Further structural characterization of ovine forestomach matrix and multi-layered extracellular matrix composites for soft tissue repair.

Decellularized extracellular matrix (dECM)-based biomaterials are of great clinical utility in soft tissue repair applications due to their regenerative properties. Multi-layered dECM devices have been developed for clinical indications where additional thickness and biomechanical performance are required. However, traditional approaches to the fabrication of multi-layered dECM devices introduce additional laminating materials or chemical modifications of the dECM that may impair the biological functionality of the material. Using an established dECM biomaterial, ovine forestomach matrix, a novel method for the fabrication of multi-layered dECM constructs has been developed, where layers are bonded via a physical interlocking process without the need for additional bonding materials or detrimental chemical modification of the dECM. The versatility of the interlocking process has been demonstrated by incorporating a layer of hyaluronic acid to create a composite material with additional biological functionality. Interlocked composite devices including hyaluronic acid showed improved in vitro bioactivity and moisture retention properties.

Crystal structures of (µ2-η(2),η(2)-4-hydroxybut-2-yn-1-yl 2-bromo-2-methylpropanoate-κ(4) C (2),C (3):C (2),C (3))bis[tricarbonylcobalt(II)](Co-Co) and [µ2-η(2),η(2)-but-2-yne-1,4-diyl bis(2-bromo-2-methyl-propanoate)-κ(4) C (2),C (3):C (2),C (3)]bis[tricarbonylcobalt(II)](Co-Co).

The title compounds, [Co2(C8H11BrO3)(CO)6], (1), and [Co2(C12H16Br2O4)(CO)6], (2), result from the replacement of two carbonyl ligands from dicobalt octa-carbonyl by the alkynes 4-hy-droxy-but-2-ynyl 2-bromo-2-methyl-propano-ate and but-2-yne-1,4-diyl bis-(2-bromo-2-methyl-propano-ate), respectively. Both mol-ecules have classic tetra-hedral C2Co2 cluster cores with the Co(II) atoms in a highly distorted octa-hedral coordination geometry. The alkyne ligands both adopt a cis-bent conformation on coordination. In the crystal structure of (1), classical O-H⋯O and non-classical C-H⋯O contacts form inversion dimers. These combine with weak O⋯O and Br⋯O contacts to stack the mol-ecules into inter-connected columns along the b-axis direction. C-H⋯O and C-H⋯Br contacts stabilize the packing for (2), and a weak Br⋯O contact is also observed. Inter-connected columns of mol-ecules again form along the b-axis direction.

2,4-Dichloro-N-p-tolyl-benzamide.

In the title compound, C(14)H(11)Cl(2)NO, the C-N-C(=O)-C amide unit is almost planar (r.m.s. deviation = 0.0317 Å) and subtends dihedral angles of 65.93 (6) and 29.45 (7)°, respectively, to the dichloro-benzene and tolyl rings. The two aromatic rings are inclined at 37.92 (6)° to one another. In the crystal structure, N-H⋯O hydrogen bonds link the mol-ecules into chains along b. Additional weak C-H⋯Cl and C-H⋯O hydrogen bonds combine with C-H⋯π and very weak π-π contacts [Cg⋯Cg distance = 4.0217 (12) Å] to stack the mol-ecules down b.

2-Fluoro-N-(4-methoxy-phen-yl)benzamide.

In the title compound, C(14)H(12)FNO(2), the fluoro-benzene and methoxy-benzene rings are inclined at 27.06 (7) and 23.86 (7)°, respectively, to the amide portion of the mol-ecule and at 3.46 (9)° to one another. The meth-oxy substituent lies close to the methoxy-benzene ring plane, with a maximum deviation of 0.152 (3) Šfor the methyl C atom. In the crystal structure, inter-molecular N-H⋯O hydrogen bonds link mol-ecules into rows along a. Weak C-H⋯O and C-H⋯F inter-actions further stabilize the packing, forming corrugated sheets in the bc plane.

1-(2-Fluoro-phen-yl)-6,7-dimethoxy-isochroman.

In the title compound, C(17)H(17)FO(3), the benzene ring of the isochroman unit is inclined at 84.96 (7)° to the fluoro-benzene ring plane, and the pyran ring adopts a half-boat conformation. In the crystal structure, C-H⋯O hydrogen bonds link mol-ecules into rows along the c axis, while C-H⋯O inter-actions and C-H⋯F hydrogen bonds to the fluorine acceptor stack the mol-ecules down the b axis. In addition, the crystal structure exhibits a weak C-H⋯π inter-action between a methyl H atom of the meth-oxy group and the dimethoxy-benzene ring of an adjacent mol-ecule.

2,4-Dichloro-N-o-tolyl-benzamide.

In the title compound, C(14)H(11)Cl(2)NO, the central C-C(O)-N-C amide unit makes dihedral angles of 68.71 (11) and 54.92 (12)°, respectively, with the dichloro-benzene and tolyl rings. The two aromatic rings are inclined at 16.25 (17)°. In the crystal, N-H⋯O hydrogen bonds link mol-ecules into zigzag chains propagating in [001]. C-H⋯Cl contacts link these chains and additional C-H⋯O contacts generate stacks down b. Weak C-H⋯π and C-Cl⋯π inter-actions [Cl⋯centroid distance = 3.5422 (15) Å] may also stabilize the structure.

1-(2-Chloro-5-nitro-phen-yl)-3-(2,2-di-methyl-propion-yl)thio-urea.

With the exception of the C atoms of two of the methyl groups of the tert-butyl substituent, all of the non-H atoms of the title compound, C(12)H(14)ClN(3)O(3)S, lie on a mirror plane. The 2-chloro-5-nitro-phenyl and 2,2-dimethyl-propionyl substituents are, respectively, cis and trans relative to the thio-carbonyl S atom across the two C-N bonds. Intra-molecular N-H⋯O and C-H⋯S hydrogen bonds form S(6) ring motifs, also in the mirror plane. Despite the presence of two N-H subsituents, no inter-molecular hydrogen bonds are observed in the crystal structure. Weak π-π contacts [centroid-centroid distances of 4.2903 (17) Å] involving adjacent aromatic rings link the mol-ecules in a head-to-tail fashion above and below the mol-ecular plane.

4-Chloro-N-(3-methoxy-phen-yl)-benz-amide.

The title benzamide derivative, C(14)H(12)ClNO(2), crystallizes with two independent mol-ecules in the asymmetric unit. Both are close to being planar, with dihedral angles between the two benzene rings of 11.92 (6) and 12.80 (7)°. In the crystal structure, N-H⋯O hydrogen bonds link mol-ecules into chains along a. These inter-actions are augmented by C-H⋯O hydrogen bonds to form two-dimensional layers in the ac plane. Additional C-H⋯O inter-actions result in a three-dimensional network consisting of undulating rows along c. The crystal studied was an inversion twin with a 0.59 (3):0.41 (3) domain ratio.

N-Cyclo-hexyl-2-fluoro-benzamide.

In the title compound, C(13)H(16)FNO, the fluoro-benzene ring plane and the plane through the amide unit are inclined at a dihedral angle of 29.92 (7)°. The cyclo-hexane ring adopts a chair conformation. In the crystal structure, N-H⋯O hydrogen bonds, augmented by weak C-H⋯O inter-actions, link the mol-ecules into transverse chains along a. These chains are linked into zigzag columns down a by C-H⋯F hydrogen bonds and C-H⋯π inter-actions.

N-Butyl-4-chloro-benzamide.

In the title benzamide derivative, C(11)H(14)ClNO, the chloro-benzene and butyl-amine groups are each planar, with mean deviations from the planes of 0.013 and 0.030 Å, respectively, and a dihedral angle of 2.54 (9)° between the two planes. In the crystal structure, N-H⋯O hydrogen bonds link mol-ecules in rows along a. Short inter-molecular Cl⋯Cl inter-actions [3.4225 (5) Å] link these rows into sheets in the ac plane. Additional weak C-H⋯O and C-H⋯π inter-actions generate a three-dimensional network.

2-Fluoro-N-o-tolyl-benzamide.

In the title compound, C(14)H(12)FNO, the ortho-F atom and corresponding H atom on the fluoro-benzene ring are disordered over two positions with occupancies of 0.856 (4) and 0.144 (4). The amide unit is planar with a maximum deviation of 0.0057 (16) Šand the amide plane makes dihedral angles of 38.27 (11)° with the fluoro-benzene ring plane and 37.53 (10)° with the tolyl ring. The two benzene rings are inclined at an angle of 4.17 (15)°. In the crystal structure, chains form along b through N-H⋯O hydrogen bonds augmented by C-H⋯π inter-actions. Additional inter-molecular C-H⋯O and C-H⋯F hydrogen bonds further stabilize the structure, forming layers in the ac plane.