of gold nanoparticles.


Assuntos
Ouro/química , Nanopartículas Metálicas/administração & dosagem , Nanopartículas/metabolismo , Administração Intravenosa , Animais , Masculino , Ratos
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