Evaluation of the osteoconductivity and the degradation of novel hydroxyapatite/polyurethane combined with mesoporous silica microspheres in a rabbit osteomyelitis model.

Bone defects caused by osteomyelitis can lead to severe disability. Surgeons still face significant challenges in treating bone defects. Nano-hydroxyapatite (n-HA) plays an important role in bone tissue engineering due to its excellent biocompatibility and osteoconductivity. Levofloxacin (Levo) was encapsulated in mesoporous silica nanoparticles (MSNs) via electrostatic attraction to serve as a drug delivery system. MSNs were incorporated with n-HA and polyurethane (PU). The degradation and osteoconductivity properties of these novel composite scaffolds and their effectiveness in treating chronic osteomyelitis in a rabbit model were assessed. Gross pathology, radiographic imaging, micro-computed tomography, Van Gieson staining, and hematoxylin and eosin staining were conducted at 6 and 12 weeks. The group of composite scaffolds combining n-HA/PU with MSNs containing 5 mg Levo (n-HA/PU + Nano +5 mg Levo) composite scaffolds showed superior antibacterial properties compared to the other groups. At 12 weeks, the n-HA/PU + Nano +5 mg Levo composite scaffolds group exhibited significantly greater volume of new trabecular bone formation compared to the other three groups. The surface of the novel composite scaffolds exhibited degradation after 6 weeks implantation. The internal structure of the scaffolds collapsed noticeably after 12 weeks of implantation. The rate of material degradation corresponded to the rate of new bone ingrowth. This novel composite scaffold, which is biodegradable and osteoconductive, has potential as a drug delivery system for treating chronic osteomyelitis accompanied by bone defects.

A copper-seamed coordination nanocapsule as a semiconductor photocatalyst for molecular oxygen activation.

Here we report that a Cu2+-seamed coordination nanocapsule can serve as an efficient semiconductor photocatalyst for molecular oxygen activation. This capsule was constructed through a redox reaction facilitated self-assembly of cuprous bromide and C-pentyl-pyrogallol[4]arene. Photophysical and electrochemical studies revealed its strong visible-light absorption and photocurrent polarity switching effect. This novel molecular solid material is capable of activating molecular oxygen into reactive oxygen species under simulated sunlight irradiation. The oxygen activation process has been exploited for catalyzing aerobic oxidation reactions. The present work provides new insights into designing nonporous discrete metal-organic supramolecular assemblies for solar-driven molecular oxygen activation.

Hijacking the self-replicating machine of bacteriophage for PCR-based cascade signal amplification in detecting SARS-CoV-2 viral marker protein in serum.

In this work, the nucleic acid detection of SARS-Cov-2 is extended to protein markers of the virus, utilizing bacteriophage. Specifically, the phage display technique enables the main protease of SARS-Cov-2 to control the self-replication of m13 phage, so that the presence of the viral protease can be amplified by phage replication as the first round of signal amplification. Then, the genome of replicated phage can be detected using polymer chain reaction (PCR), as the second round of signal amplification. Based on these two types of well-established biotechnology, the proposed method shows satisfactory sensitivity and robustness in the direct serum detection of the viral protease. These results may point to clinical application in the near future.

A recyclable self-supported nanoporous PdCu heterogeneous catalyst for aqueous Suzuki-Miyaura cross-coupling.

Nanoporous PdCu (NP-PdCu) was prepared by the dealloying strategy from a PdCuAl ternary alloy precursor and characterized systematically using SEM, TEM, XRD, and XPS. NP-PdCu was demonstrated to be a competent self-supported heterogenous catalyst for Suzuki-Miyaura cross-coupling, affording a series of synthetically valuable biaryl compounds in good to excellent yields. This catalyst could be easily separated from the product via centrifugation and reused several times without obvious loss of catalytic performance.

Minimalist Design for a Hand-Held SARS-Cov-2 Sensor: Peptide-Induced Covalent Assembly of Hydrogel Enabling Facile Fiber-Optic Detection of a Virus Marker Protein.

The rampaging COVID-19 needs bioassaying methods of low cost and high robustness for those living in the poorly developed regions. Here, we propose such a method that does not need expensive and complicated equipment. Only a set of hand-held small devices is sufficient. A section along an optic fiber cable is stripped, so that laser light travelling through it will leak outside, while biosensing process taken place on this stripped section can form a new cladding layer of hydrogel, restoring the laser output of the fiber. A short peptide probe immobilized on the stripped section of the fiber can covalently capture a biomarker protein of SARS-Cov-2 from the serum sample. Through the cross-linking of the target protein with the interfering proteins in the serum sample, a hydrogel is covalently immobilized around the stripped section, highly resistant to detergent rinsing that is indispensable for removing nonspecific interference from the clinical sample. Using this "covalent biosensing" strategy, only one peptide probe is sufficient to simultaneously achieve ultrahigh affinity toward the biomarker protein of SARS-Cov-2 and effective signal amplification.

Controlled hierarchical self-assembly of networked coordination nanocapsules via the use of molecular chaperones.

Supramolecular chaperones play an important role in directing the assembly of multiple protein subunits and redox-active metal ions into precise, complex and functional quaternary structures. Here we report that hydroxyl tailed C-alkylpyrogallol[4]arene ligands and redox-active MnII ions, with the assistance of proline chaperone molecules, can assemble into two-dimensional (2D) and/or three-dimensional (3D) networked nanocapsules. Dimensionality is controlled by coordination between the exterior of nanocapsule subunits, and endohedral functionalization within the 2D system is achieved via chaperone guest encapsulation. The tailoring of surface properties of nanocapsules via coordination chemistry is also shown as an effective method for the fine-tuning magnetic properties, and electrochemical and spectroscopic studies support that the nanocapsule is an effective homogeneous water-oxidation electrocatalyst, operating at pH 6.07 with an exceptionally low overpotential of 368 mV.

A Highly Active and Robust Copper-Based Electrocatalyst toward Hydrogen Evolution Reaction with Low Overpotential in Neutral Solution.

Although significant progress has been made recently, copper-based materials have long been considered to be ineffective catalysts toward the hydrogen evolution reaction (HER), in most cases, requiring high overpotentials more than 300 mV. We report here that a Cu(0)-based nanoparticle film electrodeposited in situ from a Cu(II) oxime complex can act as a highly active and robust HER electrocatalyst in neutral phosphate buffer solution. The as-prepared nanoparticle film is of poor crystallization, which incorporates significant amounts of oxime ligand residues and buffer anions PO43-. The proposed mechanism suggests that the Cu(0)-based nanoparticle film is activated with incorporated or adsorbed PO43- anions and the PO43- anions-anchored sites might serve as the actual catalytic active sites with efficient proton transport mediators. Catalysis occurs with a low onset overpotential (η) of 65 mV, and a current density of 1 mA/cm2 can be achieved with η = 120 mV. The nanoparticle film shows an excellent catalytic durability with slightly rising current density during electrolysis, presumably due to further incorporation or adsorption of PO43- anions in the process. This electrocatalyst not only forms in situ from earth-abundant materials but also operates in neutral water with low overpotential and high stability.

Cs(I) Cation Enhanced Cu(II) Catalysis of Water Oxidation.

We report here a new catalytic water oxidation system based on Cu(II) ions and a remarkable countercation effect on the catalysis. In a concentrated fluoride solution at neutral to weakly basic pHs, simple Cu(II) salts are highly active and robust in catalyzing water oxidation homogeneously. F(-) in solution acts as a proton acceptor and an oxidatively robust ligand. F(-) coordination prevents precipitation of Cu(II) as CuF2/Cu(OH)2 and lowers potentials for accessing high-oxidation-state Cu by delocalizing the oxidative charge over F(-) ligands. Significantly, the catalytic current is greatly enhanced in a solution of CsF compared to those of KF and NaF. Although countercations are not directly involved in the catalytic redox cycle, UV-vis and (19)F nuclear magnetic resonance measurements reveal that coordination of F(-) to Cu(II) is dependent on countercations by Coulombic interaction. A less intense interaction between F(-) and well-solvated Cs(+) as compared with Na(+) and K(+) leads to a more intense coordination of F(-) to Cu(II), which accounts for the improved catalytic performance.

A half-reaction alternative to water oxidation: chloride oxidation to chlorine catalyzed by silver ion.

Chloride oxidation to chlorine is a potential alternative to water oxidation to oxygen as a solar fuels half-reaction. Ag(I) is potentially an oxidative catalyst but is inhibited by the high potentials for accessing the Ag(II/I) and Ag(III/II) couples. We report here that the complex ions AgCl2(-) and AgCl3(2-) form in concentrated Cl(-) solutions, avoiding AgCl precipitation and providing access to the higher oxidation states by delocalizing the oxidative charge over the Cl(-) ligands. Catalysis is homogeneous and occurs at high rates and low overpotentials (10 mV at the onset) with µM Ag(I). Catalysis is enhanced in D2O as solvent, with a significant H2O/D2O inverse kinetic isotope effect of 0.25. The results of computational studies suggest that Cl(-) oxidation occurs by 1e(-) oxidation of AgCl3(2-) to AgCl3(-) at a decreased potential, followed by Cl(-) coordination, presumably to form AgCl4(2-) as an intermediate. Adding a second Cl(-) results in "redox potential leveling", with further oxidation to {AgCl2(Cl2)}(-) followed by Cl2 release.

Copper as a robust and transparent electrocatalyst for water oxidation.

Copper metal is in theory a viable oxidative electrocatalyst based on surface oxidation to Cu(III) and/or Cu(IV) , but its use in water oxidation has been impeded by anodic corrosion. The in situ formation of an efficient interfacial oxygen-evolving Cu catalyst from Cu(II) in concentrated carbonate solutions is presented. The catalyst necessitates use of dissolved Cu(II) and accesses the higher oxidation states prior to decompostion to form an active surface film, which is limited by solution conditions. This observation and restriction led to the exploration of ways to use surface-protected Cu metal as a robust electrocatalyst for water oxidation. Formation of a compact film of CuO on Cu surface prevents anodic corrosion and results in sustained catalytic water oxidation. The Cu/CuO surface stabilization was also applied to Cu nanowire films, which are transparent and flexible electrocatalysts for water oxidation and are an attractive alternative to ITO-supported catalysts for photoelectrochemical applications.