Synthesis, X-ray structures and reactivity of the first bis(amino)metallastibanes and bis(amino)metallabismuthanes

The reaction of Me2Si(N-t-Bu)2ECl (E = Sb, Bi) with NaM(CO)nCp (M = Fe, Mo, W; Cp = ?5-C5H5) affords metallastibanes and bismuthanes, Cp(CO)nME(N-t-Bu)2SiMe2 (4a-c, 5a-c). The structures of 4c (E = Sb, M = W) and 5c (E = Bi, M = W) have been determined by X-ray crystallography. Both compounds are isotypic and isostructural and crystallize in the triclinic space group with a = 7.030 (9) A°, b = 10.51 (1) A°, c = 16.22 (2) A°, a = 94.1 (1)°, ß = 90.4 (1)°, ? = 104.9 (1)°, Z = 2 for 4c and a = 7.014 (9) A°, b = 10.57 (1) A°, c = 16.25 (2) A°, a = 94.1 (1)°, ß= 90.1 (1)°, ? = 104.6 (1)°, Z = 2 for 5c. The E-W s-bond lengths are 3.010 (1) A° for E = Sb and 3.082 (1) A° for E = Bi. The reaction of the antimony derivatives with Fe2(CO)9 yields [Fe(CO)4]Cp(CO)nMSb(N-t-Bu)2SiMe2 (6a-c) as a result of the complexation of the antimony lone pair. The crystal structures of 6a (M = Fe) and 6b (M = Mo) have been determined. 6a crystallizes in the monoclinic space group with a = 10.399 (9) A°, b = 16.76 (2) A°, c = 15.74 (1) A°, ß = 94.16 (6)°, and Z = 4. Both Sb-Fe bond lengths are almost similar: 2.547 (1) A° for the covalent bond and 2.530 (1) A° for the dative bond. 6b crystallizes in the monoclinic space group with a = 12.305 (7) A°, b = 13.812 (7) A°, c = 16.75 (1) A°, ß = 99.03 (5)°, and Z = 4. The Sb-Mo covalent bond length is 2.871 (1) A° and the Sb-Fe dative bond 2.539 (1) A°

Physico-chemical properties of β-diketone phosphorus-containing dendrimers

Protolytic, absorbance and fluorescence properties of β-diketone phosphorus-containing dendrimers based on cyclotriphosphazene core were studied. Dendrimer solutions in acetone are characterized by intense absorbance band at ≈ 340 nm (ε340≈ 8.5·104L/mol·сm) and fluorescence band with maximum at 440 nm. Position of these maxima does not change in various solvents, unlike the bands of monomer β-diketone. It was found that dendrimer aggregation is accompanied by appearance of a second absorbance band ε400≈ 4.5·103L/mol·сm, by red shift of emission spectra ∆λ ≈ 10 nm and also by decrease in surface tension of acetone solution. Ability of dendrimer aggregates to solubilize organic substrates was observed with the fluorescent indicator acridine

Biological properties of water-soluble phosphorhydrazone dendrimers

Dendrimers are hyperbranched and perfectly defined macromolecules, constituted of branches emanating from a central core in an iterative fashion. Phosphorhydrazone dendrimers constitute a special family of dendrimers, possessing one phosphorus atom at each branching point. The internal structure of these dendrimers is hydrophobic, but hydrophilic terminal groups can induce the solubility of the whole structure in water. Indeed, the properties of these compounds are mainly driven by the type of terminal groups their bear; this is especially true for the biological properties. For instance, positively charged terminal groups are efficient for transfection experiments, as drug carriers, as anti-prion agents, and as inhibitor of the aggregation of Alzheimer's peptides, whereas negatively charged dendrimers have anti-HIV properties and can influence the human immune system, leading to anti-inflammatory properties usable against rheumatoid arthritis. This review will give the most representative examples of the biological properties of water-soluble phosphorhydrazone dendrimers, organized depending on the type of terminal groups they bear.Dendrímeros são macromoléculas extremamente ramificadas e perfeitamente definidas constituídas de ramificações que partem de um foco central de uma forma iterativa. Dendrímeros de fosforidrazona constituem uma família especial de dendrímeros, que possuem um átomo de fósforo em cada ponto da ramificação. A estrutura interna destes dendrímeros é hidrofóbica, mas grupos hidrofílicos terminais podem induzir a solubilidade em água de toda estrutura. De fato, as propriedades destes compostos são principalmente orientadas pelos grupos terminais que apresentam, especialmente para as propriedades biológicas. Por exemplo, grupos terminais carregados positivamente são eficientes para experimentos de transfecção, como transportadores de fármacos, agentes antipríons e como inibidores da agregação de peptídeos do Alzheimer, enquanto que dendrímeros carregados negativamente têm propriedades anti-HIV e podem influenciar o sistema imune humano, levando propriedades antiinflamatórias úteis contra artrite reumatoide. Essa revisão dará os exemplos mais representativos das propriedades biológicas de dendrímeros de fosforidrazona solúveis em água, organizados de acordo com os grupos terminais que possuem

Dielectric study of local relaxations in dendritic macromolecules

The aim of this work is to characterize the dielectric properties of amorphous dendritic macromolecules as a function of architectural complexity. By combining thermostimulated currents and dynamic dielectric spectroscopy, the dielectric permittivity has been obtained as a function of temperature, in a very broad frequency range (10−4–106 Hz). Generations g = 0 to g = 2 were investigated. The molecular origin of the quasi-Debye mode observed for g = 0 at low temperature is common to all generations: localized reorientations of aldehyde end groups. The interactions with the phosphorus/sulfur (P = S) dipoles are probably responsible for the broadening pointed out in upper generations

PPH dendrimers grafted on silica nanoparticles: surface chemistry, characterization, silver colloids hosting and antibacterial activity

Polyphosphorhydrazone (PPH) dendrimers have been grafted on silica nanoparticles, and the surface functions of the dendrimers have been derivatized to phosphonates with lateral poly(ethyleneglycol) (PEG) chains. All materials have been thoroughly characterized by MAS NMR, FT-IR, electron microscopy, TGA and elemental analysis. These materials successfully hosted silver and silver oxide nanoparticles. The resulting composites exhibit antibacterial activity

Synthesis and characterization of bifunctional dendrimers: preliminary use for the coating of gold surfaces and the proliferation of human osteoblasts (HOB)

Open Access Article. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.Two different novel families of bifunctional water-soluble dendrimers are synthesized, using the specific functionalization of one function of the cyclotriphosphazene core. Dendrimers are grown from the 5 remaining functions, up to generation 2. Water-solubility is attained in the last step of the synthesis by grafting either ammonium terminal groups or carboxylate terminal groups, on generations 1 and 2 of these bifunctional dendrimers. 12 new compounds are synthesized and fully characterized, in particular by multi-nuclear NMR. The function linked to the core is thioctic acid, suitable for grafting onto gold, thus both types of water-soluble dendrimers can be used to coat gold surfaces. These macromolecular assemblies are characterized by surface plasmon resonance (SPR). In a preliminary attempt, the gold surfaces modified by either positively or negatively charged dendrimers are used for studying their interaction with cells. Exposed to human osteoblast cells (OBC), the influence of the surface coatings on the cell responses is investigated. Polycationic dendrimers provoke cell apoptosis, whereas negatively charged dendrimers support cell adhesion and proliferation

Modulation of pro-inflammatory activation of monocytes and dendritic cells by aza-bis-phosphonate dendrimer as an experimental therapeutic agent

INTRODUCTION: Our objective was to assess the capacity of dendrimer aza-bis-phosphonate (ABP) to modulate phenotype of monocytes (Mo) and monocytes derived dendritic cells (MoDC) activated in response to toll-like receptor 4 (TLR4) and interferon γ (IFN- γ) stimulation. METHODS: Mo (n = 12) and MoDC (n = 11) from peripheral blood of healthy donors were prepared. Cells were preincubated or not for 1 hour with dendrimer ABP, then incubated with lipopolysaccharide (LPS; as a TLR4 ligand) and (IFN-γ) for 38 hours. Secretion of tumor necrosis factor α (TNFα), interleukin (IL) -1, IL-6, IL-12, IL-10 and IL-23 in the culture medium was measured by enzyme-linked immunosorbent assay (ELISA) and Cytokine Bead Array. Differentiation and subsequent maturation of MoDC from nine donors in the presence of LPS were analyzed by flow cytometry using CD80, CD86, CD83 and CD1a surface expression as markers. RESULTS: Mo and MoDC were orientated to a pro-inflammatory state. In activated Mo, TNFα, IL-1β and IL-23 levels were significantly lower after prior incubation with dendrimer ABP. In activated MoDC, dendrimer ABP promoted IL-10 secretion while decreasing dramatically the level of IL-12. TNFα and IL-6 secretion were significantly lower in the presence of dendrimer ABP. LPS driven maturation of MoDC was impaired by dendrimer ABP treatment, as attested by the significantly lower expression of CD80 and CD86. CONCLUSION: Our data indicate that dendrimer ABP possesses immunomodulatory properties on human Mo and MoDC, in TLR4 + IFN-γ stimulation model, by inducing M2 alternative activation of Mo and promoting tolerogenic MoDC