We report two ternary phase diagrams that show the synthesis conditions to prepare protein@ZIF biocomposites with different phases, including BSA@ZIF-C and insulin@ZIF-C. For each biocomposite, we measured distinct encapsulation efficiency and release profile properties.

Integrating metal-organic frameworks (MOFs) in microelectronics has disruptive potential because of the unique properties of these microporous crystalline materials. Nanoscale patterning is a fundamental step in the implementation of MOFs in miniaturised solid-state devices. Conventional MOF patterning methods suffer from a low resolution and poorly defined pattern edges. Here, we demonstrate for the first time resist-free, direct X-ray and e-beam lithography of MOFs. This process avoids etching damage and contamination, and leaves the porosity and crystallinity of the patterned MOFs intact. The resulting highquality patterns have a record sub-50 nm resolution, far beyond the state of the art in MOF patterning and approaching the mesopore regime. The excellent compatibility of X-ray and e-beam lithography with existing microfabrication processes, both in research and production facilities, provides an avenue to explore the integration of MOFs in microelectronics further. This approach is the first example of direct lithography of any type of microporous crystalline network solid, and marks an important milestone in the processing of such materials.

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This study examined the direct effect of solvent on the chemical composition and structure of supramolecular assemblies formed from triphenylboroxine ((PhBO) 3 ) and piperazine (ppz) through N→B bonds. Oxygen-containing solvents with a molecular size smaller than 4.1 Å produce 1D polymeric structures (1:1 boroxine/piperazine) of compositions {(PhBO) 3 (ppz)} n •nTHF (1a• THF) and {(PhBO) 3 (ppz)} n •nAcetone (1a•Acetone), in which the boroxine B 3 O 3 rings are linked through N→B bonded piperazine molecules in a cis-conformation. In both cases, a pseudocavity is generated between two polymer chains, which is occupied by a solvent molecule interacting through bifurcated N−Hbonds with one of the chains. In contrast, oxygen-based solvents with a size larger than 6.3 Å give rise to discrete 2:1 assemblies, {(PhBO) 3 } 2 (ppz)•2Ethyl acetate (2•AcOEt) and {(PhBO) 3 } 2 (ppz)•2Pentanone (2•Pentanone), with the piperazine molecule bridging two B 3 O 3 rings and interacting with two solvent molecules via N−H•••O hydrogen bonds. In chloroform or dichloromethane 2:3 adducts, {(PhBO) 3 } 2 (ppz) 3 •4CHCl 3 (3•CHCl 3 ) and {(PhBO) 3 } 2 (ppz) 3 •2.09CH 2 Cl 2 (3•CH 2 Cl 2 ), were obtained, with N−H•••N interactions formed between the piperazine molecules directing the crystal lattice. Finally, unlike with THF and acetone, the presence of two coordination sites in dioxane gives rise to a 1D polymeric 1:1 clathrate-type assembly with trans-conformation, {(PhBO) 3 (ppz)} n •3.5nDioxane (1b•Dioxane). In accordance with the structural characterization, the thermogravimetric analysis of compounds 1−2 evidenced relatively high decomposition (solvent elimination) temperatures for the inclusion complexes derived from oxygen-containing solvents (T peak = 76.4 to 145.4 °C). On the contrary, solvates based on halogenated solvents (3•CHCl 3 and 3•CH 2 Cl 2 ) or 1,4-dioxane started to decompose already at room temperature. In view of potential applications for the storage and structural characterization of volatile or highly reactive reagents, a final inclusion experiment was carried out with racemic 1,2-epoxybutane. As expected, the resulting N→B bonded inclusion complex exhibited a 1:1 cis-polymeric structure, in which the guest molecules were bonded by bifurcated N pip −H•••O epoxy •••H−N pip hydrogen bonds.

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Reaction between the silanediol (HO)(2)Si(OtBu)(2) and gallium amides, LGaCl(NHtBu) and LGa(NHEt)(2) (L = [HC{C(Me)N(Ar)}(2)](-), Ar = 2,6-iPr(2)C(6)H(3)), respectively, resulted in the facile isolation of molecular gallosilicates LGaCl(μ-O)Si(OH)(OtBu)(2) (1) and LGa(NHEt)(μ-O)Si(OH)(OtBu)(2) (2). Compound 2 easily reacts with 1 equiv of water to form the unique gallosilicate-hydroxide LGa(OH·THF)(μ-O)Si(OH)(OtBu)(2) (3). Compounds 1-3 contain the simple Ga-O-SiO(3) framework and are the first structurally authenticated molecular gallosilicates. These compounds may be used not only as models for gallosilicate-based materials but also as further reagents because of the presence of reactive functional groups attached to both gallium and silicon atoms. Accordingly, seven molecular heterometallic compounds were obtained from the reactions between compound 3 and group 4 amides M(NMe(2))(4) (M = Ti, Zr) or M(NEt(2))(4) (M = Ti, Zr, Hf). Hence, by tuning the reactions conditions and stoichiometries, it was possible to isolate and structurally characterize the complete 1:1 and 2:1 series (4-10). Completely inorganic cores of types M-O-Ga-O-Si-O and spiro M[O-Ga-O-Si-O](2) were obtained and characterized by common spectroscopic techniques.

The Sc(III) MOF-type MFM-300(Sc) is demonstrated in this study to be stable under physiological conditions (PBS), biocompatible (to human skin cells), and an efficient drug carrier for the long-term controlled release (through human skin) of antioxidant ferulate. MFM-300(Sc) also preserves the antioxidant pharmacological effects of ferulate while enhancing the bio-preservation of dermal skin fibroblasts, during the delivery process. These discoveries pave the way toward the extended use of Sc(III)-based MOFs as drug delivery systems (DDSs).

Metal-organic framework (MOF) coatings on cells enhance viability in cytotoxic environments. Here, we show how protective multi-layered MOF bio-composite shells on a model cell system (yeast) enhance the proliferation of...