Effects of Fe Ions, Ultraviolet Irradiation, and Heating on Microscopic Structures of Black Lacquer Films.

The chemical reaction between Fe and lacquer has been used to create the black color in lacquer coatings since ancient times. Here, the effects of Fe ion addition, UV irradiation, and heating on the microscopic structures of black lacquer films were investigated by using X-ray absorption near edge structure (XANES), extended X-ray absorption fine structure (EXAFS), Fourier transform-infrared spectroscopy (FT-IR), small-angle X-ray scattering (SAXS), and small angle neutron scattering (SANS). The EXAFS result indicated that heating and UV irradiation made the coordination structure of Fe3+ in the lacquer nonuniform, and that heating caused the greatest nonuniformity. The FT-IR, SAXS, and SANS results demonstrated that the microscopic structural changes in the black lacquer films were induced by both heating and UV irradiation, but the changes were different. Heating caused a substantial structural change on the nanoscale, and UV irradiation mainly caused changes in the molecular binding mode. The results provide important knowledge for analyzing archeological lacquer samples and for developing lacquer-based materials. This work also demonstrates the utility of the complementary use of XANES, EXAFS, FT-IR, SAXS, and SANS for nondestructive analysis of black lacquer in precious cultural relics.

Soft, skin-interfaced microfluidic systems with integrated immunoassays, fluorometric sensors, and impedance measurement capabilities.

Soft microfluidic systems that capture, store, and perform biomarker analysis of microliter volumes of sweat, in situ, as it emerges from the surface of the skin, represent an emerging class of wearable technology with powerful capabilities that complement those of traditional biophysical sensing devices. Recent work establishes applications in the real-time characterization of sweat dynamics and sweat chemistry in the context of sports performance and healthcare diagnostics. This paper presents a collection of advances in biochemical sensors and microfluidic designs that support multimodal operation in the monitoring of physiological signatures directly correlated to physical and mental stresses. These wireless, battery-free, skin-interfaced devices combine lateral flow immunoassays for cortisol, fluorometric assays for glucose and ascorbic acid (vitamin C), and digital tracking of skin galvanic responses. Systematic benchtop evaluations and field studies on human subjects highlight the key features of this platform for the continuous, noninvasive monitoring of biochemical and biophysical correlates of the stress state.

Soft, Skin-Interfaced Microfluidic Systems with Wireless, Battery-Free Electronics for Digital, Real-Time Tracking of Sweat Loss and Electrolyte Composition.

Sweat excretion is a dynamic physiological process that varies with body position, activity level, environmental factors, and health status. Conventional means for measuring the properties of sweat yield accurate results but their requirements for sampling and analytics do not allow for use in the field. Emerging wearable devices offer significant advantages over existing approaches, but each has significant drawbacks associated with bulk and weight, inability to quantify volumetric sweat rate and loss, robustness, and/or inadequate accuracy in biochemical analysis. This paper presents a thin, miniaturized, skin-interfaced microfluidic technology that includes a reusable, battery-free electronics module for measuring sweat conductivity and rate in real-time using wireless power from and data communication to electronic devices with capabilities in near field communications (NFC), including most smartphones. The platform exploits ultrathin electrodes integrated within a collection of microchannels as interfaces to circuits that leverage NFC protocols. The resulting capabilities are complementary to those of previously reported colorimetric strategies. Systematic studies of these combined microfluidic/electronic systems, accurate correlations of measurements performed with them to those of laboratory standard instrumentation, and field tests on human subjects exercising and at rest establish the key operational features and their utility in sweat analytics.

Super-Absorbent Polymer Valves and Colorimetric Chemistries for Time-Sequenced Discrete Sampling and Chloride Analysis of Sweat via Skin-Mounted Soft Microfluidics.

This paper introduces super absorbent polymer valves and colorimetric sensing reagents as enabling components of soft, skin-mounted microfluidic devices designed to capture, store, and chemically analyze sweat released from eccrine glands. The valving technology enables robust means for guiding the flow of sweat from an inlet location into a collection of isolated reservoirs, in a well-defined sequence. Analysis in these reservoirs involves a color responsive indicator of chloride concentration with a formulation tailored to offer stable operation with sensitivity optimized for the relevant physiological range. Evaluations on human subjects with comparisons against ex situ analysis illustrate the practical utility of these advances.

Structural changes of water in poly(vinyl alcohol) hydrogel during dehydration.

To investigate the mechanism of structural changes of water and polymer networks with drying and swelling, we measured the Raman spectra of a physically cross-linked poly(vinyl alcohol) (PVA) hydrogel synthesized using the freezing-thawing method. The results show that the vibrational frequencies of the O-H and C-H stretching modes decrease with dehydration. The frequency shifts observed are attributed to reduction of free water inside the polymer network. The C-H bonds elongate as the water density decreases, and the average length of the O-H bonds increases with increasing proportion of bound water to the total amount of water. On the basis of the dependence of the frequency shifts on the PVA concentration of the original solution, it was found that the structure of the polymer network in the reswollen hydrogel becomes inhomogeneous due to shrinkage of the polymer network with drying. Furthermore, to investigate the effects of the cross-linking structure on the drying process, these results were compared with those of a chemically cross-linked PVA hydrogel synthesized using glutaraldehyde as a cross-linker. The result shows that the vibrational frequency of the O-H stretching mode for the chemically cross-linked hydrogel increases with dehydration, whereas that of the C-H stretching mode decreases. The opposite trend observed in the O-H stretching mode between the physically and chemically cross-linked hydrogels is due to the difference in the shrinkage rate of the polymer network. Because the rate of shrinking is slow compared with that of dehydration in the chemically cross-linked hydrogel, water density in the polymer network decreases. For the physically cross-linked hydrogel, the polymer network structure can be easily shrunken, and the average strength of hydrogen bonds increases with dehydration. The results show that the structures of the polymer network and water change with the gel preparation process, cross-linking method, and drying and reswelling processes. The structure of the polymer network and the behavior of water accommodated in the network are important factors governing the chemical and physical properties of gel materials.

Freeze-crosslinking approach for preparing carboxymethyl cellulose nanofiber/zirconium hydrogels as fluoride adsorbents.

Tough carboxymethylcellulose nanofibers (CMF)/zirconium (Zr) hydrogels were easily obtained by a freeze-crosslinking method, where Zr-containing HCl solution was added to frozen CMF sol and the mixture was allowed to thaw. The Zr content of the hydrogels increased with increasing Zr concentration in the initial HCl solution. Furthermore, the mechanical strength increased with increasing Zr content. The Young's modulus value was improved by approximately 6 times compared to the CMF hydrogel without Zr, i.e., from 4.5 kPa to 27.2 kPa. The hydrogel had a porous structure with a pore size of 133 ± 37 µm and a CMF-Zr sheet structure around the pores. The obtained CMF-Zr hydrogel exhibited high adsorptivity for fluoride. The maximum adsorption capacity (Qmax) was estimated to be 24.1 mg g-1. This simple gelation method provides useful insights for the development of easy-to-handle hydrogel-based adsorbents.

Nanocellulose hydrogels formed via crystalline transformation from cellulose I to II and subsequent freeze cross-linking reaction.

We describe nanocellulose (NC) hydrogels formed from chemically unmodified NC by cellulose crystalline transformation and subsequent freeze cross-linking reaction. The freeze cross-linked NC hydrogel with macropores (~100 µm) was prepared by freezing a mixture of NC and NaOH (0.2 mol L-1), adding citric acid to the frozen mixture, and thawing it. Using NaOH and freezing together induced the crystalline transformation of NC from cellulose I to II via freeze concentration. After the crystalline transformation, cross-linking between the NC and CA in the freeze concentration layer provided a strong NC network structure, forming NC hydrogels with high mechanical strength. The structural changes in NC caused by NaOH, freezing, and freeze cross-linking on the angstrom to micrometer scale were investigated with FT-IR, SAXS, PXRD, and SEM. The freeze cross-linked NC hydrogel easily retained powder adsorbents in its inner space by mixing the NC-NaOH sol and the powder, and the hydrogel showed high removal efficiency for heavy metals. The results highlight the versatility of chemically unmodified celluloses in developing functional materials and suggest possible practical applications. This study also provides new insights into the efficient use of chemical reactions of cellulose under freezing conditions.

Polarized Neutrons Observed Nanometer-Thick Crystalline Ice Plates in Frozen Glucose Solution.

Spin-contrast-variation (SCV) small-angle neutron scattering (SANS) is a technique to determine the nanostructure of composite materials from the scattering of polarized neutrons that changes with proton polarization of samples. The SCV-SANS enabled us to determine structure of nanoice crystals that were generated in rapidly frozen sugar solutions by separating the overlapped signals from the nanoice crystals and frozen amorphous solutions. In the frozen glucose solution, we found that the nanoice crystals formed a planar structure with a radius larger than several tens of nanometers and a thickness of 2.5 ± 0.5 nm, which was close to the critical nucleation size of ice crystals in supercooled water. This result suggests that the glucose molecules were preferentially bound to a specific face of nanoice crystals and then blocked the crystal growth perpendicular to that face.

3D-printed epidermal sweat microfluidic systems with integrated microcuvettes for precise spectroscopic and fluorometric biochemical assays.

Systems for capture, storage and analysis of eccrine sweat can provide insights into physiological health status, quantify losses of water, electrolytes, amino acids and/or other essential species, and identify exposures to adverse environmental species or illicit drugs. Recent advances in materials and device designs serve as the basis for skin-compatible classes of microfluidic platforms and in situ colorimetric assays for precise assessments of sweat rate, sweat loss and concentrations of wide-ranging types of biomarkers in sweat. This paper presents a set of findings that enhances the performance of these systems through the use of microfluidic networks, integrated valves and microscale optical cuvettes formed by three dimensional printing in hard/soft hybrid materials systems, for accurate spectroscopic and fluorometric assays. Field studies demonstrate the capability of these microcuvette systems to evaluate the concentrations of copper, chloride, and glucose in sweat, along with the pH of sweat, with laboratory-grade accuracy and sensitivity.

Structure and dynamics of water in mixed solutions including laponite and PEO.

To investigate the structure and dynamics of water in mixed solutions including laponite clay particles and poly(ethylene oxide) (PEO), we measured the Raman spectra of the mixed solutions in the temperature range 283-313 K. The results show that the vibrational energies of the O-H stretching modes in the mixed solutions depend on the water content and temperature. The energy shifts of the O-H stretching modes are attributed to changes in the water structure. By applying a structural model of bulk water to the spectra in the O-H stretching region, the local structures of water in the solutions were analyzed. The result shows that the formation probability of hydrogen bonds in the solutions decreases as the water content decreases. Laponite and PEO have effects to disrupt the network structure of hydrogen bonds between water molecules. Further, it was found that laponite and PEO cause increase in the strength of hydrogen bonds of surrounding water,although the strength of the hydrogen bonds increases with the order water-laponite < water-water < water-PEO. It is concluded that water in laponite-PEO mixed solutions has a less-networked structure with strong hydrogen bonds compared with bulk water.

Sewage sludge ash contaminated with radiocesium: Solidification with alkaline-reacted metakaolinite (geopolymer) and Portland cement.

This study contributes toward developing measures for the disposal of radiocesium-contaminated sewage sludge ash (SSA). Here, we prepared two types of solidified bodies containing 30 wt% radiocesium-bearing SSA. The material used for the two solidified bodies were alkaline-reacted metakaolinite (geopolymer) and ordinary Portland cement (OPC). Cement has been used for solidification of low-level radioactive wastes, and geopolymer is a candidate of cement alternative materials. The characteristics of these solidified bodies were investigated by various aspects including mechanical strength, transformation of SSA components during solidification, and radiocesium confinement ability by leaching test. The compressive strength of geopolymer- and OPC-solidified bodies at 30 wt% SSA content was more than 40 MPa. After static leaching test at 60 °C, 137Cs was hardly leached out from the geopolymer-solidified bodies containing SSA at 30 wt% to ultrapure water (<0.1%), whereas more than 30% 137Cs was leached from the OPC-solidified bodies containing SSA at 30 wt% even though only ~9% of 137Cs in the SSA is soluble. These results strongly indicate that geopolymer is far superior to OPC for solidifying radiocesium-bearing SSA.

Magnetically Navigated Protein Transduction In Vivo using Iron Oxide-Nanogel Chaperone Hybrid.

Systems for "protein transduction," intracellular delivery of functional proteins, are needed to address deliverability challenges of protein therapeutics. However, in vivo protein transduction remains challenging because of instability in serum, extracellular protease digestion and rapid excretion from the bloodstream. Here, a magnetically guided in vivo protein transduction using magnetic nanogel chaperone (MC) composed of iron oxide nanoparticles and a polysaccharide nanogel, a protein carrier inspired by "catch and release" mechanisms of molecular chaperones is demonstrated. The MC system enables efficient delivery of anti-cancer proteins, saporin and RNaseA, into cultured tumor lines and inhibits cell proliferation, mainly via apoptosis. Magnetic in vivo protein transduction via intravenous whole body administration is demonstrated in a fibrosarcoma model. By in vivo optical imaging, MC accumulated in tumor tissues under magnetic field three times more than without irradiation. With subcutaneous injection, saporin is delivered by MC to the cytoplasm in magnetically targeted tissues. In an oral cancer model, MC-delivered magnetically targeted saporin decreased tumor volume without significant body weight changes and no regrowth of tumor at 3 months after complete regression. Protein transduction with MC shows promise for cancer therapeutics and, potentially, for regenerative medicine and other biomedical applications.

Structural changes of water in a hydrogel during dehydration.

Raman spectra of poly-N,N,-dimethylacrylamide hydrogel were measured in order to investigate the mechanism of the structural changes in water and the polymer network during dehydration. The results show that the vibrational energies of the C=O and the O-H stretching modes increase with the extent of dehydration, whereas that of the CH(3) rocking mode decreases. The energy shifts observed in the C=O stretching and CH(3) rocking modes indicate that the polymer network shrinks with the dehydration and undergoes a glass transition at some point. The energy shifts of the O-H stretching modes are attributed to changes in the water structure with the structural change of the polymer network. By applying a structural model of bulk water to the spectra of the O-H stretching region, the local water structures in the gel and the dried glassy polymer were analyzed. The result shows that a tetragonal water structure consisting of four hydrogen bonds increases in the residual water of the dried glassy polymer, suggesting that the residual water forms a two-dimensional hydrogen-bonded network. The local water structure in a polymer might have important implications for the interpretation of properties of localized water, for instance, water in a mineral crack.

Root-endophytic Chaetomium cupreum chemically enhances aluminium tolerance in Miscanthus sinensis via increasing the aluminium detoxicants, chlorogenic acid and oosporein.

Miscanthus sinensis Andersson is a pioneer plant species that grows naturally at mining sites. Miscanthus sinensis can detoxify aluminium (Al) by producing phytosiderophores, such as chlorogenic acid, citric acid, and malic acid, and localizing Al in cell walls. Root-endophytic Chaetomium cupreum, which produces microbial siderophores, enhances Al tolerance in M. sinensis. However, we could not determine whether the siderophores produced by C. cupreum actually enhance Al tolerance in M. sinensis, because the microbial siderophores have not yet been identified in previous research. The purpose of this study was to clarify how C. cupreum chemically increases Al tolerance in M. sinensis under acidic mining site conditions, especially considering siderophores. Using instrumental analyses, the siderophore produced by C. cupreum was identified as oosporein. Comparison of the stability constant between Al and phytosiderophores and oosporein indicated that oosporein could detoxify Al similarly to chlorogenic acid, which shows higher stability constant than citric acid and malic acid. Inoculation test of C. cupreum onto M. sinensis in acidic mine soil showed that C. cupreum promoted seedling growth, and enhanced Al tolerance via inducing chlorogenic-acid production and producing oosporein. These results suggested that C. cupreum could chemically enhance Al tolerance and might promote growth via reducing excessive Al in cell walls, the main site of Al accumulation. In addition, the chemical enhancement of Al tolerance by C. cupreum might be important for M. sinensis to adapt to acidic mining sites.

Passive sweat collection and colorimetric analysis of biomarkers relevant to kidney disorders using a soft microfluidic system.

The rich range of biomarkers in sweat and the ability to collect sweat in a non-invasive manner create interest in the use of this biofluid for assessments of health and physiological status, with potential applications that range from sports and fitness to clinical medicine. This paper introduces two important advances in recently reported classes of soft, skin-interfaced microfluidic systems for sweat capture and analysis: (1) a simple, broadly applicable means for collection of sweat that bypasses requirements for physical/mental exertion or pharmacological stimulation and (2) a set of enzymatic chemistries and colorimetric readout approaches for determining the concentrations of creatinine and urea in sweat, throughout ranges that are physiologically relevant. The results allow for routine, non-pharmacological capture of sweat for patient populations, such as infants and the elderly, that cannot be expected to sweat through exercise, and they create potential opportunities in the use of sweat for kidney disease screening/monitoring. Studies on human subjects demonstrate these essential capabilities, with quantitative comparisons to standard methods. The results expand the range of options available in microfluidic sampling and sensing of sweat for disease diagnostics and health monitoring.

Battery-free, skin-interfaced microfluidic/electronic systems for simultaneous electrochemical, colorimetric, and volumetric analysis of sweat.

Wearable sweat sensors rely either on electronics for electrochemical detection or on colorimetry for visual readout. Non-ideal form factors represent disadvantages of the former, while semiquantitative operation and narrow scope of measurable biomarkers characterize the latter. Here, we introduce a battery-free, wireless electronic sensing platform inspired by biofuel cells that integrates chronometric microfluidic platforms with embedded colorimetric assays. The resulting sensors combine advantages of electronic and microfluidic functionality in a platform that is significantly lighter, cheaper, and smaller than alternatives. A demonstration device simultaneously monitors sweat rate/loss, pH, lactate, glucose, and chloride. Systematic studies of the electronics, microfluidics, and integration schemes establish the key design considerations and performance attributes. Two-day human trials that compare concentrations of glucose and lactate in sweat and blood suggest a potential basis for noninvasive, semi-quantitative tracking of physiological status.

A fluorometric skin-interfaced microfluidic device and smartphone imaging module for in situ quantitative analysis of sweat chemistry.

The rich composition of solutes and metabolites in sweat and its relative ease of collection upon excretion from skin pores make this class of biofluid an attractive candidate for point of care analysis. Wearable technologies that combine electrochemical sensors with conventional or emerging semiconductor device technologies offer valuable capabilities in sweat sensing, but they are limited to assays that support amperometric, potentiometric, and colorimetric analyses. Here, we present a complementary approach that exploits fluorometric sensing modalities integrated into a soft, skin-interfaced microfluidic system which, when paired with a simple smartphone-based imaging module, allows for in situ measurement of important biomarkers in sweat. A network array of microchannels and a collection of microreservoirs pre-filled with fluorescent probes that selectively react with target analytes in sweat (e.g. probes), enable quantitative, rapid analysis. Field studies on human subjects demonstrate the ability to measure the concentrations of chloride, sodium and zinc in sweat, with accuracy that matches that of conventional laboratory techniques. The results highlight the versatility of advanced fluorescent-based imaging modalities in body-worn sweat microfluidics platforms, and they suggest some practical potential for these ideas.

Calcium-deficient Hydroxyapatite as a Potential Sorbent for Strontium.

A calcium (Ca)-deficient hydroxyapatite was investigated for its potential to remove Sr2+ from environmentally relevant water. We conducted sorption tests on solutions containing magnesium ion (Mg2+) and calcium ion (Ca2+) as competing cations at a strontium ion (Sr2+) concentration of 0.05 mmol/L. The Ca-deficient hydroxyapatite maintained a high Sr2+ sorption ratio of above 80% in the presence of Mg2+ and Ca2+ at the concentrations between 0.1 and 1.0 mmol/L, whereas the stoichiometric hydroxyapatite showed a lower ratio even in the presence of small amounts of Mg2+ and Ca2+ (72% for Mg2+ and 51% for Ca2+ at 0.1 mmol/L). For solutions with various Sr2+ concentrations between 0.01 and 10 mmol/L, Ca-deficient hydroxyapatite exhibited a higher Sr2+ sorption ratio than stoichiometric hydroxyapatite. The bonding states of Sr2+ on the Ca-deficient hydroxyapatite were evaluated by extended X-ray absorption fine structure measurements. The results indicated that there are specific sorption sites in Ca-deficient hydroxyapatite where Sr2+ is stably and preferentially immobilized.

Nanoscopic Structural Investigation of Physically Cross-Linked Nanogels Formed from Self-Associating Polymers.

The detailed structure of a nanogel formed by self-association of cholesterol-bearing pullulans (CHPs) was determined by contrast variation small-angle neutron scattering. The decomposition of scattering intensities into partial scattering functions of each CHP nanogel component, i.e., pullulan, cholesterol, and the cross-term between the pullulan and the cholesterol, allows us to investigate the internal structure of the nanogel. The effective spherical radius of the skeleton formed by pullulan chains was found to be 8.1 ± 0.3 nm. In the CHP nanogel, there are about 19 cross-linking points where a cross-linking point is formed by aggregation of trimer cholesterol molecules, and the spatially inhomogeneous distribution of the cross-linking points in the nanogel can be represented by the mass fractal dimension of 2.6. The average radius of gyration of the partial chains can also be determined to be 1.7 ± 0.1 nm by analyzing the extracted cross-correlation between the cross-linker and the tethered polymer chain quantitatively, and the size agrees with the value assuming random distribution of the cross-linkers on the chains. As the result, the complex structure of the nanogels is coherently revealed at the nanoscopic level.

Neutron diffraction of ice in hydrogels.

Neutron diffraction patterns for deuterated poly-N,N,-dimethylacrylamide (PDMAA) hydrogels were measured from 10 to 300 K to investigate the structure and properties of water in the gels. Diffraction peaks observed below 250 K indicate the existence of ice in the hydrogels. Some diffraction peaks from the ice are at lower diffraction angles than those in ordinary hexagonal ice (Ih). These shifts in peaks indicate that the lattice constants of the a and c axes in the ice are about 0.29 and 0.3% higher than those in ice Ih, respectively. The results show that bulk low-density ice can exist in PDMAA hydrogels. The distortions in the lattice structure of ice imply significant interactions between water molecules and the surrounding polymer chains, which play an important role in the chemical and mechanical properties of the hydrogel.