Synthesis, Experimental and Density Functional Theory (DFT) Studies on Solubility of Camptothecin Derivatives.

Two camptothecin derivatives, 10-cyclohexyl-7-methyl-20(S)-camptothecin and 7-methyl-10-morpholino-20(S)-camptothecin, were synthesized and their differences in solubility were investigated using four chosen solvent systems. Based on our results, 10-cyclohexyl-7-methyl-20(S)-camptothecin exhibited higher solubilities than 7-methyl-10-morpholino-20(S)-camptothecin in polar aprotic solvents. However, these two camptothecin derivatives did not exhibit apparent differences in solubility between 5% dimethyl sulfoxide (DMSO)/95% normal saline co-solvent system and 5% dimethylacetamide (DMAC)/95% normal saline co-solvent system. To rationalize their differences in solubility, we also tried to perform a DFT-B3LYP study to investigate their interaction with one water molecule.

Study of the Rolling Effect on MoS2-Carbon Fiber Density and Its Consequences for the Functionality of Li-Ion Batteries.

In this study, an electrode slurry composed of molybdenum disulfide (MoS2) and vapor-grown carbon fiber (VGCF) prepared through a solid-phase synthesis method was blade-coated onto copper foil to form a thick film as the anode for lithium-ion batteries. In previously reported work, MoS2-based lithium-ion batteries have experienced gradual deformation, fracture, and pulverization of electrode materials during the charge and discharge cycling process. This leads to an unstable electrode structure and rapid decline in battery capacity. Furthermore, MoS2 nanosheets tend to aggregate over charge and discharge cycles, which diminishes the surface activity of the material and results in poor electrochemical performance. In this study, we altered the density of the MoS2-carbon fiber/Cu foil anode electrode by rolling. Three different densities of electrode sheets were obtained through varying rolling repetitions. Our study shows the best electrochemical performance was achieved at a material density of 2.2 g/cm3, maintaining a capacity of 427 mAh/g even after 80 cycles.

Methylboronic acid MIDA ester (ADM) as an effective additive in electrolyte to improve cathode electrolyte interlayer performance of LiNi0.8Co0.15Al0.05O2 electrode.

We investigated the effectiveness of using methylboronic acid MIDA ester (ADM) as an additive in an electrolyte to enhance the overall electrochemical and material properties of an LNCAO (LiNi0.8Co0.15Al0.05O2) cathode. The cyclic stability of the cathode material measured at 40 °C (@ 0.2 C) showed an enhanced capacity of 144.28 mAh g-1 (@ 100 cycles), a capacity retention of 80%, and a high coulombic efficiency (99.5%), in contrast to these same properties without the electrolyte additive (37.5 mAh g-1, ~ 20%, and 90.4%), thus confirming the effectiveness of the additive. A Fourier transform infrared spectroscopy (FTIR) analysis distinctly showed that the ADM additive suppressed the EC-Li+ ion coordination (1197 cm-1 and 728 cm-1) in the electrolyte, thereby improving the cyclic performance of the LNCAO cathode. The cathode after 100 charge/discharge cycles revealed that the ADM-containing system exhibited better surface stability of the grains in the LNCAO cathode, whereas distinct cracks were observed in the system without the ADM in the electrolyte. A transmission electron microscopy (TEM) analysis revealed the presence of a thin, uniform and dense cathode electrolyte interface (CEI) film on the surface of LNCAO cathode. An operando synchrotron X-ray diffraction (XRD) test identified the high structural reversibility of the LNCAO cathode with a CEI layer formed by the ADM, which effectively maintained the structural stability of the layered material. The additive effectively inhibited the decomposition of electrolyte compositions, as confirmed by X-ray photoelectron spectroscopy (XPS).

The centrifugal viscometer.

In this study, a viscometer, which can measure the viscosity of low-volume liquids (25 µl) within 30 s, was developed on a centrifugal platform. The centrifugal viscometer consists of a disk platform and a motor. Under disk rotation, centrifugal, Coriolis, and viscosity-induced drag forces result in deflection of liquid flow. The viscosity of the liquid sample is determined by the deflection angle of the liquid, which can be examined through image analysis or visual inspection. The viscosities of a series of Newtonian model fluids were tested by the centrifugal viscometer and the results showed good agreement with the ones tested by a conventional rotational viscometer. Since the centrifugal viscometer only requires a motor to function, the microfluidic disk can be produced in large quantities at a low cost through injection molding, and the deflection angle can be detected through visual inspection, it provides an inexpensive, easy to operate, and portable approach to measure low-volume liquid viscosity.

Dietary exposure assessment of methylmercury and polyunsaturated fatty acids in saltwater fish and processed foods among Taiwanese women of child-bearing age and children: A novel core food-matching approach.

Saltwater fish is rich in health-promoting polyunsaturated fatty acids such as eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA). Excessive fish intake may also cause health hazards due to methylmercury (MeHg). A novel dose estimation method was proposed in this study to improve the quality of food matching by considering the usage ratio of cooking and processing methods in sampling design. In total, 39 table-ready samples were specified according to 2-3 common cooking methods, and MeHg and total mercury (THg) were analyzed. The results showed that mercury was detected in 20 samples (LOD = 0.01 µg/g). High MeHg samples included fried-Spanish mackerel (1.23 µg/g), non-cooked shredded swordfish (0.325 µg/g), pan-fried Spanish mackerel (0.248 µg/g), and non-cooked shredded salmon (0.208 µg/g). Consumption data (n = 166,911) were obtained from 24-h recalls in the 2005-2008 Nutrition and Health Surveys in Taiwan (NAHSIT). The average whole-group estimated daily intake (EDI_WG) was 0.018 (7.9% tolerable daily intake, TDI) for women of child-bearing age and 0.031 µg/day per kg body weight (13.6% TDI) for children. However, 95th percentile values (P95) of 90.4% TDI and 185% TDI were estimated for the two consumer-only populations, which have raised public health concerns. The ratio of % TDI to % daily reference intake (% DRI) was used as a risk-benefit (R/B) indicator. The top 4 R/B foods were: tuna sashimi (0.089 and 0.14), non-cooked shredded swordfish (0.033 and 0.052), fried-Spanish mackerel (0.027 and 0.043) and deep-fried fish balls (0.022 and 0.035) in the two perspective populations.

Preferential lattice expansion of polypropylene in a trilayer polypropylene/polyethylene/polypropylene microporous separator in Li-ion batteries.

The abnormal lattice expansion of commercial polypropylene (PP)/polyethylene (PE)/polypropylene (PP) separator in lithium-ion battery under different charging current densities was observed by in-situ X-ray diffraction. Significant lattice changes of both PP and PE were found during the low current density charging. The capacity fading and the resistance value of the cell measured at 0.025 C (5th retention, 92%) is unexpectedly larger than that at 1.0 C (5th retention, 97.3%) from the electrochemical impedance spectroscopic data. High-resolution scanning electron microscopy is employed to witness the pore changes of the trilayered membrane. Density functional theory calculations were used to investigate the mechanism responsible for the irregular results. The calculations revealed that the insertion of Li-ion and EC molecule into PP or PE are thermodynamically favourable process which might explain the anomalous significant lattice expansion during the low current density charging. Therefore, designing a new separator material with a more compact crystalline structure or surface modification to reduce the Li insertion during the battery operation is desirable.

Cyclability evaluation on Si based Negative Electrode in Lithium ion Battery by Graphite Phase Evolution: an operando X-ray diffraction study.

Artificial graphite (FSN) additive is employed as internal structural label for projecting cyclability of Si material native electrode in a mass ratio of Si/FSN = 1.0 in Li ion battery (LIB). Results of operando X-ray diffraction analysis on Si-FSN negative electrode in LIB demonstrate that one can evaluate the lithiation and delithiation affinity of active material by referring phase transition delay of graphite as affected by experimental splits in a formation process of LIB. We prove that a thin layer of surface amorphous structure and residual lattice strain are formed in Si by high energy ball-milling treatment. Those manipulations improve Li intercalation kinetics and thus enabling a capacity fading of less than 10% (from 1860 to 1650 mAhg-1) for Si negative electrode in 50 cycles. Of utmost importance, this study discloses a robust assessment for revealing mechanism on amorphous and strain related silicide formation and predicting cyclability of negative electrode by quantitative phase evolution rate of FSN additive in LIB.

Mechanochemical synthesis of Si/Cu3Si-based composite as negative electrode materials for lithium ion battery.

Mechanochemical synthesis of Si/Cu3Si-based composite as negative electrode materials for lithium ion battery is investigated. Results indicate that CuO is decomposed and alloyed with Si forming amorphous Cu-Si solid solution due to high energy impacting during high energy mechanical milling (HEMM). Upon carbonization at 800 °C, heating energy induces Cu3Si to crystallize in nanocrystalline/amorphous Si-rich matrix enhancing composite rigidity and conductivity. In addition, residual carbon formed on outside surface of composite powder as a buff space further alleviates volume change upon lithiation/delithiation. Thus, coin cell made of C-coated Si/Cu3Si-based composite as negative electrode (active materials loading, 2.3 mg cm-2) conducted at 100 mA g-1 performs the initial charge capacity of 1812 mAh g-1 (4.08 mAh cm-2) columbic efficiency of 83.7% and retained charge capacity of 1470 mAh g-1 (3.31 mAh cm-2) at the end of the 100th cycle, opening a promised window as negative electrode materials for lithium ion batteries.

Freestanding Three-Dimensional CuO/NiO Core-Shell Nanowire Arrays as High-Performance Lithium-Ion Battery Anode.

We demonstrate significant improvement of CuO nanowire arrays as anode materials for lithium ion batteries by coating with thin NiO nanosheets conformally. The NiO nanosheets were designed two kinds of morphologies, which are porous and non-porous. By the NiO nanosheets coating, the major active CuO nanowires were protected from direct contact with the electrolyte to improve the surface chemical stability. Simultaneously, through the observation and comparison of TEM results of crystalline non-porous NiO nanosheets, before and after lithiation process, we clearly prove the effect of expected protection of CuO, and clarify the differences of phase transition, crystallinity change, ionic conduction and the mechanisms of the capacity decay further. Subsequently, the electrochemical performances exhibit lithiation and delithiation differences of the porous and non-porous NiO nanosheets, and confirm that the presence of the non-porous NiO coating can still effectively assist the diffusion of Li+ ions into the CuO nanowires, maintaining the advantage of high surface area, and improves the cycle performance of CuO nanowires, leading to enhanced battery capacity. Optimally, the best structure is validated to be non-porous NiO nanosheets, in contrary to the anticipated porous NiO nanosheets. In addition, considering the low cost and facile fabrication process can be realized further for practical applications.

Sampling design by the core-food approach for the Taiwan total diet study on veterinary drugs.

The core-food (CF) approach, first adopted in the United States in the 1980s, has been widely used by many countries to assess the exposure to dietary hazards at a population level. However, the reliability of exposure estimates (C × CR) depends critically on sampling methods designed for the detected chemical concentrations (C) of each CF to match with the corresponding consumption rate (CR) estimated from the surveyed intake data. In order to reduce the uncertainty of food matching, this study presents a sampling design scheme, namely the subsample method, for the 2016 Taiwan total diet study (TDS) on veterinary drugs. We first combined the four sets of national dietary recall data that covered the entire age strata (1-65+ years), and aggregated them into 307 CFs by their similarity in nutritional values, manufacturing and cooking methods. The 40 CFs pertinent to veterinary drug residues were selected for this study, and 16 subsamples for each CF were designed by weighing their quantities in CR, product brands, manufacturing, processing and cooking methods. The calculated food matching rates of each CF from this study were 84.3-97.3%, which were higher than those obtained from many previous studies using the representative food (RF) method (53.1-57.8%). The subsample method not only considers the variety of food processing and cooking methods, but also it provides better food matching and reduces the uncertainty of exposure assessment.

Investigation of electro-oxidation of methanol and benzyl alcohol at boron-doped diamond electrode: evidence for the mechanism for fouling film formation.

Boron-doped diamond (BDD) and glassy carbon (GC) electrodes are compared for electrochemical oxidation of methanol and benzyl alcohol. Cyclic voltammograms reveal that BDD electrode produces good oxidation signals for both methanol and benzyl alcohol, while GC produces no significant oxidation signal for either methanol or benzyl alcohol. Amperometric measurement of oxidation of methanol and benzyl alcohol on BDD shows development of a fouling film for benzyl alcohol but not for methanol. Prolonged (24 h) polarization of the BDD electrode at +2.0 V in benzyl alcohol generated enough fouling film for investigation by AFM, SEM, Raman, and FTIR techniques. AFM and SEM microscopy images confirm a fouling film confined to the low-lying regions of the polycrystallite BDD surface, indicating that the active sites of benzyl alcohol oxidation are located within these low-lying regions. The fouling material generated in the process of benzyl alcohol oxidation was identified from Raman and FTIR spectroscopy as polyester. Experiments confirm the fouling film can be removed and the electrode surface reactivated by brief polarization at +3.0 V. Amperometric results of concentration dependence confirm the BDD electrode is well suited for quantitative analysis applications of methanol and benzyl alcohol, with recognizable oxidation currents at micromolar concentration levels.

Rutile-type (Ti,Sn)O2 nanorods as efficient anode materials toward its lithium storage capabilities.

A series of rutile-type (Ti,Sn)O2 solid solutions with nanorod architecture were successfully synthesized in this study by varying their calcination temperatures of tin-modified titanium dioxide (Sn/TiO2) nanocomposites under a nitrogen atmosphere. During the delithiation process, the (Ti,Sn)O2 nanorods obtained at 500 °C delivered a specific capacity of about 300 mA h g(-1) and showed minimal capacity fading even at a high current density of 3 A g(-1).