Entropy and Random Walk Trails Water Confinement and Non-Thermal Equilibrium in Photon-Induced Nanocavities.

Molecules near surfaces are regularly trapped in small cavitations. Molecular confinement, especially water confinement, shows intriguing and unexpected behavior including surface entropy adjustment; nevertheless, observations of entropic variation during molecular confinement are scarce. An experimental assessment of the correlation between surface strain and entropy during molecular confinement in tiny crevices is difficult because strain variances fall in the nanometer scale. In this work, entropic variations during water confinement in 2D nano/micro cavitations were observed. Experimental results and random walk simulations of water molecules inside different size nanocavitations show that the mean escaping time of molecular water from nanocavities largely deviates from the mean collision time of water molecules near surfaces, crafted by 157 nm vacuum ultraviolet laser light on polyacrylamide matrixes. The mean escape time distribution of a few molecules indicates a non-thermal equilibrium state inside the cavity. The time differentiation inside and outside nanocavities reveals an additional state of ordered arrangements between nanocavities and molecular water ensembles of fixed molecular length near the surface. The configured number of microstates correctly counts for the experimental surface entropy deviation during molecular water confinement. The methodology has the potential to identify confined water molecules in nanocavities with life science importance.

Inducing bioactivity of dental ceramic/bioactive glass composites by Nd:YAG laser.

OBJECTIVES: Aims of this study were to investigate the optimal conditions of laser irradiation of a novel Bioactive Glass/Dental Ceramic-BP67 composite for acceleration of hydroxyapatite-HA formation and to assess cellular responses on the precipitated HA region. METHODS: BP67 (Bioactive Glass: 33.3%, Dental Ceramic: 66.7%) was fabricated by the sol-gel method. A laser assisted biomimetic-LAB process was applied to BP67 sintered specimens immersed in 1.5-times concentrated simulated body fluid-1.5×-SBF. The effect of various energy densities of pulsed nanosecond Nd-YAG (1064nm) laser and irradiation exposure times (30min, 1 and 3h) were evaluated for HA precipitation. The HA film was characterized by FTIR, XRD, SEM and micro Raman techniques. ICP-AES was used for revealing changes in chemical composition of the 1.5×-SBF during irradiation. Cell viability and morphological characteristics of periodontal ligament fibroblasts-PDLFs, human gingival fibroblasts-HGFs and SAOS-2 osteoblasts on the HA surface were evaluated by MTT assays and SEM. RESULTS: At optimal energy fluence of 1.52J/cm2 and irradiation time for 3h followed by immersion in 1.5×-SBF at 60°C, a dense HA layer was formed on laser-irradiated BP67 within 7 days. The resulting HA film was tightly bonded to the underlying substrate and had mineral composition similar to cementum. MTT assay showed a consistent reduction of cell proliferation on the HA layer in comparison to conventional control ceramic and BP67 for all 3 cell lines studied. SIGNIFICANCE: These findings suggest LAB is an effective method for acceleration of HA formation on materials with low bioactivity, while cellular responses need further investigation.

Charge transport mechanisms and memory effects in amorphous TaNx thin films.

Amorphous semiconducting materials have unique electrical properties that may be beneficial in nanoelectronics, such as low leakage current, charge memory effects, and hysteresis functionality. However, electrical characteristics between different or neighboring regions in the same amorphous nanostructure may differ greatly. In this work, the bulk and surface local charge carrier transport properties of a-TaNx amorphous thin films deposited in two different substrates are investigated by conductive atomic force microscopy. The nitride films are grown either on Au (100) or Si [100] substrates by pulsed laser deposition at 157 nm in nitrogen environment. For the a-TaNx films deposited on Au, it is found that they display a negligible leakage current until a high bias voltage is reached. On the contrary, a much lower threshold voltage for the leakage current and a lower total resistance is observed for the a-TaNx film deposited on the Si substrate. Furthermore, I-V characteristics of the a-TaNx film deposited on Au show significant hysteresis effects for both polarities of bias voltage, while for the film deposited on Si hysteresis, effects appear only for positive bias voltage, suggesting that with the usage of the appropriate substrate, the a-TaNx nanodomains may have potential use as charge memory devices.

Raman spectroscopy for intracellular monitoring of carotenoid in Blakeslea trispora.

In the present study, we explore the feasibility of Raman spectroscopy for intracellular monitoring of carotenoid in filamentous fungi Blakeslea trispora. Although carotenoid production from this fungus has been extensively studied through various chromatographic methods and ultraviolet-visible spectroscopy, no intracellular monitoring has been demonstrated until now. The intensity of the Raman spectrum, and more conveniently that of the strongest nu(1) carotenoid band at approximately 1,519 cm(-1), exhibits a good linear correlation with the carotenoid content of the sample as determined by high-performance liquid chromatography (HPLC) and ultraviolet-visible (UV-Vis) spectroscopy. Our results suggest that Raman spectroscopy can serve as an alternative method for the study and quantification of carotenoid in batch-mated submerged cultivations of B. trispora and similar organisms. Although not as accurate as HPLC, it allows a rapid sampling and analysis, avoiding the prolonged and tedious classical isolation procedures required for carotenoid determination by HPLC and UV-Vis spectroscopy.

Evaluating a Cumaean Sibyl: Domenichino or later? A multi analytical approach.

The purpose of this study is to clarify important details about a Cumaean Sibyl painting that is preserved in a private collection. This work, bearing neither signature nor date, has never undergone conservation. It was executed after Domenichino's Cumaean Sibyl, a work known to have been used as a model by many 18th century painters. Investigation of the anonymous artist's painting technique and identification of its constituent materials were facilitated by employing optical microscopy (OM), scanning electron microscopy (SEM/EDS), FTIR and microRaman spectroscopies and high performance liquid chromatography with diode array detection (HPLC-DAD). The painter's palette comprised lead white, yellow ochre, lead-antimonate yellow (Naples yellow), cinnabar, cochineal lake, madder lake, haematite, Prussian blue and carbon black. The detection of Prussian blue (synthesized in 1704 and widely used as artist's pigment after 1750) was decisive in establishing the work's authenticity for, as such, it cannot be attributed either to Domenico Zampieri (1581-1641) or to his apprentices. In addition, the identification of Naples yellow, which prevailed in the period from 1750 to 1850, supports this statement. Nevertheless, its elaborate painting technique strongly suggests an artist greatly influenced by the Renaissance masters. A comparison of its stylistic features with those of the Cumaean Sibyl of Angelica Kauffmann (1741-1807), a prolific 18th century artist known to have studied and to have copied Domenichino's Sibyl, reveals significant similarities between the two in composition and palette. The unsigned Sibyl, therefore, could well be by Kauffmann.