Interplay of magnetic exchange interactions and Ni-S-Ni bond angles in polynuclear nickel(II) complexes.

The ability of bridging thiophenolate groups (RS(-)) to transmit magnetic exchange interactions between paramagnetic Ni(II) ions is examined. Specific attention is paid to complexes with large Ni-SR-Ni angles. For this purpose, dinuclear [Ni(2)L(1)(mu-OAc)I(2)][I(5)] (2) and trinuclear [Ni(3)L(2)(OAc)(2)][BPh(4)](2) (3), where H(2)L(1) and H(2)L(2) represent 24-membered macrocyclic amino-thiophenol ligands, are prepared and fully characterized by IR- and UV/Vis spectroscopy, X-ray crystallography, static magnetization M measurements and high-field electron spin resonance (HF-ESR). The dinuclear complex 2 has a central N(3)Ni(2)(mu-S)(2)(mu-OAc)Ni(2)N(3) core with a mean Ni-S-Ni angle of 92 degrees . The macrocycle L(2) supports a trinuclear complex 3, with distorted octahedral N(2)O(2)S(2) and N(2)O(3)S coordination environments for one central and two terminal Ni(II) ions, respectively. The Ni-S-Ni angles are at 132.8 degrees and 133.5 degrees . We find that the variation of the bond angles has a very strong impact on the magnetic properties of the Ni complexes. In the case of the Ni(2)-complex, temperature T and magnetic field B dependencies of M reveal a ferromagnetic coupling J=-29 cm(-1) between two Ni(II) ions (H=JS(1)S(2)). HF-ESR measurements yield a negative axial magnetic anisotropy (D<0) which implies a bistable (easy axis) magnetic ground state. In contrast, for the Ni(3)-complex we find an appreciable antiferromagnetic coupling J'=97 cm(-1) between the Ni(II) ions and a positive axial magnetic anisotropy (D>0) which implies an easy plane situation.

Biodegradable and adjustable sol-gel glass based hybrid scaffolds from multi-armed oligomeric building blocks.

Biodegradability is a crucial characteristic to improve the clinical potential of sol-gel-derived glass materials. To this end, a set of degradable organic/inorganic class II hybrids from a tetraethoxysilane(TEOS)-derived silica sol and oligovalent cross-linker oligomers containing oligo(d,l-lactide) domains was developed and characterized. A series of 18 oligomers (Mn: 1100-3200Da) with different degrees of ethoxylation and varying length of oligoester units was established and chemical composition was determined. Applicability of an established indirect rapid prototyping method enabled fabrication of a total of 85 different hybrid scaffold formulations from 3-isocyanatopropyltriethoxysilane-functionalized macromers. In vitro degradation was analyzed over 12months and a continuous linear weight loss (0.2-0.5wt%/d) combined with only moderate material swelling was detected which was controlled by oligo(lactide) content and matrix hydrophilicity. Compressive strength (2-30MPa) and compressive modulus (44-716MPa) were determined and total content, oligo(ethylene oxide) content, oligo(lactide) content and molecular weight of the oligomeric cross-linkers as well as material porosity were identified as the main factors determining hybrid mechanics. Cytocompatibility was assessed by cell culture experiments with human adipose tissue-derived stem cells (hASC). Cell migration into the entire scaffold pore network was indicated and continuous proliferation over 14days was found. ALP activity linearly increased over 2weeks indicating osteogenic differentiation. The presented glass-based hybrid concept with precisely adjustable material properties holds promise for regenerative purposes. STATEMENT OF SIGNIFICANCE: Adaption of degradation kinetics toward physiological relevance is still an unmet challenge of (bio-)glass engineering. We therefore present a glass-derived hybrid material with adjustable degradation. A flexible design concept based on degradable multi-armed oligomers was combined with an established indirect rapid prototyping method to produce a systematic set of porous sol-gel-derived class II hybrid scaffolds. Mechanical properties in the range of cancellous bone were narrowly controlled by hybrid composition. The oligoester introduction resulted in significantly increased compressive moduli. Cytocompatible hybrids degraded in physiologically relevant time frames and a promising linear and controllable weight loss profile was found. To our knowledge, our degradation study represents the most extensive long-term investigation of sol-gel-derived class II hybrids. Due to the broad adjustability of material properties, our concept offers potential for engineering of biodegradable hybrid materials for versatile applications.

Indirect rapid prototyping of sol-gel hybrid glass scaffolds for bone regeneration - Effects of organic crosslinker valence, content and molecular weight on mechanical properties.

We present a series of organic/inorganic hybrid sol-gel derived glasses, made from a tetraethoxysilane-derived silica sol (100% SiO2) and oligovalent organic crosslinkers functionalized with 3-isocyanatopropyltriethoxysilane. The material was susceptible to heat sterilization. The hybrids were processed into pore-interconnected scaffolds by an indirect rapid prototyping method, described here for the first time for sol-gel glass materials. A large panel of polyethylene oxide-derived 2- to 4-armed crosslinkers of molecular weights ranging between 170 and 8000Da were incorporated and their effect on scaffold mechanical properties was investigated. By multiple linear regression, 'organic content' and the 'content of ethylene oxide units in the hybrid' were identified as the main factors that determined compressive strength and modulus, respectively. In general, 3- and 4-armed crosslinkers performed better than linear molecules. Compression tests and cell culture experiments with osteoblast-like SaOS-2 cells showed that macroporous scaffolds can be produced with compressive strengths of up to 33±2MPa and with a pore structure that allows cells to grow deep into the scaffolds and form mineral deposits. Compressive moduli between 27±7MPa and 568±98MPa were obtained depending on the hybrid composition and problems associated with the inherent brittleness of sol-gel glass materials could be overcome. SaOS-2 cells showed cytocompatibility on hybrid glass scaffolds and mineral accumulation started as early as day 7. On day 14, we also found mineral accumulation on control hybrid glass scaffolds without cells, indicating a positive effect of the hybrid glass on mineral accumulation. STATEMENT OF SIGNIFICANCE: We produced a hybrid sol-gel glass material with significantly improved mechanical properties towards an application in bone regeneration and processed the material into macroporous scaffolds of controlled architecture by indirect rapid prototyping. We were able to produce macroporous materials of relevant porosity and pore size with compressive moduli, covering the range reported for cancellous bone while an even higher compressive strength was maintained. By multiple linear regression, we identified crosslinker parameters, namely organic content and the content of ethylene oxide units in the hybrids that predominantly determined the mechanics of the hybrid materials. The scaffolds proved to be cytocompatible and induced mineralization in SaOS-2 cells. This provides new insight on the critical parameters for the design of the organic components of covalent hybrid sol-gel glasses.

The first binucleating amino-thiophenolate macrocycles with pendant hydroxyethyl groups.

The synthesis of pendant donor macrocyclic amino-thiophenolate ligands with up to six hydroxyethyl arms has been achieved. The crystal structures of two proligands and a Ni(2)Na(4) complex of one deprotected derivative are reported.