Fabrication of polycrystalline phosphorus-doped diamond electrodes from red phosphorus.

Polycrystalline phosphorus-doped diamond was fabricated by the quartz-tube-type microwave plasma-assisted chemical vapor deposition method. Significantly, red phosphorus was used as a source of phosphorous, instead of PH3. Phosphorus-doped diamond electrodes with hydrogen-terminated and oxygen-terminated surfaces were investigated for the redox reactions of K3[Fe(CN)6] and [Ru(NH3)6]Cl3. The carrier concentration was estimated as 2.1-5.3 × 1018 cm-3 from electrochemical impedance measurements. Polycrystalline phosphorus-doped diamond shows great promise as chemical electrode materials.

In Situ and Ex Situ Studies of Ring-Like Assembly of Silica Nanoparticles in the Presence of Poly(propylene oxide)-Poly(ethylene oxide) Block Copolymers.

Block copolymer-mediated self-assembly of colloidal nanoparticles has attracted great attention for fabricating various nanoparticle arrays. We have previously shown that silica nanoparticles (SNPs) assemble into ring-like nanostructures in the presence of temperature-responsive block copolymers poly[(2-ethoxyethyl vinyl ether)-block-(2-methoxyethyl vinyl ether)] (PEOVE-PMOVE) in an aqueous phase. The ring-like nanostructures formed within an aggregate of PEOVE-PMOVE when the temperature was increased to 45 °C, at which the polymer is amphiphilic. Herein, we report that SNPs assemble into ring-like nanostructures even with a different temperature-responsive, amphiphilic block copolymer poly(propylene oxide)-block-poly(ethylene oxide) (PPO-PEO) at 45 °C. Field-emission scanning electron microscopy for SNP assemblies that were spin-coated on a substrate indicated that SNP first assembled into chain-like nanostructures and then bent into closed loops over several days. In contrast, in situ small-angle X-ray diffraction measurements revealed the formation of SNP nanorings within 75 s at 45 °C in the liquid phase. These results indicated that ring-like assembly of SNPs occurs quickly in the liquid phase, but the slow formation of Si-O-Si bonds between SNPs leads to their structure being destroyed by spin-coating. Intriguingly, SNPs with a diameter of 15 nm form a well-defined nanoring structure, with five SNPs located at the vertex points of a regular pentagon. Additionally, small-angle neutron scattering, where the contrast of the solvent (a mixture of H2O and D2O) matches that of SNPs, clarified that SNPs are contained within the spherical micelle formed from PPO-PEO. This work offers a facile and versatile approach to preparing ring-like arrays from inorganic colloidal nanoparticles, leading to applications including sensing, catalysis, and nanoelectronics.

Transformation behaviour of salts composed of calcium ions and phosphate esters with different linear alkyl chain structures in a simulated body fluid modified with alkaline phosphatase.

Ceramic biomaterials have been used for the treatment of bone defects and have stimulated intense research on such materials. We have previously reported that a salt composed of calcium ions and a phosphate ester (SCPE) transformed into hydroxyapatite (HAp) in a simulated body fluid (SBF) modified with alkaline phosphatase (ALP), and proposed SCPEs as a new category of ceramic biomaterials, namely bioresponsive ceramics. However, the factors that affect the transformation of SCPEs to HAp in the SBF remained unclear. Therefore, in this study, we investigated the behaviour of calcium salts of methyl phosphate (CaMeP), ethyl phosphate (CaEtP), butyl phosphate (CaBuP), and dodecyl phosphate (CaDoP) in SBF with and without ALP modification. For the standard SBF, an X-ray diffraction (XRD) analysis indicated that these SCPEs did not readily transform into calcium phosphate. However, CaMeP, CaEtP, and CaBuP were transformed into HAp and octacalcium phosphate in the SBF modified with ALP; therefore, these SCPEs can be categorised as bioresponsive ceramics. Although CaDoP did not exhibit a sufficient response to ALP to be detected by XRD, it is likely to be a bioresponsive ceramic based on the results of morphological observations. The transformation rate for the SCPEs decreased with increasing size of the linear alkyl group of the phosphate esters. The rate-determining steps for the transformation reaction of the SCPEs were changed from the dissolution of the SCPEs to the hydrolysis of the phosphate esters with increasing size of the phosphate ester alkyl groups. These findings contribute to designing novel bioresponsive ceramic biomaterials.

Spatiotemporal ATP Dynamics during AKI Predict Renal Prognosis.

BACKGROUND: Depletion of ATP in renal tubular cells plays the central role in the pathogenesis of kidney diseases. Nevertheless, inability to visualize spatiotemporal in vivo ATP distribution and dynamics has hindered further analysis. METHODS: A novel mouse line systemically expressing an ATP biosensor (an ATP synthase subunit and two fluorophores) revealed spatiotemporal ATP dynamics at single-cell resolution during warm and cold ischemic reperfusion (IR) with two-photon microscopy. This experimental system enabled quantification of fibrosis 2 weeks after IR and assessment of the relationship between the ATP recovery in acute phase and fibrosis in chronic phase. RESULTS: Upon ischemia induction, the ATP levels of proximal tubule (PT) cells decreased to the nadir within a few minutes, whereas those of distal tubule (DT) cells decreased gradually up to 1 hour. Upon reperfusion, the recovery rate of ATP in PTs was slower with longer ischemia. In stark contrast, ATP in DTs was quickly rebounded irrespective of ischemia duration. Morphologic changes of mitochondria in the acute phase support the observation of different ATP dynamics in the two segments. Furthermore, slow and incomplete ATP recovery of PTs in the acute phase inversely correlated with fibrosis in the chronic phase. Ischemia under conditions of hypothermia resulted in more rapid and complete ATP recovery with less fibrosis, providing a proof of concept for use of hypothermia to protect kidney tissues. CONCLUSIONS: Visualizing spatiotemporal ATP dynamics during IR injury revealed higher sensitivity of PT cells to ischemia compared with DT cells in terms of energy metabolism. The ATP dynamics of PTs in AKI might provide prognostic information.

Organic modification of layered zirconium phosphate/phosphonate for controlled release of therapeutic inorganic ions.

The present study aims to develop a layered zirconium phosphate/phosphonate (LZP) powder to control the release of therapeutic inorganic ions. Organically modified LZPs were successfully prepared with various contents of phenyl groups via a reflux method in an aqueous solution containing phosphoric and phenylphosphonic acids. Powder X-ray diffraction analysis and Fourier transform infrared spectroscopy revealed that the crystal structure of the synthesized LZP samples was identical to that of α-zirconium phosphate, even after modification. The amount of incorporated organic molecules increased with increasing molar fractions of phenylphosphonic acid in the starting composition, as determined from the thermal analysis. Cobalt ion (Co2+), a type of therapeutic inorganic ion, was incorporated into the organically modified LZP through treatment with an acetonitrile solution containing tetrabutylammonium ions, followed by treatment with an acetonitrile solution containing CoCl2. The amount of incorporated Co2+ depended on the concentration of the phenyl groups. Furthermore, the highest amount of Co2+ was incorporated in the sample (ZP-Ph-0.5) prepared with equimolar phosphoric/phenylphosphonic acid. The ZP-Ph-0.5 sample additionally showed the ability to incorporate copper or iron ions (Cu2+ or Fe3+). The incorporated ion, either Co2+ or Cu2+, was continuously released from the ZP-Ph-0.5 sample in a saline solution over a period of three weeks, whereas the release of Fe3+ was negligible. The quantity of Co2+ released was higher than that of Cu2+. The controlled release of Co2+ from the ZP-Ph-0.5 sample was also observed in a simulated body fluid that mimicked the ionic concentration of human blood plasma. These results confirm that a specific degree of phenyl modification makes LZP a candidate host material for releasing therapeutic inorganic ions.

Emerging Atomic Energy Levels in Zero-Dimensional Silicon Quantum Dots.

Driven by the emergence of colloidal semiconductor quantum dots (QDs) of tunable emission wavelengths, characteristic of exciton absorption peaks, outstanding photostability and solution processability in device fabrication have become a key tool in the development of nanomedicine and optoelectronics. Diamond cubic crystalline silicon (Si) QDs, with a diameter larger than 2 nm, terminated with hydrogen atoms are known to exhibit bulk-inherited spin and valley properties. Herein, we demonstrate a newly discovered size region of Si QDs, in which a fast radiative recombination on the order of hundreds of picoseconds is responsible for photoluminescence (PL). Despite retaining a crystallographic structure like the bulk, controlling their diameters in the 1.1-1.7 nm range realizes the strong PL with continuous spectral tunability in the 530-580 nm window, the narrow spectral line widths without emission tails, and the fast relaxation of photogenerated carriers. In contrast, QDs with diameters greater than 1.8 nm display the decay times on the microsecond order as well as the previous Si QDs. In addition to the five-orders-of-magnitude variation in the PL decay time, a systematic study on the temperature dependence of PL properties suggests that the energy structure of the smaller QDs does not retain an indirect band gap character. It is discussed that a 1.7 nm diameter is critical to undergo changes in energy structure from bulky to molecular configurations.

Thixotropic Hydrogels Composed of Self-Assembled Nanofibers of Double-Hydrophobic Elastin-Like Block Polypeptides.

Physically crosslinked hydrogels with thixotropic properties attract considerable attention in the biomedical research field because their self-healing nature is useful in cell encapsulation, as injectable gels, and as bioinks for three-dimensional (3D) bioprinting. Here, we report the formation of thixotropic hydrogels containing nanofibers of double-hydrophobic elastin-like polypeptides (ELPs). The hydrogels are obtained with the double-hydrophobic ELPs at 0.5 wt%, the concentration of which is an order of magnitude lower than those for previously reported ELP hydrogels. Although the kinetics of hydrogel formation is slower for the double-hydrophobic ELP with a cell-binding sequence, the storage moduli G' of mature hydrogels are similar regardless of the presence of a cell-binding sequence. Reversible gel-sol transitions are demonstrated in step-strain rheological measurements. The degree of recovery of the storage modulus G' after the removal of high shear stress is improved by chemical crosslinking of nanofibers when intermolecular crosslinking is successful. This work would provide deeper insight into the structure-property relationships of the self-assembling polypeptides and a better design strategy for hydrogels with desired viscoelastic properties.

Myofibroblasts acquire retinoic acid-producing ability during fibroblast-to-myofibroblast transition following kidney injury.

Tubular injury and interstitial fibrosis are the hallmarks of chronic kidney disease. While recent studies have verified that proximal tubular injury triggers interstitial fibrosis, the impact of fibrosis on tubular injury and regeneration remains poorly understood. We generated a novel mouse model expressing diphtheria toxin receptor on renal fibroblasts to allow for the selective disruption of renal fibroblast function. Administration of diphtheria toxin induced upregulation of the tubular injury marker Ngal and caused tubular proliferation in healthy kidneys, whereas administration of diphtheria toxin attenuated tubular regeneration in fibrotic kidneys. Microarray analysis revealed down-regulation of the retinol biosynthesis pathway in diphtheria toxin-treated kidneys. Healthy proximal tubules expressed retinaldehyde dehydrogenase 2 (RALDH2), a rate-limiting enzyme in retinoic acid biosynthesis. After injury, proximal tubules lost RALDH2 expression, whereas renal fibroblasts acquired strong expression of RALDH2 during the transition to myofibroblasts in several models of kidney injury. The retinoic acid receptor (RAR) RARγ was expressed in proximal tubules both with and without injury, and αB-crystallin, the product of an RAR target gene, was strongly expressed in proximal tubules after injury. Furthermore, BMS493, an inverse agonist of RARs, significantly attenuated tubular proliferation in vitro. In human biopsy tissue from patients with IgA nephropathy, detection of RALDH2 in the interstitium correlated with older age and lower kidney function. These results suggest a role of retinoic acid signaling and cross-talk between fibroblasts and tubular epithelial cells during tubular injury and regeneration, and may suggest a beneficial effect of fibrosis in the early response to injury.

Rheology of Dispersions of High-Aspect-Ratio Nanofibers Assembled from Elastin-Like Double-Hydrophobic Polypeptides.

Elastin-like polypeptides (ELPs) are promising candidates for fabricating tissue-engineering scaffolds that mimic the extracellular environment of elastic tissues. We have developed a "double-hydrophobic" block ELP, GPG, inspired by non-uniform distribution of two different hydrophobic domains in natural elastin. GPG has a block sequence of (VGGVG)5-(VPGXG)25-(VGGVG)5 that self-assembles to form nanofibers in water. Functional derivatives of GPG with appended amino acid motifs can also form nanofibers, a display of the block sequence's robust self-assembling properties. However, how the block length affects fiber formation has never been clarified. This study focuses on the synthesis and characterization of a novel ELP, GPPG, in which the central sequence (VPGVG)25 is repeated twice by a short linker sequence. The self-assembly behavior and the resultant nanostructures of GPG and GPPG were when compared through circular dichroism spectroscopy, atomic force microscopy, and transmission electron microscopy. Dynamic rheology measurements revealed that the nanofiber dispersions of both GPG and GPPG at an extremely low concentration (0.034 wt%) exhibited solid-like behavior with storage modulus G' > loss modulus G" over wide range of angular frequencies, which was most probably due to the high aspect ratio of the nanofibers that leads to the flocculation of nanofibers in the dispersion.

Ring-Like Assembly of Silica Nanospheres in the Presence of Amphiphilic Block Copolymer: Effects of Particle Size.

Block copolymer-mediated self-assembly of colloidal nanoparticles has attracted great attention for the fabrication of a wide variety of nanoparticle arrays. We have previously shown that silica nanospheres (SNSs) 15 nm in diameter assemble into ring-like nanostructures in the presence of amphiphilic block copolymers poly[(2-ethoxyethyl vinyl ether)- block-(2-methoxyethyl vinyl ether)] (EOVE-MOVE) in an aqueous phase. Here, the effects of particle size of SNSs on this polymer-mediated self-assembly are studied systematically using scanning electron microscopy to observe SNSs of seven different sizes between 13 to 42 nm. SNSs of 13, 16, 19, and 21 nm in diameter assemble into nanorings in the presence of EOVE-MOVE. In contrast, larger SNSs of 26, 34, and 42 nm aggregate heavily, form chain-like networks, and remain dispersed, respectively, instead of forming ring-like nanostructures. The assembly trend for 26-42 nm-SNSs agrees with that expected from the increased colloidal stability for larger particles. Time-course observation for the assembled morphology of 16 nm-SNSs reveals that the nanorings, once formed, assemble further into network-like structures, as if the nanorings behave as building units for higher-order assembly. This indicates that the ring-like assembly is a fast process that can proceed onto random colloidal aggregation. Detailed analysis of nanoring structures revealed that the average number of SNSs comprising one ring decreased from 5.0 to 3.1 with increasing the SNS size from 13 to 21 nm. A change in the number of ring members was also observed when the length of EOVE-MOVE varied while the size of SNSs was fixed. Dynamic light scattering measurements and atomic force microscopy confirmed the SNSs/polymer composite structures. We hypothesize that a stable composite morphology may exist that is influenced by both the size of SNSs and the polymer molecular structures.

Severity and Frequency of Proximal Tubule Injury Determines Renal Prognosis.

AKI increases the risk of developing CKD, but the mechanisms linking AKI to CKD remain unclear. Because proximal tubule injury is the mainstay of AKI, we postulated that proximal tubule injury triggers features of CKD. We generated a novel mouse model to induce proximal tubule-specific adjustable injury by inducing the expression of diphtheria toxin (DT) receptor with variable prevalence in proximal tubules. Administration of high-dose DT in mice expressing the DT receptor consistently caused severe proximal tubule-specific injury associated with interstitial fibrosis and reduction of erythropoietin production. Mild proximal tubule injury from a single injection of low-dose DT triggered reversible fibrosis, whereas repeated mild injuries caused sustained interstitial fibrosis, inflammation, glomerulosclerosis, and atubular glomeruli. DT-induced proximal tubule-specific injury also triggered distal tubule injury. Furthermore, injured tubular cells cocultured with fibroblasts stimulated induction of extracellular matrix and inflammatory genes. These results support the existence of proximal-distal tubule crosstalk and crosstalk between tubular cells and fibroblasts. Overall, our data provide evidence that proximal tubule injury triggers several features of CKD and that the severity and frequency of proximal tubule injury determines the progression to CKD.

Exploring the origin and limitations of kidney regeneration.

Epidemiological findings indicate that acute kidney injury (AKI) increases the risk for chronic kidney disease (CKD), although the molecular mechanism remains unclear. Genetic fate mapping demonstrated that nephrons, functional units in the kidney, are repaired by surviving nephrons after AKI. However, the cell population that repairs damaged nephrons and their repair capacity limitations remain controversial. To answer these questions, we generated a new transgenic mouse strain in which mature proximal tubules, the segment predominantly damaged during AKI, could be genetically labelled at desired time points. Using this strain, massive proliferation of mature proximal tubules is observed during repair, with no dilution of the genetic label after the repair process, demonstrating that proximal tubules are repaired mainly by their own proliferation. Furthermore, acute tubular injury caused significant shortening of proximal tubules associated with interstitial fibrosis, suggesting that proximal tubules have a limited capacity to repair. Understanding the mechanism of this limitation might clarify the mechanism of the AKI-to-CKD continuum.

Apatite Formation on α-Tricalcium Phosphate Modified with Bioresponsive Ceramics in Simulated Body Fluid Containing Alkaline Phosphatase.

Bioresponsive ceramics, a new concept in ceramic biomaterials, respond to biological molecules or environments, as exemplified by salts composed of calcium ions and phosphate esters (SCPEs). SCPEs have been shown to form apatite in simulated body fluid (SBF) containing alkaline phosphatase (ALP). Thus, surface modification with SCPEs is expected to improve the apatite-forming ability of a material. In this study, we modified the surface of α-tricalcium phosphate (α-TCP) using methyl, butyl, or dodecyl phosphate to form SCPEs and investigated their apatite formation in SBF and SBF containing ALP. Although apatite did not form on the surface of the unmodified α-TCP in SBF, apatite formation was observed following surface modification with methyl or butyl phosphate. When ALP was present in SBF, apatite formation was especially remarkable on α-TCP modified with butyl phosphate. These SCPEs accelerated apatite formation by releasing calcium ions through dissolution and supplying inorganic phosphate ions, with the latter process only occurring in SBF containing ALP. Notably, no apatite formation occurred on α-TCP modified with dodecyl phosphate, likely because of the low solubility of the resulting calcium dodecyl phosphate/calcium phosphate composites. This new method of using SCPEs is anticipated to contribute to the development of novel ceramic biomaterials.

Enhancement of apatite formation on Ti-50Zr alloy in simulated body environment.

Ti-50Zr alloy is 2.5 times as strong as pure Ti and has a lower Young's modulus, making it a useful material for repairing bone and teeth. However, Ti-50Zr alloy has a limited ability to bond with bone in vivo. Under biological conditions, apatite formation at the surface of a Ti or alloy implant is necessary for its bonding with bone. Various approaches to surface modification have been proposed to impart bone-bonding ability to Ti-50Zr alloy; however, there remains a need for further improvements to the alloy's apatite-forming ability. Hence, in this study, we compared apatite formation at the surface of alloy substrates in simulated body fluid, after various surface treatments. Treatment with 5 M NaOH followed by 1 M CaCl2 was the most effective procedure, whereas a sample subjected to a hot water post-treatment formed less apatite. Notably, no apatite formed on samples treated with 10 M NaOH.

Biological properties of self-assembled nanofibers of elastin-like block polypeptides for tissue-engineered vascular grafts: platelet inhibition, endothelial cell activation and smooth muscle cell maintenance.

Strategic materials design is essential for the development of small-diameter, tissue-engineered vascular grafts. Self-assembled nanofibers of elastin-like polypeptides represent promising vascular graft components as they replicate the organized elastin structure of native blood vessels. Further, the bioactivity of nanofibers can be modified by the addition of functional peptide motifs. In the present study, we describe the development of a novel nanofiber-forming elastin-like polypeptide (ELP) with an arginine-glutamic acid-aspartic acid-valine (REDV) sequence. The biological characteristics of the REDV-modified ELP nanofibers relevant to applications in vascular grafting were compared to ELP without ligands for integrin, ELP with arginine-glycine-aspartic acid (RGD) sequence, collagen and cell culture glass. Among them, REDV-modified ELP nanofibers met the preferred biological properties for vascular graft materials, i.e. (i) inhibition of platelet adhesion and activation, (ii) endothelial cell adhesion and proliferation and (iii) maintenance of smooth muscle cells in a contractile phenotype to prevent cell overgrowth. The results indicate that REDV-modified ELP nanofibers represent promising candidates for the further development of small-diameter vascular grafts.

Design and analysis for the SPICE parameters of waveform-selective metasurfaces varying with the incident pulse width at a constant oscillation frequency.

In this study, we numerically demonstrate how the response of recently reported circuit-based metasurfaces is characterized by their circuit parameters. These metasurfaces, which include a set of four diodes as a full wave rectifier, are capable of sensing different waves even at the same frequency in response to the incident waveform, or more specifically the pulse width. This study reveals the relationship between the electromagnetic response of such waveform-selective metasurfaces and the SPICE parameters of the diodes used. In particular, we draw conclusions about how the SPICE parameters are related to (1) the high-frequency operation, (2) input power requirement and (3) dynamic range of waveform-selective metasurfaces with supporting simulation results. First, we show that reducing a parasitic capacitive component of the diodes is important for realization of the waveform-selective metasurfaces in a higher frequency regime. Second, we report that the operating power level is closely related to the saturation current and the breakdown voltage of the diodes. Moreover, the operating power range is found to be broadened by introducing an additional resistor into the inside of the diode bridge. Our study is expected to provide design guidelines for circuit-based waveform-selective metasurfaces to select/fabricate optimal diodes and enhance the waveform-selective performance at the target frequency and power level. Our results are usefully exploited to ensure the selectivity based on the pulse duration of the incident wave in a range of potential applications including electromagnetic interference, wireless power transfer, antenna design, wireless communications, and sensing.

Human stem cell response to layered zirconium phosphate.

This study aims to evaluate the in vitro cytocompatibility of layered zirconium phosphate (ZP) and its derivative material that was organically modified using glycerophosphate (ZGP). The ZP and ZGP particles were prepared via a reflux method in an aqueous solution containing phosphoric acid. The field emission scanning electron microscopy showed the prepared samples were fine particles with 70-100 nm diameter. X-ray diffraction and Raman spectrometry indicated the presence of a layered crystal structure. The interlayer distance of ZP was estimated to be 0.76 nm from the 002 diffraction. Modification of ZP with ß-glycerophosphate, lead to expansion of the interlayer distance of 0.85 nm. Grazing incidence X-ray diffraction and Raman spectrometry showed that the crystal structures of ZP and ZGP were maintained even after the samples were coated onto polyethylene (PE) substrates via hot pressing. The water droplet contact angles on the PE substrates coated with the ZP and ZGP particles (ZP/PE and ZGP/PE) were 2 ∼ 6° lesser than that on the uncoated PE substrate. After human adipose-derived stem cells (hASCs) were cultured on the substrates, 2.5-3.5 times higher numbers of adhered cells were observed on the substrates coated with ZP and ZGP than on the uncoated PE substrates and 1.1-1.6 times higher than on the substrate coated with hydroxyapatite particles (HAp/PE). Increasing cell numbers were observed after culturing for 24 h, indicating that the ZP/PE and ZGP/PE showed low cytotoxicity to the hASCs. Furthermore, the ZP/PE showed the highest area of hASC adhesion among all the samples. These results highlight the possibility that layered zirconium phosphate and its organically modified substances can be applied to biomaterials for tissue repair.

Tearable and Fillable Composite Sponges Capable of Heat Generation and Drug Release in Response to Alternating Magnetic Field.

Tearable and fillable implants are used to facilitate surgery. The use of implants that can generate heat and release a drug in response to an exogenous trigger, such as an alternating magnetic field (AMF), can facilitate on-demand combined thermal treatment and chemotherapy via remote operation. In this study, we fabricated tearable sponges composed of collagen, magnetite nanoparticles, and anticancer drugs. Crosslinking of the sponges by heating for 6 h completely suppressed undesirable drug release in saline at 37 °C but allowed drug release at 45 °C. The sponges generated heat immediately after AMF application and raised the cell culture medium temperature from 37 to 45 °C within 15 min. Heat generation was controlled by switching the AMF on and off. Furthermore, in response to heat generation, drug release from the sponges could be induced and moderated. Thus, remote-controlled heat generation and drug release were achieved by switching the AMF on and off. The sponges destroyed tumor cells when AMF was applied for 15 min but not when AMF was absent. The tearing and filling properties of the sponges may be useful for the surgical repair of bone and tissue defects. Moreover, these sponges, along with AMF application, can facilitate combined thermal therapy and chemotherapy.

Conformational change detection in nonmetal proteins by direct electrochemical oxidation using diamond electrodes.

In this report, we established a new electrochemical method for the detection of conformational changes in large, non-metalloproteins such as bovine serum albumin, using flow injection analysis coupled with hydrogen-terminated, boron-doped diamond electrodes. The oxidation current was used as a signal reporter in the monitoring of urea-induced BSA denaturation. In the denatured state at high urea concentrations, the electrochemical signal increased, and the amperometric responses for the oxidation potential at 1300 mV were consistent with the results of conventional methods of denaturation monitoring using fluorescence spectroscopy. The oxidation involved at least five redox-active species (cysteine, tryptophan, tyrosine, methionine, and disulfide bonds). Furthermore, the method also showed high sensitivity for quantitative analysis of protein. A linear dynamic in the concentration range 50-400 microg/mL (r(2) = 0.977) with a lower detection limit of 190 ng/mL was achieved for BSA. Direct electrochemical detection of conformation changes of proteins using BDD electrodes can be performed with advantages in terms of simplicity and sensitivity.

Origin of the Photoluminescence Quantum Yields Enhanced by Alkane-Termination of Freestanding Silicon Nanocrystals: Temperature-Dependence of Optical Properties.

On the basis of the systematic study on temperature dependence of photoluminescence (PL) properties along with relaxation dynamics we revise a long-accepted mechanism for enhancing absolute PL quantum yields (QYs) of freestanding silicon nanocrystals (ncSi). A hydrogen-terminated ncSi (ncSi:H) of 2.1 nm was prepared by thermal disproportination of (HSiO1.5)n, followed by hydrofluoric etching. Room-temperature PL QY of the ncSi:H increased twentyfold only by hydrosilylation of 1-octadecene (ncSi-OD). A combination of PL spectroscopic measurement from cryogenic to room temperature with structural characterization allows us to link the enhanced PL QYs with the notable difference in surface structure between the ncSi:H and the ncSi-OD. The hydride-terminated surface suffers from the presence of a large amount of nonradiative relaxation channels whereas the passivation with alkyl monolayers suppresses the creation of the nonradiative relaxation channels to yield the high PL QY.