We investigated what is really meant by so-called positional or frequency fluctuation of spectral features. To show the difference between the true frequency shift of a single band and apparent peak maximum shift caused by relative intensity changes of overlapped adjacent bands, we analyzed infrared (IR) spectra of the OH stretching band of ethylene glycol during the heating process and the C=O stretching band of acetone in a mixed solvent CHCl(3)/CCl(4) with varying solvent compositions. These spectra are well-known examples of so-called "band shift" phenomena often interpreted as the manifestation of gradual changes in the IR frequency associated with a specific chemical bond under the influence of molecular interactions. Analyses of IR spectra showed that the apparent positional shifts of peak maxima in these systems are actually due to relative contribution changes of two overlapped bands, instead of the gradual frequency shift of a single band induced by the change in the strength of molecular interactions. To further clarify our interpretation of "peak maximum shifts", we also analyzed simulated spectral datasets, comparing the true band frequency shift and change in the relative contributions of overlapped bands. It was found that principal component analysis (PCA) is a surprisingly sensitive tool to distinguish the two possible mechanisms of peak maximum shift. The new insight revealed by this study should help the interpretation of molecular interactions probed by vibrational spectroscopy.
In order to fabricate a digital microfluidic (DMF) chip, which requires a patterned array of electrodes coated with a dielectric film, we explored two simple methods: Ballpoint pen printing to generate the electrodes, and wrapping of a dielectric plastic film to coat the electrodes. For precise and programmable printing of the patterned electrodes, we used a digital plotter with a ballpoint pen filled with a silver nanoparticle (AgNP) ink. Instead of using conventional material deposition methods, such as chemical vapor deposition, printing, and spin coating, for fabricating the thin dielectric layer, we used a simple method in which we prepared a thin dielectric layer using pre-made linear, low-density polyethylene (LLDPE) plastic (17-μm thick) by simple wrapping. We then sealed it tightly with thin silicone oil layers so that it could be used as a DMF chip. Such a treated dielectric layer showed good electrowetting performance for a sessile drop without contact angle hysteresis under an applied voltage of less than 170 V. By using this straightforward fabrication method, we quickly and affordably fabricated a paper-based DMF chip and demonstrated the digital electrofluidic actuation and manipulation of drops.
A simple programmable contact printing method using ballpoint pens with silver nanoparticle (AgNP) and carbon nanotube (CNT) ink and a digital plotter were developed for quick patterning of electrodes on paper. This printing method enables sequential and programmable printing with two different inks and with ink consisting of high viscosity materials and is amenable to reproducibility of printed electrodes and customized designs. With this printing method, AgNP and CNT patterns with low electrical resistance and high density of the material can be printed. Using these AgNP and CNT inks, we fabricated disposable electrochemical sensors (ECSs) on paper. The ECSs were successfully used to detect glucose at various concentrations from 0 to 15 mM. The characteristics of the printed AgNP and CNT patterns, such as the printing resolution, surface morphology, and electrical properties, were also studied. The proposed contact printing method opens an avenue for printing paper-based electronics and devices.
We investigated the thermal behavior of spin-coated films of biodegradable poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P(HB-co-HHx)) copolymers at the molecular level. To better understand details of thermal behavior of spin-coated films of P(HB-co-HHx) copolymers, we applied two-dimensional (2D) correlation analysis to the spectra of P(HB-co-HHx) (HHx = 12.0, 10.0, and 3.8 mol %) copolymers during the heating process from 30 to 150 degrees C as obtained by temperature-dependent infrared-reflection absorption spectroscopy and X-ray photoelectron spectroscopy (XPS). 2D IR and 2D XPS correlation spectra of spin-coated films of P(HB-co-HHx) copolymers clearly revealed the sequence of intensity changes with increasing temperature: an amorphous band increases first and then a band for less ordered secondary crystals decreases before a band for well-ordered primary crystals. Furthermore, the synchronous 2D heterospectral XPS/IR correlation spectrum elucidated the correlation between the IR and XPS bands, confirming their band assignments. The asynchronous 2D heterospectral correlation spectrum revealed the probe-dependent asynchronicity between XPS and IR signals arising from the same species even under identical perturbation conditions because of the different scales of molecular changes probed. It clearly provides a complete interpretation of the phase transition phenomenon of P(HB-co-HHx) copolymers, which could not have been obtained through XPS or IR study alone, and also, the results obtained thereof offer a new insight into the molecular interactions as well observed by two different probes.
We investigated bleached human hair by FT-IR microspectroscopy and chemical imaging. The cross sectioned hair is approximately 90 μm in diameter, showed cuticle and cortex in chemical imaging. Differential amide I/II absorbance ratio and broadening amide I band between in the cortex and cuticle were confirmed in FT-IR microspectroscopy and chemical imaging. The cystine monoxide band from the products of disulfide oxidation of the amino acid cystine is associated with hair damaging during bleaching process. With increase bleaching time, the band for cystine monoxide shows more intense and larger area in chemical image. The spatially chemical change was investigated in detail by FT-IR microspectroscopy and chemical imaging during the bleached process.
A suture is a ubiquitous medical device to hold wounded tissues together and support the healing process after surgery. Surgical sutures, having incomplete biocompatibility, often cause unwanted infections or serious secondary trauma to soft or fragile tissue. In this research, UV/ozone (UVO) irradiation or polystyrene sulfonate acid (PSS) dip‐coating is used to achieve a fibronectin (FN)‐coated absorbable suture system, in which the negatively charged moieties produced on the suture cause fibronectin to change from a soluble plasma form into a fibrous form, mimicking the actions of cellular fibronectin upon binding. The fibrous fibronectin coated on the suture can be exploited as an engineered interface to improve cellular migration and adhesion in the region around the wounded tissue while preventing the binding of infectious bacteria, thereby facilitating wound healing. Furthermore, the FN‐coated suture is found to be associated with a lower friction between the suture and the wounded tissue, thus minimizing the occurrence of secondary wounds during surgery. It is believed that this surface modification can be universally applied to most kinds of sutures currently in use, implying that it may be a novel way to develop a highly effective and safer suture system for clinical applications.
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