Organic/Inorganic bioactive materials Part III: in vitro bioactivity of gelatin/silicocarnotite hybrids

In this work we present our experimental results on synthesis, structure evolution and in vitro bioactivity assessment of new gelatin/silicocarnotite hybrid materials. The hybrids were obtained by diluting gelatin (G) and silicocarnotite (S) ceramic powder with G:S ratios of 75:25 and 25:75 wt.% in hot (40°C) water. The hybrids were characterized using XRD, FTIR, SEM/EDS and XPS. FTIR depicts that the “red shift” of amide I and COO⁻ could be attributed to the fact that the gelatin prefers to chelate Ca²⁺ from S. The growth of calcium phosphates on the surface of the hybrids synthesized and then immersed in 1.5 SBF for 3 days was studied by using of FTIR, XRD and SEM/EDS. According to FTIR results, after an immersion of 3 days, A and B-type CO₃HA can be observed on the surface. XRD results indicate the presence of hydroxyapatite with well defined crystallinity. SEM/EDS of the precipitated layers show the presence of CO₃HA and amorphous calcium phosphate on the surface of samples with different G/S content when immersed in 1.5 SBF. XPS of the G/S hybrid with 25:75 wt.% proved the presence of Ca-deficient hydroxyapatite after an in vitro test for 3 days.     

Organic/Inorganic bioactive materials Part II: in vitro bioactivity of Collagen-Calcium Phosphate Silicate/Wollastonite hybrids

In the present study, novel hybrid materials of Collagen (C) and Calcium Phosphate Silicate/Wollastonite (CPS/W) were synthesized. The CPS/W ceramic was prepared via polystep sol-gel method. The dissolution test of CPS/W ceramic was filled with TRIS-HCl buffer. FTIR depicts that hydroxyl carbonate apatite (OHCO₃HA) was observed after 3 days of immersion in TRIS-HCl buffer. Biohybrids of C-CPS/W were produced from diluted hydrochloric acid collagen type I and ceramic powder with different ratios of C and CPS/W equal to 25:75 and 75:25 wt.%. The synthesized hybrids were characterized by FTIR, XRD and SEM. FTIR depicts a “red shift” if amide I could be attributed to the fact that the collagen prefers to chelate Ca²⁺ from partial dissolution of CPS/W ceramic. The growth of B-type carbonate containing hydroxyapatite (B-CO₃HA) on the C-CPS/W hybrids soaked in 1.5SBF was observed. The negatively charged carboxylate groups from the collagen may be responsible for hydroxyapatite (HA) deposition. This fact was confirmed by the “red shift” of carboxylate groups of collagen in FTIR spectra. The formation of HA was observed by FTIR, XRD and SEM.     

Synthesis and application of inorganic/organic composite materials

A new type of inorganic-organic composite has been developed using organic monomeric or polymerizable silanes (with appropriate organic groupings like double bonds or epoxides) as monomers or in situ prepared or separately added nano-scale ceramic or metal particles. Due to the small size of the particulate phase, these composites are still highly transparent but show properties at least partially to be attributed to the inorganic phase. The introduction of special functions into these materials has been used for the fabrication of interesting functions like non-linear optical properties, low surface free energy coatings, controlled release properties or special mechanical properties (scratch resistance).     

Organic/inorganic bioactive materials part IV: <Emphasis Type="Italic">In vitro</Emphasis> assessment of bioactivity of gelatin-calcium phosphate silicate/wollastonite hybrids

Biohybrids consisting of gelatin (G) and calcium phosphate silicate/wollastonite (CPS/W) have not been prepared so far. In this work our results are focused on the possibility of obtaining G-CPS/W bioactive hybrids in vitro. XRD, FTIR, SEM/EDS techniques were employed to characterize the synthesized hybrid materials. FTIR shows that before immersion in 1.5 SBF the “red shift” of COO- band for pure G is observed. The presence of this bond could be attributed to the formation of COO-Ca²⁺ via non-biomimetic route. After immersion in 1.5 SBF, FTIR shows the presence of A- and B-type carbonate containing hydroxyapatite (A/B-CO₃HA). ESD and FTIR show that small amount of calcite (CaCO₃) are present after in vitro test in 1.5 SBF for 3 days. XRD reveals that CO₃HA and small amounts of CaCO₃ can be detected after in vitro test. SEM results obtained for immersed samples show that hydroxyapatite (HA) particles fully covered the surface of the hybrids by a layer composed of spherulites. At higher magnification, very small elongated crystallites could be observed.      

Sol-gel bioactive glass-ceramics Part I: Calcium phosphate silicate/wollastonite glass-ceramics

In this work we present experimental results about synthesis, structure evolution and in vitro bioactivity of new calcium phosphate silicate/wollastonite (CPS/W) glass-ceramics. The samples obtained were synthesized via polystep sol-gel process with different Ca/P+Si molar ratio (R). The structure of the materials obtained was studied by XRD, FTIR spectroscopy and SEM. XRD showed the presence of Ca₁₅(PO₄)₂(SiO₄)₆, β-CaSiO₃ and α-CaSiO₃ for the sample with R=1.89 after thermal treatment at 1200°C/2h. The XRD results are in good agreement with FTIR analysis. SEM denotes that apatite formation can be observed after soaking in simulated body fluid (SBF).      

Organic/inorganic hybrid materials and nanocomposites based upon layered silicates modified with cyclic amidines

Various cyclic amidinium cations were used to exchange intergallery sodium cations of water‐swellable fluorohectorite in order to produce novel families of organic/inorganic hybrid materials. Oligomeric cyclic amidinium cations, such as mono(imidazolinium)‐terminated oligostyrene, oligostyrene‐co‐oligo(acrylonitrile), and oligo(methyl methacrylate) with number‐average molecular masses around 3 000 g/mol afforded effective exfoliation during melt processing. Morphology and dynamic mechanical properties were measured as a function of silicate content and silicate modification.     

Synthesis and Studies of Some Ketosulfones,Part I

New ketosulfones have been prepared. Their chemical composition and structure were proved by analytical and spectral methods. The kinetics of 1,4-addition of arenesulfinic acids to 1,3-diphenyl-2-nitropropenone and 3-nitro-4-phenyl-3-butene-2-on were studied by LC. The overall reaction is second order, while it is first order regarding each reagent and substrate. On the basis of the experimental results for the dependence of rate constants on the temperature and the influence of the substituents on the rate, a probable mechanism of the nucleophilic addition was suggested.     

Synthesis of naturally occurring bioactive butyrolactones: maculalactones A-C and nostoclide I

Starting from citraconic anhydride (13), a simple multistep (9-10 steps) synthesis of naturally occurring butyrolactones maculalactone A (3), maculalactone B (1), maculalactone C (2) and nostoclide I (4) have been described with good overall yields via dibenzylmaleic anhydride (20) and benzylisopropylmaleic anhydride (27). The two anhydrides 20 and 27 were prepared by S_N2′ coupling reactions of appropriate Grignard reagents with dimethyl bromomethylfumarate (14), LiOH-induced hydrolysis of esters to acids, bromination of carbon-carbon double bond, in situ dehydration followed by dehydrobromination and chemoselective allylic substitution of bromoatom in disubstituted anhydrides 19 and 26 with appropriate Grignard reagents. The NaBH₄ reduction of these anhydrides 20 and 27 furnished the desired lactones 21 and 29, respectively. The lactone 21 on Knoevenagel condensation with benzaldehyde, furnished maculalactone B (1), which on isomerization gave maculalactone C (2). Selective catalytic hydrogenation of 1 gave maculalactone A (3). The conversion of lactone 29 to nostoclide I (4) is known.     

Associative thickeners. Part I: Synthesis,rheology and aggregation behavior

Nonionic associative thickeners with systematic changes in chemical composition have been synthesized. Rheological measurements of thickened latexes are presented as well as measurements of relaxation times, intrinsic viscosity and osmotic pressure of polymers in pure water solution. We find that the general hydrophobicity of the polymers' end groups control both rheology and efficiency. Hydrophobic parts in the interior of the polymer do not seem to effect rheology in latex systems. Viscosity increases with molecular weight in the low molecular region (Mw<10000), and passes through a maximum in the high molecular region. The thickeners seem to form micelle-like aggregates even at very low concentrations, while at higher concentrations the viscoelastic properties may be modeled by means of one Maxwell element. Only the network relaxation times but not the network structure seems to be dependent on the polymers' end group.     

Rare-earth/inorganic/organic polymeric hybrid materials: molecular assembly, regular microstructure and photoluminescence

2-Hydroxynicotinic acid (HNA) was grafted by 3-(triethoxysilyl)propyl isocyanate (TEPIC) to achieve the molecular precursor HNA-Si through the hydrogen-transfer nucleophilic addition reaction between the hydroxyl group of HNA and the isocyanate group of TEPIC. Then, a chemically bonded rare-earth/inorganic polymeric hybrid material (A) was constructed using HNA-Si as a bridge molecule that can both coordinate to rare-earth ions (HNA-Si-RE) and form an inorganic Si-O network with tetraethoxysilane (TEOS) after cohydrolysis and copolycondensation processes. Further, three types of novel rare-earth/inorganic/organic polymeric hybrids (B-D) were assembled by the introduction of three different organic polymeric chains into the above system. First, methacrylic acid (MAA) [or methacrylic acid and acrylamide (ALM) in the molar ratio of 1:1] was mixed to polymerize (or copolymerize) with benzoyl peroxide (BPO) as the initiator to form poly(methacrylic acid) (PMAA) [or poly(methacrylic and acrylamide) (PMAALM)], and then PMAA or PMAALM was added to the precursor HNA-Si before the assembly of HNA-Si-RE, resulting in the hybrid materials HNA-Si-RE-PMAA (B) and HNA-Si-RE-PMAALM (C). Second, poly(vinylpyrrolidone) (PVP) was added to coordinate to the rare-earth ions by the carbonyl group in the complex HNA-Si-RE, to achieve the hybrid HNA-Si-RE-PVP (D). All of these hybrid materials exhibit homogeneous, regular, and ordered microstructures and morphologies, suggesting the occurrence of self-assembly of the inorganic network and organic chain. Measurements of the photoluminescent properties of these materials show that the ternary rare-earth/inorganic/organic polymeric hybrids present stronger luminescent intensities, longer lifetimes, and higher luminescent quantum efficiencies than the binary rare-earth/inorganic polymeric hybrids, indicating that the introduction of the organic polymer chain is a benefit for the luminescence of the overall hybrid system.     

Anhydrous tin and lead hexacyanoferrates (II).: Part I. Synthesis and crystal structure.

The crystal structure of Pb₂Fe(CN)₆ and Sn₂Fe(CN)₆ has been first determined and refined using the Rietveld method with combined CuKα₁ X-ray and constant-wavelength neutron powder diffraction data in space group P-3 (147, Z=1). The unit cell constants are a=7.1346(1) and 7.1805(1) Å, c=5.4531(2) and 5.3639(1) Å, respectively. The compounds are layered, groups of three nearest [Fe(CN)₆]⁴⁻-complexes are joined to layers by means of Pb or Sn atoms. The same Pb or Sn atoms (c.n.=3+3) joint three nearest complexes from the next layer. The jointing goes through ‘nitrogenlead(tin)nitrogen’ bonds.     

Synthesis,structure and optical properties of different dimensional organic–inorganic perovskites

By varying the substituent position of aminomethyl on pyridine ring in acid solution, different dimensional lead bromide frameworks ranging from zero-dimension and one-dimension to two-dimension were obtained. 2-(Aminomethyl)pyridine (2-AMP) or 3-(aminomethyl)pyridine (3-AMP) and PbBr₂ construct hybrid perovskites, of which (H₂2-AMP)PbBr₄ (1) exhibits two-dimensional perovskite sheets with special hydrogen bonds and (H₂3-AMP)₂PbBr₆ (2) shows an uncommon zero-dimensional inorganic framework with isolated octahedra. The characteristic exciton peaks in absorption spectra are located at 431 nm for compound 1 and at 428 nm for compound 2. (H₂4-AMP)PbBr₄ (3) with one-dimensional zigzag edge-sharing octahedral PbBr₄²⁻chains can be obtained using 4-(aminomethyl)pyridine (4-AMP) as organic component under the same experimental conditions as those for 2-AMP and 3-AMP.     

Quadricyclanes. Part I: Photoelectron spectra and electronic structure

The photoelectron spectra of quadricyclane ( 3 ) and 3-methylidene quadricyclane ( 4 ) have been measured. The results served as a basis for the elucidation of the electronic structure of these compounds, which agreed with theoretical calculations. It is found that the symmetry of the HOMO of 3 is different when compared to that of its valence isomer norbornadiene ( 1 ). The results also indicate that the structure of the highest occupied orbitals cannot be derived by only considering the Walsh-orbitals of the two three-membered rings. In addition one of the Walsh-components of the four-memebered ring has to be taken into account.     

Synthesis, network structure and morphology of s-triazine-organosilane glassy hybrid materials

A series of five hybrid materials are synthesized by the reaction of cyanuric chloride (C₃N₃Cl₃) with different alkoxysilanes (R_xSi(OC₂H₅)_4−x, R=CH₃, C₆H₅ and x=0, 1, 2) in ethanol using sol–gel technique. The resulting s-triazine-organosilane products were examined using spectroscopic (UV–visible, FT-IR), thermal (thermogravimetric analysis, TGA), powder X-ray diffraction (P-XRD), BET analysis and microscopic (scanning electron microscopy, SEM) techniques. These hybrid materials exhibit globular and two-dimensional morphological textures with varying degrees of crystalline microstructures. Depending on the functionality of the organosilane building blocks the obtained hybrid materials exhibit different material characteristics including their solid state, Vicat softening point (Vicat hardness), density and porosity. BET surface area measurements indicate that these materials possess small specific surface areas of 0.36–2.3 m²/g with external surface area of ~0.02 m²/g. The phenyl-containing hybrids exhibit pronounced hydrolytic stability compared to the methyl- and silica-based analogs. The DMSO and sulfolane solutions of the prepared hybrids are transparent to visible light whereas their cold-compressed discs are optically opaque.     

Synthesis and structure of a pure inorganic polyoxo-metalate-based porous framework

A pure inorganic porous framework based on the tungstoferrate[FeW₁₂O₄₀]^5-,Fe（H₂O）₆H[Na₆FeW₁₂O₄₀]₂·44H₂O（1） was obtained by the conventional aqueous solution method and characterized by elemental analysis,TG,FT-IR,UV-vis spectroscopy. Single-crystal X-ray diffraction analyses reveal that compound 1 crystallizes in the space group Fm-3m,which is composed of a porous inorganic framework[Na₆FeW₁₂O₄₀]_n with two kinds of pores A and B,accommodating Fe（H₂O）₆ units in pore A,which was observed rarely in the pure inorganic framework.     

The analysis of inorganic siliceous materials by atomic absorption spectrophotometry and the hydrofluoric acid decomposition technique : Part I. the analysis of silicate rocks

The analysis of various inorganic siliceous materials of geological and industrial interest is discussed. The methods proposed are based on decomposition of a single sample by hydrofluoric acid and determination by atomic absorption spectrophotometry of up to 10 constituents. General procedures are described, and details are given for the determination of silicon, aluminium, total iron, magnesium, calcium, sodium, potassium, titanium and manganese in silicate rocks. Analytical data are given for the analysis of reference rocks G-2 and W-1.     

Acyl Iodides in Organic Synthesis: I. Reactions with Alcohols

Reaction of acyl iodides RC(O)I (R = Me, Ph) with alcohols R'OH (R' = Me, Et, i-Pr, t-Bu, CH₂ = CHCH₂, HCCCH₂) provides in the corresponding organyl iodides R'I. Unlike that 2-chloroethanol and phenol (R' = CH₂CH₂Cl, Ph) react with RC(O)I in the same way as with acyl chlorides yielding esters RCO₂R'. This reaction path occurs partially also with methanol and ethanol.     

Standardization of methods for the determination of traces of mercury : Part I. Determination of total inorganic mercury in inorganic samples

A method is described for the routine determination of mercury in the process and product streams of chlor alkali electrolysis plants (with the exception of chlorine) and also in the plant waste waters. The procedure is based on flameless atomic absorption spectrophotometry. Results for interlaboratory trials involving up to 37 participating laboratories are presented. Both synthetic and technical samples were analysed with mercury contents varying between 20 μg kg^-1 and 20 mg kg^-1. Statistical evaluation of the results gave a value of from 4 to 8% for the repeatability and from 6 to 22% for the reproducibility.     

Novel ammonium phosphinates containing peptide moiety: Synthesis, structure, and in vitro antimicrobial activity

Five new ammonium phosphinates with formula [XC₆H₄NHC(O)NHP(O)YO]^?[H₂Y]⁺ (Y = N(CH₃)(CH₂C₆H₅), X = H (IV), CH₃ (V), NO₂ (VI); Y = NH(CH₂C₆H₅), X = H (VII), NO₂ (VIII)) were synthesised by the reaction of N-arylureidophoshoryl dichlorides with N-methylbenzylamine or benzylamine in the presence of an excess amount of the corresponding amine. All new compounds were characterised by NMR and IR spectral data and elemental analysis. Their antimicrobial activity was tested against some Gram-positive and Gram-negative bacteria and fungi. Compounds IV and VIII exhibited moderate activity in vitro against Bacillus subtilis. In addition, compound VIII moderately inhibited Pseudomonas aeruginosa. The crystal structure of benzylmethylammonium(3-phenylureido)(benzylmethylamino)phosphinate (IV) was also determined. This compound crystallises in the orthorhombic system.     

Isomannide monoundecenoate-based 1,2,3-triazoles: Design,synthesis, and in vitro bioactive evaluation

A new series of isomannide monoundecenoate-based 1,2,3-triazole analogs 6a–e were designed by employing click chemistry in good yields. in vitro bioactive assay manifested that the several target compounds exhibited promising antibacterial and antifungal activities. Notably, compounds having phenyl substituted triazole 6a , and hydroxy phenyl substituted triazole 6b possessed highly selective promising inhibition towards Gram-positive bacterial strains namely Bacillus subtilis and Staphylococcus aureus with MIC value of 3.9 μg/mL. Further, these potential hybrids ( 6a and 6b) also exhibited highly impressive antifungal activity against the tested panel of Candida strains with MIC value of 3.9 μg/mL. Based on our in vitro preliminary antimicrobial study, these two compounds 6a and 6b have been identified as potential antimicrobial lead compounds. Moreover, all prepared derivatives were also evaluated for their in vitro cytotoxic activities against A549, MCF7, DU145 and HeLa cancer cell lines. The results indicated that only the hydroxy phenyl substituted triazole analog 6b displayed good cytotoxic activity towards all tested human cancer cell lines without any significant effects on normal cell line (HUVEC).