Observation of Highly Anisotropic Thermal Expansion of Polymer Films.

While dimensional change under thermal loading dictates various device failure mechanisms in soft materials, the interplay between microstructures and thermal expansion remains underexplored. Here, we develop a novel method to directly probe the thermal expansion for nanoscale polymer films using an atomic force microscope as well as confining active thermal volume. In a model system, spin-coated poly(methyl methacrylate), we find that the in-plane thermal expansion is enhanced by 20-fold compared to that along the out-of-plane directions in confined dimensions. Our molecular dynamics simulations show that the collective motion of side groups along backbone chains uniquely drives the enhancement of thermal expansion anisotropy of polymers in the nanoscale limit. This work unveils the intimate role of the microstructure of polymer films on its thermal-mechanical interaction, paving a route to judiciously enhance the reliability in a broad range of thin-film devices.

MALDI-MS analysis of disaccharide isomers using graphene oxide as MALDI matrix.

Disaccharides are sugars composed of two monosaccharides joined by a glycosidic linkage. The specific properties of a disaccharide depend on the type of the glycosidic linkage and the identity of the two component monosaccharides. In this work, seven disaccharide isomers (gentiobiose, isomaltose, melibiose, lactose, maltose, cellobiose, and sucrose) were analyzed by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) using a graphene oxide matrix. Each disaccharide was identified by its unique cleavage pattern. To determine the feasibility of quantitative analyses based on specific fragment patterns, mixtures of sucrose with cellobiose or maltose were prepared at different ratios and analyzed by MALDI-MS, where a strong linear correlation was observed between the relative peak intensity of the sucrose fragment peak at m/z 185 and the amount of sucrose in the mixture. The calibration curve was successfully applied to obtain the relative amount of maltose and sucrose in four different honey samples.

Assessment of PM2.5-bound nitrogen-containing organic compounds (NOCs) during winter at urban sites in China and Korea.

In this study, ambient fine particles (PM2.5) were collected in two urban cities in China and Korea (Beijing and Gwangju, respectively) simultaneously in January 2018. Analysis of the nonpolar and semipolar organic matter (OM) using atmospheric pressure photoionization (APPI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) revealed that compounds containing only C, H, and O (CHO) and those containing C, H, O, and N (CHON) accounted for more than 90% of the total intensity of the OM peaks. Higher proportions of CHON compounds were observed during days with abnormally high PM2.5 concentrations at both sites than on regular or non-event days. The proportion of CHON species at the Beijing site was not correlated with secondary ionic species (i.e., NO3-, SO42-, and NH4+) or gaseous components (i.e., O3, NO2, and SO2). In contrast, the proportion of CHON species at the Gwangju site was positively correlated with the concentrations of particulate nitrate and ammonium ions, assuming that ambient ammonium nitrate plays a role in the atmospheric formation of nitrogen-containing organic compounds (NOCs) at the Gwangju site and that Gwangju is more strongly influenced by secondary aerosols than Beijing is. In particular, a significant proportion of the compounds observed at the Beijing site contained only C, H and N (CHN), while negligible amounts of CHN were detected at the Gwangju site. The CHN species in Beijing were identified as quinoline compounds and the corresponding -CH2 homologous series using complementary GC × GC-TOF MS analysis. These results suggest that NOCs and their -CH2 homologous series from primary emissions may be significant contributors to nonpolar and semipolar OM during winter in Beijing, while NOCs with high oxidation states, likely formed via ambient-phase nitrate-mediated reactions, may be the dominant OM constituents in Gwangju.

Compartmentalized Arrays of Matrix Droplets for Quantitative Mass Spectrometry Imaging of Adsorbed Peptides.

Mass spectrometry imaging (MSI) based on matrix-assisted laser desorption/ionization (MALDI) provides information on the identification and spatial distribution of biomolecules. Quantitative analysis, however, has been challenging largely due to heterogeneity in both the size of the matrix crystals and the extraction area. In this work, we present a compartmentalized elastomeric stamp for quantitative MALDI-MSI of adsorbed peptides. Filling the compartments with matrix solution and stamping onto a planar substrate extract and concentrate analytes adsorbed in each compartment into a single analyte-matrix cocrystal over the entire stamped area. Walls between compartments help preserve spatial information on the adsorbates. The mass intensity of the cocrystals directly correlates with the surface coverage of analytes, which enables not only quantitative analysis but estimation of an equilibrium constant for the adsorption. We demonstrate via MALDI-MSI relative quantitation of peptides adsorbed along a microchannel with varying surface coverages.

In-depth compositional analysis of water-soluble and -insoluble organic substances in fine (PM2.5) airborne particles using ultra-high-resolution 15T FT-ICR MS and GC×GC-TOFMS.

Airborne particulate matter consisting of ionic species, salts, heavy metals and carbonaceous material is one of the most serious environmental pollutants owing to its impacts on the environment and human health. Although elemental and organic carbon compounds are known to be major components of aerosols, information on the elemental composition of particulate matter remains limited because of the broad range of compounds involved and the limits of analytical instruments. In this study, we investigated water-soluble and -insoluble organic compounds in fine (PM2.5) airborne particles collected during winter in Korea to better understand the elemental compositions and distributions of these compounds. To collect ultra-high-resolution mass profiles, we analyzed water-soluble and -insoluble organic compounds, extracted with water and dichloromethane, respectively, using an ultra-high-resolution 15 T Fourier transform ion cyclotron resonance (15T FT-ICR) mass spectrometer in positive ion mode (via both electrospray ionization [ESI] and atmospheric pressure photoionization [APPI] for water-extracts and via APPI for dichloromethane-extracts). In conjunction with the FT-ICR mass spectrometry (MS) data, subsequent two-dimensional gas chromatography time-of-flight mass spectrometry (GC×GC-TOFMS) data were used to identify potentially hazardous organic components, such as polycyclic aromatic hydrocarbons. This analysis provided information on the sources of ambient particles collected during winter season and partial evidence of contributions to the acidity of organic content in PM2.5 particles. The compositional and structural features of water-soluble and -insoluble organic compounds from PM2.5 particles are important for understanding the potential impacts of aerosol-carried organic substances on human health and global ecosystems in future toxicological studies.

Metabolite profiling study on the toxicological effects of polybrominated diphenyl ether in a rat model.

Polybrominated diphenyl ethers (PBDEs) are commonly used to retard the combustion of materials such as foam padding, textiles, or plastics, and numerous studies have confirmed the accumulation thereof in the environment and in fish, mammals, and humans. In this study, we used metabolomics to conduct an environmental risk assessment of the PBDE-209. We profiled the urinary metabolites of control and PBDE-treated rats (exposed to PBDE-209) using nuclear magnetic resonance (NMR) and mass spectrometry (MS). Global metabolic profiling indicated that the effects of PBDE-209 on the urinary metabolic profile were not significant. However, targeted metabolic profiling revealed progressive effects of PBDE-209 over a 7-day PBDE-209 treatment. Moreover, despite the weak PBDE-209 effects, we observed that choline, acetylcholine, 3-indoxylsulfate, creatinine, urea, and dimethyl sulfone levels were decreased, whereas that of pyruvate was significantly increased. Furthermore, we suggest that the increased pyruvate level and decreased levels of choline, acetylcholine, and uremic toxins were suggestive of endocrine disruption and neurodevelopmental toxicity caused by PBDEs. © 2016 Wiley Periodicals, Inc. Environ Toxicol 32: 1262-1272, 2017.

Evaluation of the accuracy of dose delivery for IMRT based on transit dosimetry.

The authors have developed and evaluated a new method that uses transit dose in the treatment room in verification of dose delivery to patients. Five intensity modulated radiotherapy (IMRT) plans were selected from actual cancer patients, and transit dose was measured using MapCHECK 2 and an anthropomorphic phantom. The criteria used as a verification tool for the dose delivery to the patient were gamma-index-based dose comparison between the computed dose and measured dose. When the doses were delivered to an anthropomorphic phantom normally, the average passing rate was 95.2% based on a gamma index analysis. This feasibility study suggested that transit dose-based quality assurance can provide information about the accuracy of an inhomogeneity correction algorithm and patient positioning during treatment, allowing its use as a verification tool for actual dose delivery to patients in the treatment room.

1H-NMR-based profiling of organic components in leachate from animal carcasses disposal site with time.

Leachate, generated by the decomposition of animal carcasses, presents many environmental, sanitary, and food safety hazards. However, research on the characteristics of leachate is lacking. In this study, we performed biochemical profiling of leachate from two animal species (pig and cattle) in two soil types (sandy loam and sandy soil) using (1)H-NMR-based profiling, followed by multivariate data analysis. The leachate was collected from a well-controlled artificial burial site over a 31-week period. Principal components analysis (PCA) of the NMR data showed similar patterns between species and soil types. Organic components, including organic acids and phenols, predominated, and their levels increased with time. The methylamine level in leachate from pig carcasses 18 weeks following burial was significantly higher than that from cattle carcasses; leachate from cattle carcasses in sandy soil 1 week after burial contained unique components (specifically ethanol, formate, alanine, N-methylation, and taurine), in contrast with those from sandy loam soil. This study suggests that a NMR-based profiling approach is useful to characterize the organic components in leachate from animal carcasses over time.

A simplified analysis of dimethylarsinic acid by wavelength dispersive X-ray fluorescence spectrometry combined with a strong cation exchange disk.

Dimethylarsinic acid (DMA(V)) was pre-concentrated from water samples using a strong cation exchange (SCX) disk functionalized with sulfonic groups, before being analyzed by wavelength dispersive X-ray fluorescence spectrometry (WDXRF). The adsorption of DMA(V) occurred preferentially on the surface of the SCX disk, regardless of pH levels, probably due to interactions with the sulfonic functional groups. However, no other arsenic species, such as arsenate (iAs(V)), arsenite (iAs(III)), and monomethylarsonic acid (MMA(V)), were retained. The SCX-WDXRF method produced a strongly linear calibration curve (R(2)=0.9996) with its limit of detection at 0.218 µgL(-1) when a one-liter water sample was used for pre-concentration. The As intensity of the system was sensitive to the Pb content retained on the SCX disk owing to the proximity of the As-Kα and Pb-Lα lines. To compensate for this interference, a correction factor was developed by considering the calibration slope ratio between the X-ray intensity measured at a Bragg angle of 48.781° and the Pb content of the SCX disks. The results of spike tests for iAs(V), iAs(III), MMA(V), and DMA(V) with and without the addition of Pb in synthetic landfill leachate exhibited reasonable recoveries (i.e., 98-105%) after the spectral adjustment for the Pb interference.

Health-related quality of life with KDQOL-36 and its association with self-efficacy and treatment satisfaction in Korean dialysis patients.

BACKGROUND AND OBJECTIVES: This study was conducted to measure the level of health-related quality of life (HRQOL) and to reveal the association of self-efficacy and treatment satisfaction with it in Korean dialysis patients. DESIGN, SETTING, PARTICIPANTS, AND MEASUREMENTS: The study subjects were 237 patients receiving either hemodialysis (HD) or peritoneal dialysis (PD) from two university hospitals, from February to June in 2010. We investigated HRQOL using the Korean version of Kidney Disease Quality of Life Short Form 36 (KDQOL-36), and self-efficacy and treatment satisfaction by self-administrative questionnaire and their dialysis-related variables by reviewing clinical records. The associations of self-efficacy and treatment satisfaction with HRQOL were assessed using multiple linear regression analysis. RESULTS: The mean HRQOL results were as follows: Physical component score (PCS) was 39.1 ± 8.5, Mental component score (MCS) 44.6 ± 6.8, symptom/problem list was 67.6 ± 17.1, effects of disease score was 58.5 ± 19.6, and burden of disease score was 41.1 ± 28.4. Between PD and HD patients, we could find significant difference only in the symptom/problem list. After removing confounder's effects by multivariate analysis, respectively, treatment goal self-efficacy and treatment management self-efficacy were significantly related with all 5 domains, except PCS. Treatment satisfaction was significantly related with PCS, MCS, and effects of kidney disease. CONCLUSIONS: Patients' self-efficacy and treatment satisfaction could influence their HRQOL. Regular and systematic monitoring using KDQOL-36 and interventions to increase self-efficacy and treatment satisfaction should be considered in dialysis care in Korea.

Characterizing the effect of heavy metal contamination on marine mussels using metabolomics.

Marine mussels (Mytilus) are widely used as bioindicators to measure pollution in marine environments. In this study, (1)H NMR spectroscopy and multivariate statistical analyses were used to differentiate mussel groups from a heavy metal-polluted area (Onsan Bay) and a clean area (Dokdo area). Principal component analysis and orthogonal projection to latent structure-discriminant analysis revealed significant separation between extracts of mussels from Onsan Bay and from the Dokdo area. Organic osmolytes (betaine and taurine) and free amino acids (alanine, arginine, glutamine, phenylalanine, and threonine) were more highly accumulated in Onsan Bay mussels compared with Dokdo mussels. These results demonstrate that NMR-based metabolomics can be used as an efficient method for characterizing heavy metal contamination derived from polluted area compared to clean area and to identify metabolites related to environments that are contaminated with heavy metals.

Lanostane triterpenes from the fruiting bodies of Ganoderma lucidum and their inhibitory effects on adipocyte differentiation in 3T3-L1 Cells.

Four new lanostane triterpenes, butyl ganoderate A (1), butyl ganoderate B (2), butyl lucidenate N (3), and butyl lucidenate A (4), were isolated from the fruiting bodies of Ganoderma lucidum together with 14 known compounds (5-18). The structures of the new triterpenes were established by extensive spectroscopic studies and chemical evidence. In addition, the inhibitory effect of isolated compounds on adipocyte differentiation in 3T3-L1 cells was examined.

Randomized trial to compare the dosage of darbepoetin alfa by administration route in haemodialysis patients.

AIM: The doses of darbepoetin alfa required to maintain target haemoglobin levels after s.c. or i.v. administration when recombinant human erythropoietin (rHuEpo) treatment was replaced by darbepoetin alfa treatment in haemodialysis (HD) patients were compared. METHODS: In this prospective, randomized, open-label study, 65 HD patients who were receiving stable SC doses of rHuEpo were switched to an equivalent dose of darbepoetin alfa at a reduced frequency by s.c. or i.v. administration. Patients were randomly assigned to the s.c. group (n = 32) or the i.v. group (n = 33). Darbepoetin alfa doses were titrated to maintain target haemoglobin levels of 8.0-11.0 g/dL for up to 24 weeks. A period of 20 weeks was used for dose titration and haemoglobin stabilization. This was followed by a 4 week evaluation period. RESULTS: The mean haemoglobin concentration during the evaluation period was similar in the s.c. and i.v. groups. The mean dose and mean weight-standardized dose of darbepoetin alfa during the evaluation period tended to be lower in the s.c. group than the i.v. group, although these differences were not statistically significant. The mean weekly darbepoetin alfa dose requirements during the evaluation period significantly decreased in both groups compared to the dose requirements at randomization. CONCLUSION: There is a possibility that s.c. administration of darbepoetin alfa is more efficacious than i.v. administration, but a definite benefit cannot be demonstrated with the current sample size. A bigger sample size is needed to confirm the result.

Determination of polychlorinated biphenyls in transformer oil using various adsorbents for solid phase extraction.

Various adsorbents for a solid phase extraction (SPE) method were used to study their ability to separate PCBs from transformer oil to rapidly determine their sub-ppm concentration in the transformer oil. Approximately 90% of the transformer oil could be removed from the PCBs by using a hydrophilic-lipophilic balanced copolymer (HLB) adsorbent, but the recovery of deca-chlorobiphenyl (deca-CB) used as a surrogate was only 24.5% due to lose during this cleanup process. The use of a silica adsorbent gave good results with 89.9% recovery of the deca-CB. The recovery of Aroclor 1242 and 1260 were 95.4 and 90.3% on silica, and 98.9 and 83.5% on HLB, respectively. Acid treatment was an essential step in removing the ambiguous interference peaks to help identify the PCBs. A decreased sensitivity of the electron capture detection (ECD) for PCBs was observed due to the presence of the remaining trace oil after the workup procedure. This loss in sensitivity was allowed for by using tetrachloroxylene as an internal standard, and this was found to be reliable for the criteria of quality control by employing an experiment in which LCS was spiked with 2mg/l of Aroclor 1260 and analyzed each day over a 25 day period. The MDL for the analytical method established in this study is 0.05 mg/l.

Difficulty in improving malnutrition and low-grade inflammation in diabetic patients on peritoneal dialysis.

Continuous ambulatory peritoneal dialysis (CAPD) is commonly used for renal replacement therapy in diabetes mellitus (DM) patients. We investigated the changes of peritoneal transport characteristics, nutritional status, and adequacy and inflammation parameters in diabetic CAPD patients (N = 17) compared to non-diabetic patients (N = 23). Peritoneal equilibrium testing, nutritional, biochemical, and anthropometric parameters and adequacy were prospectively assessed at 1 (baseline), 6 and 12 months after initiating CAPD. The levels of several nutritional parameters were lower and did not change in DM patients over time (P < 0.05) and significantly improved in the non-DM patients over time (P < 0.05). Total weekly creatinine clearance and residual renal function exhibited a rapid decline (P < 0.05) and inflammation parameter levels were higher in DM patients (P < 0.05). Our results showed the difficulty in improvement of nutritional status and inflammatory parameters in diabetic patients during at least the first year of CAPD compared to non-DM patients.

In vitro activity of kaempferol isolated from the Impatiens balsamina alone and in combination with erythromycin or clindamycin against Propionibacterium acnes.

The in vitro antibacterial activity against antibiotic-resistant Propionibacterium acnes of kaempferol isolated from the Impatiens balsamina alone and in combination with erythromycin or clindamycin antibiotics was investigated. The antibiotic combination effect against antibiotic-resistant P. acnes was studied by checkerboard test. Kaempferol and quercetin demonstrated antibacterial activities against P. acnes. Minimum inhibitory concentrations (MICs) for both compounds were < or =32 ug/ml and < or =64 ug/ml for clindamycin-sensitive and-resistant P. acnes, respectively. The four combination formulations (kaempferol and either erythromycin or clindamycin; quercetin and either erythromycin or clindamycin) exhibited a synergic inhibition of P. acnes growth. The combination of kaempferol with quercetin showed an indifferent effect. The combination of clindamycin with kaempferol or quercetin showed a greater synergic effect than that of erythromycin with kaempferol or quercetin. Thus, these combinations demonstrated the potential to treat acne.

Preparative isolation of four ginsenosides from Korean red ginseng (steam-treated Panax ginseng C. A. Meyer), by high-speed counter-current chromatography coupled with evaporative light scattering detection.

Ginseng (Panax ginseng C. A. Meyer) has been well known to have a variety of ginsenosides that show diverse biological activities. Especially, the components of ginsenosides are quite different depending on the processing method. Recently, there have been several reports showing that less polar ginsenosides from Korean red ginseng (steam-treated Panax ginseng) have potent biological activities such as radical scavenging, vasodilating and anti-tumor activities. In this study, we have isolated four known ginsenosides Rg3, Rk1, Rg5 and F4 from Korean red ginseng by high-speed counter-current chromatography (HSCCC) coupled with evaporative light scattering detection (ELSD). The enriched saponin fraction (350 mg) was separated by using methylene chloride-methanol-water-isopropanol (6:6:4:1, v/v) as the two-phase solvent system and yielded 28.6 mg of Rg5, 26.6 mg of Rk1, 32.2 mg of Rg3 and 8.1 mg of F4. The purity of these ginsenosides was assessed by HPLC-ELSD to be over 95%, and their structures were characterized by electrospray ionization mass spectrometry (ESI-MS), (1)H NMR and (13)C NMR.

Qualitative and quantitative determination of ten major saponins in Platycodi Radix by high performance liquid chromatography with evaporative light scattering detection and mass spectrometry.

Saponins in Platycodi Radix (platycosides) exhibit potent biological activities in mammalian systems, including several beneficial effects such as anti-inflammatory, immunomodulatory and anti-obesity activities. In this study, we developed a new HPLC separation coupled with evaporative light scattering detector (ELSD) for the simultaneous quantitative determination of ten major saponins in Platycodi Radix. Simultaneous separation of these saponins was achieved on a C18 analytical column. The mobile phase consisted of a gradient of aqueous acetonitrile. The method was validated for linearity, precision, accuracy, limit of detection and quantification. Electrospray ionization mass spectrometry (ESI-MS) and liquid chromatography coupled with on-line mass spectrometry (LC-ESI MS/MS) were applied to identify platycosides in the purified fractions and in the crude extract. Under ESI-MS/MS conditions, the fragmentation patterns of [M-H]- ions exclusively show signals corresponding to cleavage of the glycosidic bonds, thus allowing a rapid identification of saponins in the crude extract of Platycodi Radix. The validated HPLC method provides a new basis of overall assessment on quality of Platycodi Radix, and ESI-MS/MS and LC-ESI MS/MS approaches offers analytical tools for a rapid screening of platycosides in the crude extract.