Influence of mobile phase composition on the analytical sensitivity of LC-ESI-MS/MS for the concurrent analysis of bisphenols, parabens, chlorophenols, benzophenones, and alkylphenols.

Phenols are significant environmental endocrine disruptors that can have adverse health effects on exposed individuals. Correlating phenol exposure to potential health implications requires the development of a comprehensive and sensitive analytical method capable of analyzing multiple phenols in a single sample preparation and analytical run. Currently, no such method is available for multiple classes of phenols due to electrospray ionization (ESI) limitations in concurrent ionization and lack of sensitivity to certain phenols, particularly alkylphenols. In this study, we investigated the influence of mobile phase compositions in ESI on concurrent ionization and analytical sensitivity of liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) during the analysis of multiple classes of phenols, and we propose a comprehensive and sensitive analytical method for various classes of phenols (i.e., bisphenols, parabens, benzophenones, chlorophenols, and alkylphenols). The proposed method was affected by 0.5 mM ammonium fluoride under methanol conditions. It enabled the concurrent ionization of all the phenols and significantly improved the analytical sensitivity for bisphenols and alkylphenols, which typically have poor ionization efficiency. This method, combined with a "dilute and shoot" approach, allowed us to simultaneously quantify 38 phenols with good chromatographic behavior and sensitivity. Furthermore, the method was successfully applied to the analysis of 61 urine samples collected from aquatic (swimming) and land (indoor volleyball and outdoor football) athletes.

Broadband tuning of ring-type cavity-dumped femtosecond optical parametric oscillator in the near-infrared.

We report a cavity-dumped optical parametric oscillator (OPO) with a ring-type cavity configuration, which is based on periodically poled lithium niobate gain synchronously pumped by a mode-locked Ti:sapphire laser. Because of reduced cavity loss and group velocity dispersion inherent to ring-cavity employment, a wide wavelength tuning capability from 1.02 to 1.65 µm was achieved by the simple displacement of a cavity mirror. At a wavelength of 1.28 µm, the cavity-dumped system provides femtosecond pulses with 42 nJ energy and 50% dumping efficiency. The group delay dispersion (GDD) of the OPO cavity could be characterized through the wavelength tuning behavior with cavity displacement, and its validity was confirmed by the numerical GDD calculation of each optical component within the cavity.

Self-consistent dielectric constant determination for monolayer WSe2.

Frequency-dependent dielectric constant dispersion of monolayer WSe2, ε(ω)=ε1(ω)+i Îµ2(ω), was obtained from simultaneously measured transmittance and reflectance spectra. Optical transitions of the trion as well as A-, B-, and C-excitons are clearly resolved in the  Îµ2 spectrum. A consistent Kramers-Kronig transformation between the ε1 and  Îµ2 spectra support the validity of the applied analysis. It is found that the A- and B-exciton splitting in the case of the double-layer WSe2 can be attributed to the spin-orbit coupling, which is larger than that in the monolayer WSe2. In addition, the temperature-induced evolution of the A-exciton energy and its width are explained by model equations with electron-phonon interactions.

Direct Probing of the Electronic Structures of Single-Layer and Bilayer Graphene with a Hexagonal Boron Nitride Tunneling Barrier.

The chemical and mechanical stability of hexagonal boron nitride (h-BN) thin films and their compatibility with other free-standing two-dimensional (2D) crystals to form van der Waals heterostructures make the h-BN-2D tunnel junction an intriguing experimental platform not only for the engineering of specific device functionalities but also for the promotion of quantum measurement capabilities. Here, we exploit the h-BN-graphene tunnel junction to directly probe the electronic structures of single-layer and bilayer graphene in the presence and the absence of external magnetic fields with unprecedented high signal-to-noise ratios. At a zero magnetic field, we identify the tunneling spectra related to the charge neutrality point and the opening of the electric-field-induced bilayer energy gap. In the quantum Hall regime, the quantization of 2D electron gas into Landau levels (LL) is seen as early as 0.2 T, and as many as 30 well-separated LL tunneling conductance oscillations are observed for both electron- and hole-doped regions. Our device simulations successfully reproduce the experimental observations. Additionally, we extract the relative permittivity of three-to-five layer h-BN and find that the screening capability of thin h-BN films is as much as 60% weaker than bulk h-BN.

A comparison study of the potential risks induced in arable land and forest soils by carcass-derived pollutants.

Improper decisions concerning animal carcass disposal sites pose grave threats to environmental biosecurity. However, only a few studies have focused on the effects of different land-use types on the composition of carcass-derived pollutants and microbial responses to the disturbances. This study was conducted using soil microcosms with minced pork built from arable land and forest soils for 5 weeks. To compare the risk induced from different land-use types by carcass burial, the soil properties, the microbial community, and multiple-antibiotic-resistant bacteria were evaluated for microcosm containing 0, 1.5 and 7.5 g of minced pork. The abiotic properties, including pH, organic carbon, nitrogen and phosphorus compounds, significantly increased, regardless of the land-use types and applied load masses. The microbial diversity indices of the forest soil were reduced, whereas those of the arable land remained relatively stable. The disturbances produced from carcass-derived pollutants altered the bacterial community structures differently for the different land-use types. The treatment increased multiple-antibiotic-resistant bacteria in the both soil samples, although the increase in the forest soil was significantly less compared to the arable land soils.

Visible-pulse generation in gain crystal of near-infrared femtosecond optical parametric oscillator.

An optical parametric oscillator (OPO) based on magnesium-oxide-doped periodically poled lithium niobate (MgO:PPLN) is demonstrated to deliver visible femtosecond pulses, which were created through the intra-cavity nonlinear interactions within the PPLN itself. The signal from the OPO produces femtosecond pulses in the near-infrared region tunable from 1050 to 1600 nm. Visible femtosecond pulses in the range of 522-800 nm and those of 455-540 nm, respectively, were generated via second-harmonic generation (SHG) of signal photons and through sum-frequency generation (SFG) of pump and signal photons. Maximum output efficiencies of 9.2% at 614 nm and 8.0% at 522 nm for the SHG and SFG are attained, respectively, where the efficient visible pulse generation relies on the quasi-phase matching with the aid of the higher-order grating momentum.

Strong optical modulation of surface plasmon polaritons in metal/semiconductor nanostructures.

We demonstrate strong modulation of the transmission around the surface plasmon polariton (SPP) resonance in metal/semiconductor hybrid nanostructures based on Ag film on top of InGaAs. The change in the real and imaginary parts of the refractive index due to photoexcited carriers in InGaAs generates a shift in the SPP resonance and enhanced transmission near the SPP resonance. Temporal evolution of the complex refractive index was traced by comparing the transient transmission with finite-difference time-domain (FDTD) simulations.

Optimization for the removal of orthophosphate from aqueous solution by chemical precipitation using ferrous chloride.

The precipitation reaction between the orthophosphate and Fe2+ ions was studied to describe the optimum condition for the removal of orthophosphate from the aqueous solution. The effects of pH, Fe:P molar ratio, and alkalinity were evaluated for the initial orthophosphate concentrations in the range from 1.55 to 31.00 mg/L - PO4(3-) -P. The optimum pH was found to be 8.0 in all orthophosphate concentration ranges. When the stoichiometric moles of Fe2+ were added, the removal efficiencies were significantly less than the theoretical values. It is likely that the precipitation of Fe(OH)2(s) is partially formed. For the initial orthophosphate concentration of 3.10 mg/L PO4(3-) -P or greater, the removal efficiencies with the Fe:P molar ratio of 3.0:1.0 approached to the theoretical values, yielding greater than 98.5%. If the molar ratio of Fe:P was great enough, the precipitation reaction was completed within 1 h. As the alkalinity increases, the experimental removal efficiencies were significantly greater than the theoretical values. This is because the formation of vivianite is favoured over FeCO3(s). Finally, it was demonstrated that the orthophosphate (1.40-6.80 mg/L PO4(3-) -P) in the secondary effluents from wastewater treatment plants was effectively removed by dosing sufficient amount of Fe2+ ions.

Comprehensive phenotypic assessment of nonsense mutations in mitochondrial ND5 in mice.

Mitochondrial dysfunction induced by mitochondrial DNA (mtDNA) mutations has been implicated in various human diseases. A comprehensive analysis of mitochondrial genetic disorders requires suitable animal models for human disease studies. While gene knockout via premature stop codons is a powerful method for investigating the unique functions of target genes, achieving knockout of mtDNA has been rare. Here, we report the genotypes and phenotypes of heteroplasmic MT-ND5 gene-knockout mice. These mutant mice presented damaged mitochondrial cristae in the cerebral cortex, hippocampal atrophy, and asymmetry, leading to learning and memory abnormalities. Moreover, mutant mice are susceptible to obesity and thermogenetic disorders. We propose that these mtDNA gene-knockdown mice could serve as valuable animal models for studying the MT-ND5 gene and developing therapies for human mitochondrial disorders in the future.

Localized coherent phonon generation in monolayer MoSe2 from ultrafast exciton trapping at shallow traps.

We report spectroscopic evidence for the ultrafast trapping of band edge excitons at defects and the subsequent generation of defect-localized coherent phonons (CPs) in monolayer MoSe2. While the photoluminescence measurement provides signals of exciton recombination at both shallow and deep traps, our time-resolved pump-probe spectroscopy on the sub-picosecond time scale detects localized CPs only from the ultrafast exciton trapping at shallow traps. Based on occupation-constrained density functional calculations, we identify the Se vacancy and the oxygen molecule adsorbed on a Se vacancy as the atomistic origins of deep and shallow traps, respectively. Establishing the correlations between the defect-induced ultrafast exciton trapping and the generation of defect-localized CPs, our work could open up new avenues to engineer photoexcited carriers through lattice defects in two-dimensional materials.

Individual and Co-Expression Patterns of FAM83H and SCRIB at Diagnosis Are Associated with the Survival of Colorectal Carcinoma Patients.

Background: FAM83H is important in teeth development; however, an increasing number of reports have indicated a role for it in human cancers. FAM83H is involved in cancer progression in association with various oncogenic molecules, including SCRIB. In the analysis of the public database, there was a significant association between FAM83H and SCRIB in colorectal carcinomas. However, studies evaluating the association of FAM83H and SCRIB in colorectal carcinoma have been limited. Methods: The clinicopathological significance of the immunohistochemical expression of FAM83H and SCRIB was evaluated in 222 colorectal carcinomas. Results: The expressions of FAM83H and SCRIB were significantly associated in colorectal carcinoma tissue. In univariate analysis, the nuclear expressions of FAM83H and SCRIB and the cytoplasmic expression of SCRIB were significantly associated with shorter survival of colorectal carcinomas. The nuclear expressions of FAM83H and SCRIB and the cytoplasmic expression of SCRIB were independent indicators of shorter cancer-specific survival in multivariate analysis. A co-expression pattern of nuclear FAM83H and cytoplasmic SCRIB predicted shorter cancer-specific survival (p < 0.001) and relapse-free survival (p = 0.032) in multivariate analysis. Conclusions: This study suggests that FAM83H and SCRIB might be used as prognostic markers of colorectal carcinomas and as potential therapeutic targets for colorectal carcinomas.

Optimization and comparison of methane production and residual characteristics in mesophilic anaerobic digestion of sewage sludge by hydrothermal treatment.

Anaerobic digestion is the preferred method for treating sewage sludge because of its ability to reduce sludge volume and produce biogas. However, conventional anaerobic digestion has a long retention time and low degradation rate. In recent years, hydrothermal treatment has been used to improve the hydrolysis of sewage sludge and biogas production. This process tends to focus on maximizing biogas production. However, very little research has been done on anaerobic digestion residues. In this study, batch experiments were conducted to investigate the effect of hydrothermal temperature on methane production and the contents of liquid fraction after anaerobic digestion (centrate). Experimental conditions were designed using a response surface method and central composite model. A quadratic equation was used to interpret the individual and interactive effects of hydrothermal conditions on anaerobic digestion. Given the maximum biogas production and the minimum concentrate concentration, the optimal operating condition was determined by a 186 °C hydrothermal temperature and a reaction time of 106 min. Under these conditions, the following results could be obtained: methane production (200.5 ± 7.7 mL-CH4/gVSadded), TCOD (16,572 ± 348 mg/L), sCOD (1240 ± 65 mg/L), sTN (658.9 ± 8.0 mg/L) and ammonia (525 ± 27 mg/L).

Fluoride-assisted liquid chromatography-tandem mass spectrometry method for simultaneous analysis of propofol and its metabolites without derivatization in urine.

The misuse of propofol for recreational purposes has become a serious social issue. Accordingly, practical and sensitive analytical methods to investigate the chronic abuse and toxicity of propofol are required. However, current propofol determination methods using liquid chromatography-mass spectrometry (LC-MS/MS) suffer from problems associated with loss in sample preparation due to its volatility and its poor ionization efficiency and collision-induced dissociation in mass spectrometry. Herein, we have developed a sensitive and accurate fluoride-assisted LC-MS/MS method combined with direct-injection for propofol determination. Ionization via fluoride-ion attachment/induced deprotonation, effected by ammonium fluoride in the mobile phase, was found to dramatically improve the sensitivity of propofol without derivatization. Furthermore, direct injection without derivatization enables the simultaneous analysis of propofol and its phase II metabolites without analyte loss. The optimal concentration of ammonium fluoride in the mobile phase was found to be 1 mM under methanol conditions. The linearity is good (R2 ≥ 0.999) and the intra- and inter-day precisions for propofol determination are between 1.9 and 8.7%. The accuracies range from 87.5% to 105.4% and the limits of detection and quantitation for propofol in urine are 0.15 and 0.44 ng mL-1, respectively. The present method was successfully applied to human urine and showed a sufficient sensitivity to determine propofol and five phase II metabolites over 48 h in human urine after administration. Consequently, the fluoride-assisted LC-MS/MS method was demonstrated to be sensitive, accurate, and practical for the determination of propofol and its metabolites.

Valley depolarization in monolayer transition-metal dichalcogenides with zone-corner acoustic phonons.

Although single-layer transition-metal dichalcogenides with novel valley functionalities are a promising candidate to realize valleytronic devices, the essential understanding of valley depolarization mechanisms is still incomplete. Based on pump-probe experiments performed for MoSe2 and WSe2 monolayers and corroborating analysis from density functional calculations, we demonstrate that coherent phonons at the K-point of the Brillouin zone can effectively mediate the valley transfer of electron carriers. In the MoSe2 monolayer case, we identify this mode as the flexural acoustic ZA(K) mode, which has broken inversion symmetry and thus can enable electron spin-flip during valley transfer. On the other hand, in the monolayer WSe2 case where spin-preserving inter-valley relaxations are preferred, coherent LA(K) phonons with even inversion symmetry are efficiently generated. These findings establish that while the specifics of inter-valley relaxations depend on the spin alignments of energy bands, the K-point phonons should be taken into account as an effective valley depolarization pathway in transition metal dichalcogenide monolayers.

Effective Photoluminescence Imaging of Bubbles in hBN-Encapsulated WSe2 Monolayer.

Interfacial bubbles are unintentionally created during the transfer of atomically thin 2D layers, a required process in the fabrication of van der Waals heterostructures. By encapsulating a WSe2 monolayer in hBN, we study the differing photoluminescence (PL) properties of the structure resulting from bubble formation. Based on the differentiated absorption probabilities at the bubbles compared to the pristine areas, we demonstrate that the visibility of the bubbles in PL mapping is enhanced when the photoexcitation wavelength lies between the n = 1 and n = 2 resonances of the A-exciton. An appropriate choice of detection window, which includes localized exciton emission but excludes free exciton emission, further improves bubble imaging capability. The interfacial position dependence of the bubbles, whether they are located above or below the WSe2 monolayer, gives rise to measurable consequences in the PL shape.

Spectroscopic studies of atomic defects and bandgap renormalization in semiconducting monolayer transition metal dichalcogenides.

Assessing atomic defect states and their ramifications on the electronic properties of two-dimensional van der Waals semiconducting transition metal dichalcogenides (SC-TMDs) is the primary task to expedite multi-disciplinary efforts in the promotion of next-generation electrical and optical device applications utilizing these low-dimensional materials. Here, with electron tunneling and optical spectroscopy measurements with density functional theory, we spectroscopically locate the mid-gap states from chalcogen-atom vacancies in four representative monolayer SC-TMDs-WS2, MoS2, WSe2, and MoSe2-, and carefully analyze the similarities and dissimilarities of the atomic defects in four distinctive materials regarding the physical origins of the missing chalcogen atoms and the implications to SC-mTMD properties. In addition, we address both quasiparticle and optical energy gaps of the SC-mTMD films and find out many-body interactions significantly enlarge the quasiparticle energy gaps and excitonic binding energies, when the semiconducting monolayers are encapsulated by non-interacting hexagonal boron nitride layers.

Broadband Surface Plasmon Lasing in One-dimensional Metallic Gratings on Semiconductor.

We report surface plasmon (SP) lasing in metal/semiconductor nanostructures, where one-dimensional periodic silver slit gratings are placed on top of an InGaAsP layer. The SP nature of the lasing is confirmed from the emission wavelength governed by the grating period, polarization analysis, spatial coherence, and comparison with the linear transmission. The excellent performance of the device as an SP source is demonstrated by its tunable emission in the 400-nm-wide telecom wavelength band at room temperature. We show that the stimulated emission enhanced by the Purcell effect enables successful SP lasing at high energies above the gap energy of the gain. We also discuss the dependence of the lasing efficiency on temperature, grating dimension, and type of metal.

Coherent Lattice Vibrations in Mono- and Few-Layer WSe2.

We report the observation of coherent lattice vibrations in mono- and few-layer WSe2 in the time domain, which were obtained by performing time-resolved transmission measurements. Upon the excitation of ultrashort pulses with the energy resonant to that of A excitons, coherent oscillations of the A1g optical phonon and longitudinal acoustic phonon at the M point of the Brillouin zone (LA(M)) were impulsively generated in monolayer WSe2. In multilayer WSe2 flakes, the interlayer breathing mode (B1) is found to be sensitive to the number of layers, demonstrating its usefulness in characterizing layered transition metal dichalcogenide materials. On the basis of temperature-dependent measurements, we find that the A1g optical phonon mode decays into two acoustic phonons through the anharmonic decay process.

Vibrational Properties of h-BN and h-BN-Graphene Heterostructures Probed by Inelastic Electron Tunneling Spectroscopy.

Inelastic electron tunneling spectroscopy is a powerful technique for investigating lattice dynamics of nanoscale systems including graphene and small molecules, but establishing a stable tunnel junction is considered as a major hurdle in expanding the scope of tunneling experiments. Hexagonal boron nitride is a pivotal component in two-dimensional Van der Waals heterostructures as a high-quality insulating material due to its large energy gap and chemical-mechanical stability. Here we present planar graphene/h-BN-heterostructure tunneling devices utilizing thin h-BN as a tunneling insulator. With much improved h-BN-tunneling-junction stability, we are able to probe all possible phonon modes of h-BN and graphite/graphene at Γ and K high symmetry points by inelastic tunneling spectroscopy. Additionally, we observe that low-frequency out-of-plane vibrations of h-BN and graphene lattices are significantly modified at heterostructure interfaces. Equipped with an external back gate, we can also detect high-order coupling phenomena between phonons and plasmons, demonstrating that h-BN-based tunneling device is a wonderful playground for investigating electron-phonon couplings in low-dimensional systems.

A prospective study on the safety of herbal medicines, used alone or with conventional medicines.

ETHNOPHARMACOLOGICAL RELEVANCE: Along with increase of herbal medicine use worldwide, the safety of traditional herbal medicines frequently becomes a medical issue. AIM OF THE STUDY: This study aimed to investigate the incidence of herbal medicine-induced adverse effects on liver functions. SUBJECTS AND METHODS: A prospective study was performed with 313 inpatients (87 male and 226 female) receiving herbal prescriptions during hospitalization. The patients were classified into two groups based on their treatments: one group received herbal medicines only (57 patients), and another received herbal and conventional medicines concurrently (256 patients). All patients were given liver and renal function tests at the start of hospitalization (baseline) and at approximately 2-week intervals thereafter, until discharge. RESULTS: Six of the 313 patients showed abnormal liver function without related clinical symptoms (1.9%, 95% CI 0.38-3.41); none of the patients in the herbal group had abnormal result in liver function tests (0% of 57 patients) while all six had received a combination of herbal and conventional medicines (2.3% of 256 patients, 95% CI 0.46-4.14). CONCLUSION: Our findings indicate that herbal drugs used alone are relatively safe, but the risk for adverse reactions may increase when herbal and conventional drugs are taken concurrently.