Measurements of Spontaneous and External Stimuli Molecular Release Processes from a Single Optically Trapped Poly(lactic-co-glycolic) Acid Microparticle and a Liposome Containing Gold Nanospheres.

We investigated the single particle kinetics of the molecular release processes from two types of microcapsules used as drug delivery systems (DDS): biodegradable poly(lactic-co-glycolic) acid (PLGA) and a light-triggered-degradable liposome encapsulating gold nanospheres (liposome-GNP). To optimize the design of DDS capsules, it is highly desirable to develop a method for real-time monitoring of the release process. Using a combination of optical tweezers and confocal fluorescence microspectroscopy we successfully analyzed a single optically trapped PLGA particle and liposome-GNPs in solution. From temporal decay profiles of the fluorescence intensity, we determined the time constant τ of the release processes. We demonstrated that the release rate of spontaneously degradable microcapsules (PLGA) decreased with increasing size, while conversely, the release rate of external stimuli-degradable microcapsules (liposome-GNPs) increased in proportion to their size. This result is explained by the differences in the disruption mechanisms of the capsules, with PLGA undergoing hydrolysis and the GNPs in the liposome-GNP undergoing a photoacoustic effect under nanosecond pulsed laser irradiation. The present approach offers a way forward to an alternative microanalysis system for single drug delivery nanocarriers.

Development of Novel Decarboxylation-Urea Method toward Interlayer-Anion-Controlled Layered Double Hydroxides.

Layered double hydroxides (LDHs) are representative of a 2D anionic clay. Simple and homogeneous synthesis of interlayer-anion-controlled LDH is essential for studies and industrial production. In this study, we report the one-pot synthesis of an LDH that is selective for interlayer anions, which was labeled as "decarboxylation-urea method". We obtained LDHs intercalated with NO3-, Cl-, and SO42- by removing CO2 in this method. The ionic conductivities of the prepared LDHs were investigated for their applicability to electrolytes, and it was found that Zn-Al LDH intercalated with NO3- showed the highest ionic conductivity (18 mS cm-1). Therefore, the LDH intercalated with NO3- synthesized using the decarboxylation-urea method is promising as an alkaline solid electrolyte.

Molecular Insight into the Ionic Conduction of Quaternary Ammonium and Phosphonium Cation-Based Ionic Liquids Using Dielectric and Spectroscopy Analyses.

We analyzed the primary properties of ionic liquids (ILs) comprising quaternary phosphonium cations and bis(trifluoromethylsulfonyl) amide anions and compared them with those of corresponding quaternary-ammonium-cation-based ILs. Broadband dielectric spectroscopy was used to confirm the coupling between the translational and orientational motions of ions, and our results demonstrated that the high ionic conductivity of the phosphonium-based ILs was attributed to their fast rotational dynamics. The differences between ILs with different cations were further evaluated using vibrational (Raman and terahertz) spectroscopy. The Raman spectroscopy data revealed that the cation structure affected the conformation and flexibility (conformational change) of the anion. Furthermore, terahertz spectroscopy allowed us to evaluate the relationship between ion transport and intermolecular interactions between the cation and anion of ILs.

Molecular Dynamics Investigation of Hyaluronan in Biolubrication.

Aqueous solution of strongly hydrophilic biopolymers is known to exhibit excellent lubrication properties in biological systems, such as the synovial fluid in human joints. Several mechanisms have been proposed on the biolubrication of joints, such as the boundary lubrication and the fluid exudation lubrication. In these models, mechanical properties of synovial fluid containing biopolymers are essential. To examine the role of such biopolymers in lubrication, a series of molecular dynamics simulations with an all-atom classical force field model were conducted for aqueous solutions of hyaluronan (hyaluronic acid, HA) under constant shear. After equilibrating the system, the Lees-Edwards boundary condition was imposed, with which a steady state of uniform shear flow was realized. Comparison of HA systems with hydrocarbon (pentadecane, PD) solutions of similar mass concentration indicates that the viscosity of HA solutions is slightly larger in general than that of PDs, due to the strong hydration of HA molecules. Effects of added electrolyte (NaCl) were also discussed in terms of hydration. These findings suggest the role of HA in biolubirication as a load-supporting component, with its flexible character and strong hydration structure.

Adsorption Free Energy of Cellulose Nanocrystal on Water-Oil Interface.

To investigate the amphiphilicity of cellulose, a series of molecular dynamics simulations were performed with a cellulose nanocrystal and a water-octane interfacial system. Assuming that the axis of cellulose is parallel to the water-octane interface, the freedoms of motion of the nanocrystal were restricted to two, the distance from the interface and the orientation around the axis. The mean force and the mean torque on the nanocrystal were evaluated with sufficiently long simulation at each crystal configuration, and their numerical integration gave a smooth free energy surface as the potential of mean force. The cellulose sample used here was found to be much more hydrophilic than oleophilic with the free energy difference ΔFw→o=318 kcal/mol. Three adsorption states with local minimum of adsorption free energy are distinguished in the free energy surface-the direct contact type which is similar to previously reported one, the hydrophilic-surface/water/octane type where a thin water layer is sandwiched between the surface and the octane phase, and the oleophilic/water/octane type where a thin water layer also exists. Water molecules in these water layers contribute to stabilize the adsorption states by taking a special orientational order and slow self-diffusion.

Formation of Single Double-Layered Coacervate of Poly(N,N-diethylacrylamide) in Water by a Laser Tweezer.

We demonstrate liquid-liquid phase separation involving both coacervation and coil-to-globule phase transition of a thermoresponsive polymer. By focusing a near-infrared laser beam into an aqueous solution of poly(N-isopropylacrylamide) (PNIPAM), a single phase-separated polymer microdroplet can be formed and stably trapped at the focal point. Such droplet formation is induced by a local elevation in temperature (induced by a photothermal effect) and an optical force. The technique allows us to selectively analyze a single polymer droplet trapped at the focal point. In this study, we applied this technique to poly(N,N-diethylacrylamide) (PDEA) in water and generated a double-layered PDEA droplet. Such an inhomogeneous and complex microstructure has not been previously observed both in steady-state heating of a PDEA solution and in the PNIPAM system. Moreover, we used micro-Raman spectroscopy to clarify that PDEA underwent dehydration due to a coil-to-globule phase transition. Despite this, the polymer concentration (Cpoly) of the trapped PDEA droplet was very low and was around 30 wt %. Cpoly depended on the molecular weight of PDEA and the laser power that regulates the temperature elevation. These results strongly indicate that PDEA undergoes coacervation in addition to a coil-to-globule phase transition. This study will help provide us with a fundamental understanding of the phase separation mechanisms of thermoresponsive polymers.

Microanalysis of Single Poly(N-isopropylacrylamide) Droplet Produced by an Optical Tweezer in Water: Isotacticity Dependence of Growth and Chemical Structure of the Droplet.

Thermoresponsive phase separation mechanisms of aqueous poly(N-isopropylacrylamide) (PNIPAM) solutions were investigated using an optical tweezer combined with a Raman microspectroscope. A near-infrared laser beam (λ = 1064 nm) was focused into the solution to produce and trap a single polymer microdroplet under an optical microscope. The laser beam played two important roles: The first role is to locally heat the solution to induce phase separation in which numerous polymer microdroplets are generated around the focus, while the second one is to collect these microdroplets. Eventually, a single polymer droplet was stably produced and trapped at the focus. Our method enabled us to perform two types of microanalysis for the droplet. Analysis I is real-time monitoring the growth of the polymer droplets by which we can determine the growth rate of droplets. Analysis II is Raman microspectroscopy to reveal chemical components of the droplets. By means of these two analyses, we revealed important phase separation mechanisms in terms of stereoregularity (isotacticity) dependence. From analysis I, we show that droplet growth is governed by the Ostwald ripening mechanism and the growth is accelerated by increasing the isotacticity. From analysis II, we show that the gelation is promoted in the droplet (physical gel formation) with increasing isotacticity. Our technique should be a versatile tool to explore liquid-liquid phase separation mechanisms for various binary solution systems.

Lithium metal deposition/dissolution under uniaxial pressure with high-rigidity layered polyethylene separator.

The effects of mechanical uniaxial pressure and deflection of the separator on the electrochemical deposition of lithium metal were investigated. Instead of dendritic lithium growth without pressure, a much more dense and compact deposition can be achieved when pressure is applied to the cells during the lithium deposition process. This morphology is due to the formation of granular lithium followed by the generation of new lithium nuclei on the cathode surface. The improved lithium plating/stripping behavior in the cells under mechanical pressure yielded a 10% higher coulombic efficiency than cells without pressure. However, the cycle life is shortened with pressures higher than 1.39 MPa; therefore, there is an upper limit for improvement of the electrochemical characteristics near 1.39 MPa. The morphology of electrodeposited lithium becomes flatter with a large amount of electrodeposition under pressure when the number of polyethylene separators is increased to five due to the increase in the stiffness of the layered separators. Furthermore, high coulombic efficiency cycling by pressurization was increased to twice that for one separator sheet. Application of the optimal strength pressure and use of more inflexible separators are thus effective methods to control the microscopic morphology of electrodeposited lithium and improve the cycle performance of the lithium metal anode.

Polymer brush in articular cartilage lubrication: Nanoscale modelling and simulation.

Human knee joints move smoothly under high load conditions due to articular cartilage and synovial fluid. Much attention is paid to the role of proteoglycans. It is suggested that a part of proteoglycan forms aggregate on the cartilage surface, making a polymer brush, which has an important role in lubrication. In order to examine the lubrication mechanism in detail, we constructed a full atom model of a polymer brush system, and carried out a series of molecular dynamics simulations to analyze its frictional properties under constant shear. We use chondroitin 6-sulfate molecules grafted on resilient surface as the polymer brush and water with sodium ions as the synovial liquid. In the steady state, polymers have large deformation and the flow of synovial fluid becomes deviate from the Coutette flow, leading to a drastic reduction of friction. Longer chains have larger reduction.

Dynamics of the Phase Separation in a Thermoresponsive Polymer: Accelerated Phase Separation of Stereocontrolled Poly( N, N-diethylacrylamide) in Water.

We studied the dependence on tacticity of the dynamic phase separation behavior of thermoresponsive poly( N, N-diethylacrylamide) (PDEA) in an aqueous solution. Using a laser temperature-jump technique combined with transient photometry, we determined the time constants of the phase separation and found that both atactic and isotactic-rich PDEAs had fast and slow phase separation processes (τfast and τslow). The fast process (τfast) was independent of the tacticity, irrespective of the concentration. On the other hand, the slow process had a strong dependence on the tacticity. We found the slow phase separation process got considerably faster with increasing isotacticity in dilute solutions. This effect due to the tacticity of the PDEA is totally different from that of poly( N-isopropylacrylamide) and can be explained on the basis of the difference between the hydrophobicity of atactic PDEA and that of isotactic-rich PDEA.

Comparison of endometriotic cysts and ovarian cancer in association with endometriotic cysts.

OBJECTIVE: The aim of this study was to clarify the clinical, laboratory, and imaging findings of ovarian cancer in association with endometriotic cysts by detailed comparison of the findings of benign and malignant tumors. METHODS AND MATERIALS: This was a retrospective study of 138 women who had an operation for ovarian tumors at the Department of Obstetrics and Gynecology of Kochi Health Sciences Center between September 1, 2011, and July 30, 2015. The ovarian tumors were divided into two groups: the benign group (endometriotic cysts) and the malignant group (ovarian cancer in association with endometriotic cysts). RESULTS: Of the 138 patients, 28 had malignant disease, and 110 had benign endometriotic cysts. Patients in the malignant group were significantly older than patients in the benign group. The mean maximum tumor diameter was also significantly larger for the malignant tumors. Unilocular-solid and multilocular-solid type tumors were present in 25.0% and 75.0% of malignant tumors, and in 9.1% and 19.1% of benign tumors, respectively. The mean maximum solid component diameter and height were significantly larger in the malignant tumors than in the benign tumors. The solid components were present on the abdominal side of the cyst wall in 12.5% of benign tumors and in 51.9% of malignant tumors. CONCLUSION: In elderly patients, the presence of large solid components in large endometriotic cysts, especially the abdominal side of the cyst wall, might suggest malignancy. MICRO ABSTRACT: The aim of this study was to clarify the findings of ovarian cancer in association with endometriotic cysts by detailed comparison of the findings of benign and malignant tumors. The presence of solid components in large endometriotic cysts, especially the abdominal side of the cyst wall, might suggest malignancy.

Example of a Fluid-Phase Change Examined with MD Simulation: Evaporative Cooling of a Nanoscale Droplet.

We carried out a series of molecular dynamics simulations in order to examine the evaporative cooling of a nanoscale droplet of a Lennard-Jones liquid. After thermally equilibrating a droplet at a temperature Tini/Tt ≃ 1.2 (Tt is the triple-point temperature), we started the evaporation into vacuum by removing vaporized particles and monitoring the change in droplet size and the temperature inside. As free evaporation proceeds, the droplet reaches a deep supercooled liquid state of T/Tt ≃ 0.7. The temperature was found to be uniform in spite of the fast evaporative cooling on the surface. The time evolution of the evaporating droplet properties was satisfactorily explained with a simple one-dimensional phase-change model. After a sufficiently long run, the supercooled droplet was crystallized into a polycrystalline fcc structure. The crystallization is a stochastic nucleation process. The time and the temperature of inception were evaluated over 42 samples, which indicate the existence of a stability limit.

An Invasive Lepidic Predominant Adenocarcinoma Extensively Involving the Lung with Areas of Sarcomatoid Carcinoma Containing Osteoclast-like Giant Cells.

Primary lung tumor tissue exhibiting numerous multinucleated osteoclast-like giant cells (OGCs) is an extremely rare histological type. In this study, we describe the case of an 82-year-old woman. Chest CT demonstrated an extensive crazy-paving appearance in both of the lung fields and a solid round mass in the right lower lobe. A pathological examination of the tumor revealed sarcomatoid carcinoma containing OGCs combined with diffused, invasive lepidic predominant adenocarcinoma. We herein present an extremely rare lung cancer, invasive lepidic predominant adenocarcinoma extensively involving the lung with areas of sarcomatoid carcinoma containing OGCs.

High-efficiency thin and compact concentrator photovoltaics with micro-solar cells directly attached to a lens array.

We propose a thin and compact concentrator photovoltaic (CPV) module, about 20 mm thick, one tenth thinner than those of conventional CPVs that are widely deployed for mega-solar systems, to broaden CPV application scenarios. We achieved an energy conversion efficiency of 37.1% at a module temperature of 25 °C under sunlight irradiation optimized for our module. Our CPV module has a lens array consisting of 10 mm-square unit lenses and micro solar cells that are directly attached to the lens array, to reduce the focal length of the concentrator and to reduce optical losses due to reflection. The optical loss of the lens in our module is about 9.0%, which is lower than that of conventional CPV modules with secondary optics. This low optical loss enables our CPV module to achieve a high energy conversion efficiency.

[Objective and subjective measures of sleep of shift-working nurses].

OBJECTIVES: To objectively evaluate sleep quality of shift-working nurses, we used an Actiwatch 2, a watch-like actigraphy device designed to measure sleep and wakefulness based on the amount of movement. Subjective sleep quality was also assessed using the St. Mary's Hospital Sleep Questionnaire. METHODS: Nineteen shift-working nurses wore the Actiwatch 2 for 5 days. The monitoring began with 2 days of the morning shift, which were followed by a 16-hour night shift and a rest day. Sleep recordings were obtained four times: night sleep after the second morning shift ("sleep 1"), napping on the night shift ("nap 1"), daytime napping after the night shift ("nap 2") and night sleep after the night shift ("sleep 2"). Actiwatch 2 sleep measures include sleep onset latency, snooze time, sleep efficiency, and percent sleep. In addition, the perceived quality of sleep was obtained using five questions of the St. Mary's Hospital Sleep Questionnaire. Objective and subjective sleep quality were compared between different sleep/nap times: sleep 1 vs. sleep 2, and nap 1 vs. nap 2. RESULTS: Percent sleep of sleep 2 was higher than that of sleep 1. In almost all responses to the St. Mary's Hospital Sleep Questionnaire, the perceived quality of sleep on sleep 2 was better than those of sleep 1, and that of nap 2 was better than nap 1. A significant negative correlation was found between the perceived sleep quality of nap 2 and the characteristics of participants (age, number of children, and length of career). There were positive correlations between the perceived sleep quality of sleep and percent sleep, and between the perceived sleep quality of nap and sleep efficiency. Moreover, the perceived sleep quality of nap 2 tended to decrease in participants whose bedtime deviated from the mean value on morning shift days and the rest day. CONCLUSIONS: We found that perceived sleep quality is related to percent sleep, and that the perceived sleep quality of nap is related to sleep efficiency. The results suggest that improving the sleep quality of daytime napping after the night shift is necessary for nurses with children, and that keeping a regular bedtime is necessary to improve the sleep quality of napping on the night shift.