A new approach to analyzing regenerated bone quality in the mouse digit amputation model using semi-automatic processing of microCT data.

Bone regeneration is a critical area of research impacting treatment of diseases such as osteoporosis, age-related decline, and orthopaedic implants. A crucial question in bone regeneration is that of bone architectural quality, or how "good" is the regenerated bone tissue structurally? Current methods address typical long bone architecture, however there exists a need for improved ability to quantify structurally relevant parameters of bone in non-standard bone shapes. Here we present a new analysis approach based on open-source semi-automatic methods combining image processing, solid modeling, and numerical calculations to analyze bone tissue at a more granular level using µCT image data from a mouse digit model of bone regeneration. Examining interior architecture, growth patterning, spatial mineral content, and mineral density distribution, these methods are then applied to two types of 6-month old mouse digits - 1) those prior to amputation injury (unamputated) and 2) those 42 days after amputation when bone has regenerated. Results show regenerated digits exhibit increased inner void fraction, decreased patterning, different patterns of spatial mineral distribution, and increased mineral density values when compared to unamputated bone. Our approach demonstrates the utility of this new analysis technique in assessment of non-standard bone models, such as the regenerated bone of the digit, and aims to bring a deeper level of analysis with an open-source, integrative platform to the greater bone community.

Cobalt(III) tetraaza-macrocyclic complexes as efficient catalyst for photoinduced hydrogen production in water: Theoretical investigation of the electronic structure of the reduced species and mechanistic insight.

We recently reported a very efficient homogeneous system for visible-light driven hydrogen production in water based on the cobalt(III) tetraaza-macrocyclic complex [Co(CR)Cl2](+) (1) (CR=2,12-dimethyl-3,7,11,17-tetra-azabicyclo(11.3.1)-heptadeca-1(17),2,11,13,15-pentaene) as a noble metal-free catalyst, with [Ru(II)(bpy)3](2+) (Ru) as photosensitizer and ascorbate/ascorbic acid (HA(-)/H2A) as a sacrificial electron donor and buffer (PhysChemChemPhys 2013, 15, 17544). This catalyst presents the particularity to achieve very high turnover numbers (TONs) (up to 1000) at pH 4.0 at a relative high concentration (0.1mM) generating a large amount of hydrogen and having a long term stability. A similar activity was observed for the aquo derivative [Co(III)(CR)(H2O)2](3+) (2) due to substitution of chloro ligands by water molecule in water. In this work, the geometry and electronic structures of 2 and its analog [Zn(II)(CR)Cl](+) (3) derivative containing the redox innocent Zn(II) metal ion have been investigated by DFT calculations under various oxidation states. We also further studied the photocatalytic activity of this system and evaluated the influence of varying the relative concentration of the different components on the H2-evolving activity. Turnover numbers versus catalyst (TONCat) were found to be dependent on the catalyst concentration with the highest value of 1130 obtained at 0.05 mM. Interestingly, the analogous nickel derivative, [Ni(II)(CR)Cl2] (4), when tested under the same experimental conditions was found to be fully inactive for H2 production. Nanosecond transient absorption spectroscopy measurements have revealed that the first electron-transfer steps of the photocatalytic H2-evolution mechanism with the Ru/cobalt tetraaza/HA(-)/H2A system involve a reductive quenching of the excited state of the photosensitizer by ascorbate (kq=2.5×10(7) M(-1) s(-1)) followed by an electron transfer from the reduced photosensitizer to the catalyst (ket=1.4×10(9) M(-1) s(-1)). The reduced catalyst can then enter into the cycle of hydrogen evolution.