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Biomaterials-based biofabrication methods have gained much attention in recent years. Among them, 3D cell printing is a pioneering technology to facilitate the recapitulation of unique features of complex human tissues and organs with high process flexibility and versatility. Bioinks, combinations of printable hydrogel and cells, can be utilized to create 3D cell-printed constructs. The bioactive cues of bioinks directly trigger cells to induce tissue morphogenesis. Among the various printable hydrogels, the tissue- and organ-specific decellularized extracellular matrix (dECM) can exert synergistic effects in supporting various cells at any component by facilitating specific physiological properties. In this review, we aim to discuss a new paradigm of dECM-based bioinks able to recapitulate the inherent microenvironmental niche in 3D cell-printed constructs. This review can serve as a toolbox for biomedical engineers who want to understand the beneficial characteristics of the dECM-based bioinks and a basic set of fundamental criteria for printing functional human tissues and organs.

The postsynthetic modification strategy is adopted to demonstrate for the first time the syntheses of catalytically active chiral MOPMs from a preassambled achiral framework, MIL-101, by attaching L-proline-derived chiral catalytic units to the open metal coordination sites of the host framework. Various characterization techniques (including PXRD, TGA, IR, and N(2) absorption measurements) indicated that the chiral units are successfully incorporated into MIL-101, keeping the parent framework intact. The new chiral MOPMs show remarkable catalytic activities in asymmetric aldol reactions (yield up to 90% and ee up to 80%). It is interesting to note that these heterogeneous catalysts show much higher enantioselectivity than the corresponding chiral catalytic units as homogeneous catalysts. This study demonstrates a simple and efficient route for the generation of catalytically active chiral MOPMs. A variety of chiral catalytic units can be, in principle, incorporated into chemically robust achiral MOPMs with large pores by postmodification and the resulting chiral MOPMs may find useful applications in catalytic asymmetric transformations.

We report for the first time the complete and reversible exchange of metal ions constituting a robust microporous framework while maintaining not only the structural integrity of the framework but also single crystallinity. Solvothermal reaction of Cd(NO(3))(2) .4H(2)O with H(3)hett in DMF produced a new crystalline MOF 1 having a cubic network with 3D channels. The basic building unit of the framework 1 is an octahedron where the square planar tetrametallic SBUs ({Cd(4)O}(6+)) and tricarboxylate linkers (hett(3-)) occupy the vertices and triangular faces of the octahedron, respectively. The cubic framework is generated by sharing the vertices of the octahedra. The framework is exceptionally stable in open air as well as in various solutions including aqueous medium. Most interestingly, the framework constituting Cd(II) ions undergo complete and reversible exchange with Pb(II) in aqueous solution at room temperature without altering structural integrity and losing single crystallinity. We have also studied the complete exchange of framework Cd(II) ions with lanthanide ions (Dy(III) and Nd(III)) with the retention of the framework topology. The reversible exchange of framework constituting metal ions while maintaining the framework integrity and single crystallinity was confirmed by a combination of various methods including ICP-AES, in situ PXRD, TGA, IR, optical microscopy, elemental analysis, N(2) sorption and in situ single crystal X-ray structural analysis.

Direct-write assembly allows rapid fabrication of complex three-dimensional (3D) architectures, such as scaffolds simulating anatomical shapes, avoiding the need for expensive lithographic masks. However, proper selection of polymeric ink composition and tailor-made viscoelastic properties are critically important for smooth deposition of ink and shape retention. Deposition of only silk solution leads to frequent clogging due to shear-induced β-sheet crystallization, whereas optimized viscoelastic property of silk-gelatin blends facilitate the flow of these blends through microcapillary nozzles of varying diameter. This study demonstrates that induction of controlled changes in scaffold surface chemistry, by optimizing silk-gelatin ratio, can govern cell proliferation and maintenance of chondrocyte morphology. Microperiodic silk-gelatin scaffolds can influence postexpansion redifferentiation of goat chondrocytes by enhancing Sox-9 gene expression, aggregation, and driving cartilage matrix production, as evidenced by upregulation of collagen type II and aggrecan expression. The strategy for optimizing redifferentiation of chondrocytes can offer valuable consideration in scaffold-based cartilage repair strategies.

For the first time, phase-pure interpenetrated MOF-5 (1) has been synthesized and its gas sorption properties have been investigated. The phase purity of the material was confirmed by both single-crystal and powder X-ray diffraction studies and TGA analysis. A systematic study revealed that controlling the pH of the reaction medium is critical to the synthesis of phase-pure 1, and the optimum apparent pH (pH*) for the formation of 1 is 4.0-4.5. At higher or lower pH*, [Zn(2)(BDC)(2)(DMF)(2)] (2) or [Zn(5)(OH)(4)(BDC)(3)] (3), respectively, was predominantly formed. The pore size distribution obtained from Ar sorption experiments at 87 K showed only one peak, at ~6.7 Å, which is consistent with the average pore size of 1 revealed by single crystal X-ray crystallography. Compared to MOF-5, 1 exhibited higher stability toward heat and moisture. Although its surface area is much smaller than that of MOF-5 due to interpenetration, 1 showed a significantly higher hydrogen capacity (both gravimetric and volumetric) than MOF-5 at 77 K and 1 atm, presumably because of its higher enthalpy of adsorption, which may correlate with its higher volumetric hydrogen uptake compared to MOF-5 at room temperature, up to 100 bar. However, at high pressures and 77 K, where the saturated H(2) uptake mostly depends on the surface area of a porous material, the total hydrogen uptake of 1 is notably lower than that of MOF-5.

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Recent years have witnessed the advancement of silk biomaterials in bone tissue engineering, although clinical application of the same is still in its infancy. In this study, the potential of pure nonmulberry Antheraea mylitta (Am) fibroin scaffold, without preloading with bone precursor cells, to repair calvarial bone defect in a rat model is explored and compared with its mulberry counterpart Bombyx mori (Bm) silk fibroin. After 3 months of implantation, Am scaffold culminates in a completely ossified regeneration with a progressive increase in mineralization at the implanted site. On the other hand, the Bm scaffold fails to repair the damaged bone, presumably due to its low osteoconductivity and early degradation. The deposition of bone matrix on scaffolds is evaluated by scanning electron and atomic force microscopy. These results are corroborated by in vitro studies of enzymatic degradation, colony formation, and secondary conformational features of the scaffold materials. The greater biocompatibility and mineralization in pure nonmulberry fibroin scaffolds warrants the use of these scaffolds as an "ideal bone graft" biomaterial for effective repair of critical size defects.