Enhanced Photocatalytic Oxygen Evolution Using Copper-Coordinated Perylene Diimide Nanorod Assemblies.

A crystalline supramolecular photocatalyst is prepared through metal-induced self-assembly of perylene diimide with imidazole groups at the imide position (PDI-Hm). Exploiting the metal-coordination ability of imidazole, a crystalline assembly of copper-coordinated PDI-Hm (CuPDI-Hm) in a nanorod shape is prepared which displays an outstanding photocatalytic oxygen evolution rate of 25,900 µmol g-1 h-1 without additional co-catalysts. The imidazole-copper coordination, along with π-π stacking of PDI frameworks, guides the arrangement of PDI-Hm molecules to form highly crystalline assemblies. The coordination of copper also modulates the size of the CuPDI-Hm supramolecular assembly by regulating the nucleation and growth processes. Furthermore, the imidazole-copper coordination constructs the electric field within the PDI-Hm assembly, hindering the recombination of photo-induced charges to enhance the photoelectric/photocatalytic activity when compared to Cu-free PDI-Hm assemblies. Small CuPDI-Hm assembly exhibits higher photocatalytic activity due to their larger surface area and reduced light scattering. Together, the Cu-imidazole coordination presents a facile way for fabricating size-controlled crystalline PDI assemblies with built-in electric field enhancing photoelectric and photocatalytic activities substantially.

Rh-coordinated histidyl bolaamphiphile assembly: a catalyst for the isomerization of cis-stilbene and cis-alkene.

In this study, we present a colloidal assembly of histidyl bolaamphiphiles whose imidazoles coordinate with rhodium ions (HisC7[Rh]) to exhibit catalytic isomerization activity for cis-stilbene and cis-alkene molecules. The histidyl bolaamphiphiles self-assemble to form a soft scaffold that functions analogously to an apoenzyme. This scaffold exposes multiple histidyl imidazoles and carboxylates on its surface, to which rhodium ions bind, generating catalytically active sites. The Rh coordination with the biochemical functional groups was verified through comprehensive vibrational spectroscopy and calorimetry. The colloidal HisC7[Rh] demonstrated a significant catalytic effect on the isomerization of cis- to trans-stilbene under mild H2 conditions, resulting in 69% yield of trans-stilbene. In contrast, when Rh(cod)2BF4 was employed as a control catalyst, only the hydrogenated products of bibenzyl were obtained. These findings underscore the crucial role of histidyl motifs in exhibiting unique catalytic isomerization activity through the coordination with Rh. The catalytic activity of HisC7[Rh] is governed by several factors, such as rhodium content, solvent composition, temperature, and H2 pressure. Moreover, HisC7[Rh] displayed moderate isomerization activity towards not only stilbene but also unsaturated fatty acid isomers, highlighting its expansive potential as an isomerization catalyst.

Harnessing Strong Metal-Support Interaction to Proliferate the Dry Reforming of Methane Performance by In Situ Reduction.

The strong bonding at the interface between the metal and the support, which can inhibit the undesirable aggregation of metal nanoparticles and carbon deposition from reforming of hydrocarbon, is well known as the classical strong metal-support interaction (SMSI). SMSI of nanocatalysts was significantly affected by heat treatment and reducing conditions during catalyst preparation.the heat treatment and reduction conditions during catalyst preparation. SMSI can be weakened by the decrement of metal-doped sites in the supporting oxide and can often deactivate catalysts by the encapsulation of active sites through these processes. To retain SMSI near the active sites and to enhance the catalytic activity of the nanocatalyst, it is essential to increase the number of surficial metal-doped sites between nanometal and the support. Herein, we propose a mild reduction process using dry methane (CH4/CO2) gas that suppresses the aggregation of nanoparticles and increases the exposed interface between the metal and support, Ni and cerium oxide. The effects of mild reduction on the chemical state of Ni-cerium oxide nanocatalysts were specifically investigated in this study. As a result, mild reduction led to form large amounts of the Ni3+ phase at the catalyst surface of which SMSI was significantly enhanced. It can be easily fabricated while the dry reforming of methane (DRM) reaction is on stream. The superior performance of the catalyst achieved a considerably high CH4 conversion rate of approximately 60% and stable operation up to 550 h at a low temperature, 600 °C.

Self-Assembling Peptidic Bolaamphiphiles for Biomimetic Applications.

Bolaamphiphile, which is a class of amphiphilic molecules, has a unique structure of two hydrophilic head groups at the ends of the hydrophobic center. Peptidic bolaamphiphiles that employ peptides or amino acids as their hydrophilic groups exhibit unique biochemical activities when they self-organize into supramolecular structures, which are not observed in a single molecule. The self-assembled peptidic bolaamphiphiles hold considerable promise for imitating proteins with biochemical activities, such as specific affinity toward heterogeneous substances, a catalytic activity similar to a metalloenzyme, physicochemical activity from harmonized amino acid segments, and the capability to encapsulate genes like a viral vector. These diverse activities give rise to large research interest in biomaterials engineering, along with the synthesis and characterization of the assembled structures. This review aims to address the recent progress in the applications of peptidic bolaamphiphile assemblies whose densely packed peptide motifs on their surface and their stacked hydrophobic centers exhibit unique protein-like activity and designer functionality, respectively.

Pavlov's Ratio of the Cervical Spine in a Korean Population: A Comparative Study by Age in Patients with Minor Trauma without Neurologic Symptoms.

BACKGROUD: There are many studies on the vertebral body-to-canal ratio, the so-called Pavlov's ratio of the cervical spine. However, there are no studies on its relation with age to clarify each bony component's contribution to the spinal canal formation and its size. The aim of this study was to investigate differences and changes in the vertebral body-to-canal ratio according to age in an asymptomatic population. METHODS: This is a cross-sectional study of 280 asymptomatic individuals. A total of 140 men and 140 women representing each decade of life from the first to the seventh were included in this study. The anteroposterior length of the vertebral body and canal from C3 to C6 was measured on sagittal radiographs to calculate the vertebral body-to-canal ratio. RESULTS: The average Pavlov's ratio was significantly larger (p < 0.001) in the first decade of life. The average Pavlov's ratio of the individuals in the first decade of life was 1.09 between C3 and C6 (1.08 at C3, 1.07 at C4, 1.11 at C5, and 1.13 at C6; range, 0.78-1.51). There was no significant difference among the other decades of life. CONCLUSIONS: We assessed the Pavlov's ratio of the cervical spine in an asymptomatic population. It is our belief that the spinal canal size is the largest in the first decade of life, and the Pavlov's ratio becomes almost fixed throughout life after maturity.

Lysosome-Instructed Self-Assembly of Amino-Acid-Functionalized Perylene Diimide for Multidrug-Resistant Cancer Cells.

Multidrug resistance (MDR) of cancer cells reduces chemotherapeutic efficacy by preventing drug accumulation in the cells through a drug efflux pump and lysosomal sequestration/exocytosis. Herein, to overcome such anticancer resistance, lysosome-targeted self-assembly of perylene diimide (PDI) derivatives is presented as a powerful strategy for effective and selective anticancer therapy. Stimulated by the lysosomal low pH, the amphiphilic PDI derivatives functionalized with amino acids (PDI-AAs) construct fibrous self-assembled structures inside the lysosomes, causing cancer cell apoptosis by lysosomal rupture. In contrast, negligible apoptosis was observed from normal cells by PDI-AA. The agglomerated fibrous assemblies were not removed by lysosomal exocytosis, thereby displaying a 10.7-fold higher anticancer efficacy on MDR cancer cells compared to a doxorubicin chemotherapeutic agent. The MDR-circumventing capability, along with high selectivity toward cancer cells, supports PDI-AAs as potential candidates for the treatment of MDR cancer cells by lysosome-targeted self-assembly.

A near-infrared light-responsive upconversion nanoparticle micromotor propelled by oxygen bubbles.

Light-responsive micromotors using photosensitizer-decorated upconversion nanoparticles (UCNPs) are described. The UCNP motors converting near-infrared light into visible emission were propelled by oxygen bubble propulsion. The micromotor can be easily controlled by adjusting the light intensity, solution pH, and concentration of H2O2 and UCNPs.

Aggregation-driven fluorescence quenching of imidazole-functionalized perylene diimide for urea sensing.

Stimuli-responsive self-assembly of functional amphiphilic molecules by specific chemical stimulants is a promising strategy for sensor application. Herein, we demonstrate a fast optical detection of urea in human urine by exploiting bolaform perylene diimide functionalized with imidazoles (PDI-Hm), whose aggregation is induced by urea hydrolysis. The hydroxides produced from the enzymatic urea hydrolysis deprotonate the imidazoles to reduce electrostatic repulsion between PDI-Hm molecules in a HCl-methanol mixture, thereby leading to aggregation and consequent fluorescence quenching. The molecular interaction of PDI-Hm was further scrutinized to understand the aggregation behavior driven by the screening of electrical repulsion. As an optical sensing probe, PDI-Hm displays a prompt response (<1 min) to hydroxide and detection limit of 0.4 mM for urea. PDI-Hm incorporating urease offers considerable selectivity toward urea among various components in human urine. The urea sensing accuracy of this PDI-Hm fluorescence chemosensor is comparable to that of a clinical method, showing 93.4% consistency. Furthermore, the PDI-Hm was fabricated into a gel film allowed for the fast screening of excessive urea in urine.

A hydrazide organogelator for fluoride sensing with hyperchromicity and gel-to-sol transition.

Sensing of fluoride in a solvent is highly required in healthcare and environmental rehabilitation. Among the various sensing methods, optical sensing has attracted significant research interest because it can conveniently recognize fluoride. Herein, a low molecular weight organogelator, N'1,N'6-bis(3-(1-pyrrolyl)propanoyl) hexanedihydrazide (DPH), containing a central butyl chain conjugated to two pyrrole rings through hydrazide groups, was used for optical sensing of fluoride in the forms of both solution and organogel. Association of fluoride with the -NH moiety of the hydrazide group endowed the DPH solution in dimethylformamide with a hyperchromicity under 350 nm. Exploiting the UV absorptivity, the DPH solution was examined as a chemosensor, displaying good selectivity toward fluoride among various anions and moderate sensitivity with a detection limit of 0.49 µM. The practical use of the DPH solution was demonstrated for fluoride sensing in toothpaste. Binding of fluoride also changed the molecular interactions of the DPH organogel, resulting in a phase transition from gel to sol. This gel-to-sol transition enabled the sensing of fluoride by the naked eye.

Boston Ivy Disk-Inspired Pressure-Mediated Adhesive Film Patches.

Boston ivy (Parthenocissus tricuspidata) climbs brick walls using its tendril disks, which excrete a sticky substance to perform binding and attachment. While the cellular structures and adhesive substances involved have been identified for decades, their practical applicability as an adhesive has not yet been demonstrated. A Boston ivy disk-inspired adhesive film patch system is reported in which structural and compositional features of the Boston ivy disk are mimicked with a form of thin adhesive film patches. In analogy to the sticky disk of a mature ivy in which porous microchannels are occupied by catechol-containing microgranules on the bound site, 3,4-dihydroxylphenylalanine bolaamphiphile nanoparticle (DOPA-C7 NP)-coated alginate microgels are two-dimensionally positioned into the cylindrical holes that are periodically micropatterned on the flexible stencil film. Finally, it is demonstrated that the pressurization of the patch breaks the microgels filled in the holes, releasing the polysaccharides and leading to crosslinking with DOPA-C7 NPs via ligandation with combined Ca2+ and Fe3+ ions, thus enabling development of a pressure-mediated adhesion technology.

Impedimetric analysis on the mass transfer properties of intact and competent E. coli cells.

Competent Escherichia coli cells are commonly used in bacterial transformation owing to its high permeability for bioorganic macromolecules like plasmid DNA. However, the mass transfer property of competent E. coli cell has not fully investigated. In the present study, mass transfer coefficients of competent and intact E. coli cells in deionized water were evaluated by impedimetric analysis of the release of cytoplasmic compounds. Because competent cells have a higher permeability after chemical treatment, the lumped mass transfer coefficient of a competent cell was approximately 6.5 times larger than that of an intact cell at room temperature. Release of cytoplasmic components was accelerated at an elevated temperature of 42 °C, which is the heat shock temperature used during bacterial transformation. At this elevated temperature, assessed lumped mass transfer coefficients of intact and competent E. coli cells were 9.28 × 10-4 min-1 and 97.10 × 10-4 min-1, respectively. Significant increase in the mass transfer coefficient of the competent cell is caused by cytolysis of cells. The double layer capacitances were also assessed from the electrochemical spectra confirming the enhanced ion release from E. coli cells and rupture of the competent cell under prolonged exposure at the elevated temperature. Impedimetric detection of the ion release with analyses using an equivalent circuit model provides a method to evaluate mass transfer properties of biomolecules.

Cancer-Cell Imaging Using Copper-Doped Zeolite Imidazole Framework-8 Nanocrystals Exhibiting Oxidative Catalytic Activity.

Copper-doped zeolite imidazole framework-8 (Cu/ZIF-8) was prepared and its peroxidase-like oxidative catalytic activity was examined with a demonstration of its applicability for cancer-cell imaging. Through simple solution chemistry at room temperature, Cu/ZIF-8 nanocrystals were produced that catalytically oxidized an organic substrate of o-phenylenediamine in the presence of H2 O2 . In a similar manner to peroxidase, the Cu/ZIF-8 nanocrystals oxidized the substrate through a ping-pong mechanism with an activation energy of 59.2 kJ mol-1 . The doped Cu atoms functioned as active sites in which the active Cu intermediates were expected to be generated during the catalysis, whereas the undoped ZIF-8 did not show any oxidative activity. Cu/ZIF-8 nanocrystals exhibited low cell toxicity and displayed catalytic activity through interaction with H2 O2 among various reactive oxygen species in a cancer cell. This oxidative activity in vitro allowed cancer-cell imaging by exploiting the photoluminescence emitted from the oxidized product of o-phenylenediamine, which was insignificant in the absence of the Cu/ZIF-8 nanocrystals. The results of this study suggest that the Cu/ZIF-8 nanocrystal is a promising catalyst for the analysis of the microbiological systems.

Iridium-Coordinated Histidyl Bolaamphiphile Self-Assemblies as Heterogeneous Catalysts for Water Oxidation.

Catalysts that can promote oxygen evolution from water are necessary for green energy production. In this study, colloidal heterogeneous catalysts for oxygen evolution were prepared by coordination of Ir species to self-assemblies of histidyl bolaamphiphiles. When dissolved in water, the histidyl bolaamphiphiles self-assembled to form particulate structures with the exposure of densely packed histidine imidazoles on their surface. Subsequent coordination of the Ir species to the bolaamphiphile assembly gave rise to catalytic activity toward the oxygen evolution reaction. The oxygen evolution was examined by using the catalytic assemblies in the presence of a sacrificial oxidant, cerium ammonium nitrate. The Ir-coordinated assemblies showed a turnover frequency of 13 min-1 , which was comparable to those previously reported for molecular water oxidation catalysts. The catalytic activity increased with increasing histidine imidazole/Ir molar ratio, which suggested that multiple coordination of Ir to imidazoles facilitated the formation of active Ir intermediates. This study demonstrates the feasibility of constructing catalytically active interfaces from colloidal bolaamphiphile assemblies with biochemical ligands.

Catalytic Water Oxidation by Iridium-Modified Carbonic Anhydrase.

Carbonic anhydrase (CA) is a ubiquitous metalloenzyme with a Zn cofactor coordinated to trigonal histidine imidazole moieties in a tetrahedral geometry. Removal of the Zn cofactor in CA and subsequent binding of Ir afforded CA[Ir]. Under mild and neutral conditions (30 °C, pH 7), CA[Ir] exhibited water-oxidizing activity with a turnover frequency (TOF) of 39.8 min-1 , which is comparable to those of other Ir-based molecular catalysts. Coordination of Ir to the apoprotein of CA is thermodynamically preferred and is associated with an exothermic energy change (ΔH) of -10.8 kcal mol-1 , which implies that the CA apoprotein is stabilized by Ir binding. The catalytic oxygen-evolving activity of CA[Ir] is displayed only if Ir is bound to CA, which functions as an effective biological scaffold that activates the Ir center for catalysis. The results of this study indicate that the histidine imidazoles at the CA active site could be exploited as beneficial biological ligands to provide unforeseen biochemical activity by coordination to a variety of transition-metal ions.

Photoinduced Intermolecular Electron Transfer Mediated by the Colloidal Tyrosyl Bolaamphiphile Assembly.

The self-assembly of tyrosyl bolaamphiphiles is exploited to create a colloidal protein-like host matrix, upon which sacrificial electron-donor molecules associate to create a photosystem II (PSII) mimetic electron-relay system. This system harnesses the tyrosine phenol groups abundant on the surface of the assemblies to mediate photoinduced intermolecular electron transfer. Compared with the l-tyrosine molecules, the tyrosyl bolaamphiphile assembly facilitates electron transfer from the sacrificial electron donor to the oxidized photosensitizer. The enhanced electron relay is likely to be driven by the host function of the assembly associated with the sacrificial electron donor and by the suppression of the oxidative cross-linking of phenoxyl radicals. The tyrosyl bolaamphiphile assembly is advantageous in the construction of a PSII mimetic system with a protein-like nature and displaying biochemical functions.

Enhanced Cell Adhesion on a Nano-Embossed, Sticky Surface Prepared by the Printing of a DOPA-Bolaamphiphile Assembly Ink.

Inspired by adhesive mussel proteins, nanospherical self-assemblies were prepared from bolaamphiphiles containing 3,4-dihydroxyphenylalanine (DOPA) moieties, and a suspension of the bolaamphiphile assemblies was used for the preparation of a patterned surface that enhanced cell adhesion and viability. The abundant surface-exposed catechol groups on the robust bolaamphiphile self-assemblies were responsible for their outstanding adhesivity to various surfaces and showed purely elastic mechanical behaviour in response to tensile stress. Compared to other polydopamine coatings, the spherical DOPA-bolaamphiphile assemblies were coated uniformly and densely on the surface, yielding a nano-embossed surface. Cell culture tests on the surface modified by DOPA-bolaamphiphiles also showed enhanced cellular adhesivity and increased viability compared to surfaces decorated with other catecholic compounds. Furthermore, the guided growth of a cell line was demonstrated on the patterned surface, which was prepared by inkjet printing using a suspension of the self-assembled particles as an ink. The self-assembly of DOPA-bolaamphiphiles shows that they are a promising adhesive, biocompatible material with the potential to modify various substances.

Interior-filled self-assemblies of tyrosyl bolaamphiphiles regulated by hydrogen bonds.

Bolaamphiphilic molecules with tyrosyl end groups formed interior-filled spherical self-assemblies, which are distinct from the vesicular or tubular structures of other similar peptidic bolaamphiphile assemblies reported in the literature. In this study, the self-assembly mechanism of these tyrosyl bolaamphiphiles was investigated taking into consideration the solvent effects on the molecular interaction forces using molecular modeling. The dissipative particle dynamics simulation of an aqueous tyrosyl bolaamphiphile solution suggested that the interior-filled assemblies were produced by a solvent-regulated assembly of small aggregates of bolaamphiphiles. These small aggregates were generated by hydrophobic interactions at an early stage, and then further assembled to form large spherical assemblies through intermolecular forces, including hydrogen bonds between the intermediate aggregates. Additional experiments and density functional theory calculations based on solvent variations proved that smaller assembled structures could be obtained by disrupting the hydrogen bonds between the intermediates. The assembly mechanism of these peptidic bolaamphiphiles afforded a facile way to create condensed supramolecular structures with controlled sizes.

Nanodiamond-Gold Nanocomposites with the Peroxidase-Like Oxidative Catalytic Activity.

Novel nanodiamond-gold nanocomposites (NDAus) are prepared, and their oxidative catalytic activity is examined. Gold nanoparticles are deposited on carboxylated nanodiamonds (NDs) by in situ chemical reduction of gold precursor ions to produce NDAus, which exhibit catalytic activity for the oxidation of o-phenylenediamine in the presence of hydrogen peroxide similarly to a peroxidase. This remarkable catalytic activity is exhibited only by the gold nanoparticle-decorated NDs and is not observed for either Au nanoparticles or NDs separately. Kinetic oxidative catalysis studies show that NDAus exhibit a ping-pong mechanism with an activation energy of 93.3 kJ mol-1, with the oxidation reaction rate being proportional to the substrate concentration. NDAus retain considerable activity even after several instances of reuse and are compatible with a natural enzyme, allowing the detection of xanthine using cascade catalysis. Association with gold nanoparticles makes NDs a good carbonic catalyst due to charge transfer at the metal-carbon interface and facilitated substrate adsorption. The results of this study suggest that diverse carbonic catalysts can be obtained by interfacial incorporation of various metal/inorganic substances.

Non-invasive stem cell tracking in hindlimb ischemia animal model using bio-orthogonal copper-free click chemistry.

Labeling of stem cells aims to distinguish transplanted cells from host cells, understand in vivo fate of transplanted cells, particularly important in stem cell therapy. Adipose-derived mesenchymal stem cells (ASCs) are considered as an emerging therapeutic option for tissue regeneration, but much remains to be understood regarding the in vivo evidence. In this study, a simple and efficient cell labeling method for labeling and tracking of stem cells was developed based on bio-orthogonal copper-free click chemistry, and it was applied in a mouse hindlimb ischemia model. The human ASCs were treated with tetra-acetylated N-azidoacetyl-d-mannosamine (Ac4ManNAz) to generate glycoprotein with unnatural azide groups on the cell surface, and the generated azide groups were fluorescently labeled by specific binding of dibenzylcyclooctyne-conjugated Cy5 (DBCO-Cy5). The safe and long-term labeling of the hASCs by this method was first investigated in vitro. Then the DBCO-Cy5-hASCs were transplanted into the hindlimb ischemia mice model, and we could monitor and track in vivo fate of the cells using optical imaging system. We could clearly observe the migration potent of the hASCs toward the ischemic lesion. This approach to design and tailor new method for labeling of stem cells may be useful to provide better understanding on the therapeutic effects of transplanted stem cells into the target diseases.

An enzyme-coupled artificial photosynthesis system prepared from antenna protein-mimetic tyrosyl bolaamphiphile self-assembly.

An artificial photosynthesis system coupled with an enzyme was constructed using the nanospherical self-assembly of tyrosyl bolaamphiphiles, which worked as a host matrix exhibiting an antenna effect that allowed enhanced energy transfer to the ZnDPEG photosensitizer. The excited electrons from the photosensitizer were transferred to NAD+ to produce NADH, which subsequently initiated the conversion of an aldehyde to ethanol by alcohol dehydrogenase. Production of NADH and ethanol was enhanced by increasing the concentration of tyrosyl bolaamphiphiles. Spectroscopic investigations proved that the photosensitizer closely associated with the surface of the bolaamphiphile assembly through hydrogen bonds that allowed energy transfer between the host matrix and the photosensitizer. This study demonstrates that the self-assembly of bolaamphiphiles could be applicable to the construction of biomimetic energy systems exploiting biochemical activity.