MOTION OF THE ECCENTRIC ELLIPSOID: GYROSCOPIC BALANCE CONDITION AND STABILITY

本文研究了摩擦系数 和偏心距离对偏心椭球体回转平衡的影响,得到了椭球极轴与地面法向夹角 的运动方程,导出了两类稳定解.结果表明摩擦力是椭球能否旋转至直立的必要条件,当 偏心距一定, 摩擦系数 越大其运动至直立所需的时间越短.偏心距阻碍直立现象的出现,摩擦系数 一定,偏心距 越大,其运动至直立所需的时间越长.当偏心距值增大到一定程度,其将无法直立而是至一稳定的角度,并且稳定角度正比于偏心距,偏心距继续增大,将不会出现回转平衡.     

Stable Fluorescence of Green‐Emitting Carbon Nanodots as a Potential Nanothermometer in Biological Media

Temperature measurement in biology and medical diagnostics is of great importance. Herein, a novel carbon nanodot (CND) based fluorescent nanothermometry device for spatially resolved temperature measurements is demonstrated. The fluorescence CNDs are prepared by a simple one‐pot solvothermal method using sucrose as carbon source. Resultant CNDs show stable green fluorescence at 520 nm with high quantum yield (≈6%). The fluorescence of resultant CNDs exhibits a reversible linear response to temperature in a wide range of 20–85 °C. Moreover, the temperature resolution better than 0.5 °C and high sensitive variation of ≈1.3% °C^?1 are observed in a broad physiological temperature range of 20–40 °C. Therefore, the as‐prepared CNDs possess high water solubility, stable fluorescence, small size, and good biocompatibility, which make them promising candidate for thermometry and cell imaging in biological media.     

基于烷基酰胺双羧酸盐表面活性剂的合成及其性质

以四氢苯酐为起始原料,依次经酯化、酰胺化及氧化开环反应合成了新型烷基酰胺双羧酸盐双子表面活性剂(4),其结构经¹H NMR, IR和MS(ESI)表征。通过浊点法测得其Krafft点低于0 ℃;通过电导率法测得其CMC为3.729×10^-3 mol·L^-1;利用滴体积法测得CMC为3.402×10^-4 mol·L^-1, γ-CMC为36.88 mN·m-¹。 4的起泡性能、乳化性能良好,优于SDS。     

Hydrology of the North Klondike River: carbon export,water balance and inter-annual climate influences within a sub-alpine permafrost catchment

Arctic and sub-arctic watersheds are undergoing significant changes due to recent climate warming and degrading permafrost, engendering enhanced monitoring of arctic rivers. Smaller catchments provide understanding of discharge, solute flux and groundwater recharge at the process level that contributes to an understanding of how larger arctic watersheds are responding to climate change. The North Klondike River, located in west central Yukon, is a sub-alpine permafrost catchment, which maintains an active hydrological monitoring station with a record of >40 years. In addition to being able to monitor intra-annual variability, this data set allows for more complex analysis of streamflow records. Streamflow data, geochemistry and stable isotope data for 2014 show a groundwater-dominated system, predominantly recharged during periods of snowmelt. Radiocarbon is shown to be a valuable tracer of soil zone recharge processes and carbon sources. Winter groundwater baseflow contributes 20?% of total annual discharge, and accounts for up to 50?% of total river discharge during the spring and summer months. Although total stream discharge remains unchanged, mean annual groundwater baseflow has increased over the 40-year monitoring period. Wavelet analysis reveals a catchment that responds to El Niño and longer solar cycles, as well as climatic shifts such as the Pacific Decadal Oscillation.

Dedicated to Professor Peter Fritz on the occasion of his 80th birthday     

Use of stable carbon isotope ratios to determine the source of cypermethrin in so-called natural plant extract formulations used for organic farming

Some natural plant extract formulations (NPEFs, also referred to as essential oils) used in organic farming have been shown to contain synthetic pesticides. We obtained samples of four NPEFs (Muso, Hekiro, Kensogen-Ten, and Nurse Green) that were contaminated with the synthetic pyrethroid cypermethrin, and we used gas chromatography coupled with combustion, cryofocusing, and isotope ratio mass spectrometry to determine the stable carbon isotope ratios (δ¹³C) for the cypermethrin in the four NPEF samples, as well as in ten cypermethrin reagents and two commercial pesticide formulations (Agrothrin emulsion and Agrothrin water-dispersible powder). Our goal was to identify the source of the cypermethrin in the NPEFs. Cryofocusing markedly sharpened the cypermethrin peak and thus improved the accuracy and precision of the determined δ¹³C values. The δ¹³C values (±?SD) of the 16 cypermethrin samples ranged from ?28.3?±?0.2 to ?24.5?±?0.2?‰. Surprisingly, the four NPEFs showed similar δ¹³C values (?26.8 to ?27.3?‰), suggesting that the cypermethrin in all the samples came from the same source (either the same chemical reaction or the same primary material). This possibility was supported by previously published results. In addition, the δ¹³C values of the two commercial pesticides were similar to the values for the NPEFs, suggesting that the commercial pesticides had been diluted and sold as NPEFs.     

Temporal 18O and deuterium variations in hydrologic components of a small watershed during a typhoon event

The differences between δ¹⁸O and δ²H in throughfall and open rainfall were studied for a selected typhoon event in a watershed within the Taihu Lake drainage basin, eastern China. In this event, the isotopic composition of precipitation exhibited a strong temporal variation. Comparison results show that an isotopic composition difference existed not only between gross rainfall and average incremental rainfall, but also between different calculation methods used to derive average. The differences between incremental precipitation and throughfall isotopic composition were observed in this study. Considering the temporal variation in rainfall and throughfall during this typhoon event, the incremental value can have an effect on hydrograph separation more accurately in evaluating the importance of ‘new’ water. In addition, isotopic fluctuations of surface water and groundwater differed from those of rainfall and throughfall throughout the event.     

Estimating the spatial distribution of artificial groundwater recharge using multiple tracers

Stable isotopes of water, organic micropollutants and hydrochemistry data are powerful tools for identifying different water types in areas where knowledge of the spatial distribution of different groundwater is critical for water resource management. An important question is how the assessments change if only one or a subset of these tracers is used. In this study, we estimate spatial artificial infiltration along an infiltration system with stage–discharge relationships and classify different water types based on the mentioned hydrochemistry data for a drinking water production area in Switzerland. Managed aquifer recharge via surface water that feeds into the aquifer creates a hydraulic barrier between contaminated groundwater and drinking water wells. We systematically compare the information from the aforementioned tracers and illustrate differences in distribution and mixing ratios. Despite uncertainties in the mixing ratios, we found that the overall spatial distribution of artificial infiltration is very similar for all the tracers. The highest infiltration occurred in the eastern part of the infiltration system, whereas infiltration in the western part was the lowest. More balanced infiltration within the infiltration system could cause the elevated groundwater mound to be distributed more evenly, preventing the natural inflow of contaminated groundwater.

Dedicated to Professor Peter Fritz on the occasion of his 80th birthday     

Controls over spatial and seasonal variations on isotopic composition of the precipitation along the central and eastern portion of Brazil

Based on Global Network Isotopes in Precipitation (GNIP) isotopic data set, a review of the spatial and temporal variability of δ¹⁸O and δ²H in precipitation was conducted throughout central and eastern Brazil, indicating that dynamic interactions between Intertropical and South Atlantic Convergence Zones, Amazon rainforest, and Atlantic Ocean determine the variations on the isotopic composition of precipitation over this area. Despite the seasonality and latitude effects observed, a fair correlation with precipitation amount was found. In addition, Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) air mass back trajectories were used to quantify the factors controlling daily variability in stable isotopes in precipitation. Through a linear multiple regression analysis, it was observed that temporal variations were consistent with the meteorological parameters derived from HYSPLIT, particularly precipitation amount along the trajectory and mix depth, but are not dependent on vapour residence time in the atmosphere. These findings also indicate the importance of convective systems to control the isotopic composition of precipitation in tropical and subtropical regions.     

Evaluation of the performance of high temperature conversion reactors for compound-specific oxygen stable isotope analysis

In this study conversion conditions for oxygen gas chromatography high temperature conversion (HTC) isotope ratio mass spectrometry (IRMS) are characterised using qualitative mass spectrometry (IonTrap). It is shown that physical and chemical properties of a given reactor design impact HTC and thus the ability to accurately measure oxygen isotope ratios. Commercially available and custom-built tube-in-tube reactors were used to elucidate (i) by-product formation (carbon dioxide, water, small organic molecules), (ii) 2nd sources of oxygen (leakage, metal oxides, ceramic material), and (iii) required reactor conditions (conditioning, reduction, stability). The suitability of the available HTC approach for compound-specific isotope analysis of oxygen in volatile organic molecules like methyl tert-butyl ether is assessed. Main problems impeding accurate analysis are non-quantitative HTC and significant carbon dioxide by-product formation. An evaluation strategy combining mass spectrometric analysis of HTC products and IRMS ¹⁸O/¹⁶O monitoring for future method development is proposed.     

Anilinolysis of O‐butyl phenyl phosphonochloridothioate in acetonitrile: Synthesis,characterization, kinetic study,and reaction mechanism

This paper describes a simple optimized method for the synthesis of O‐butyl phenyl phosphonochloridothioate ( 4 ) under mild conditions. The target compounds were characterized by ¹H‐nuclear magnetic resonance (NMR), ¹³C‐NMR, and ³¹P‐NMR spectroscopy, as well as mass spectroscopy. The apparent structure of 4 was confirmed by optimization using the B3LYP/6‐311 + G(d,p) level in the Gaussian 09 program in acetonitrile. The nucleophilic substitution reactions of 4 with X‐anilines (XC₆H₄NH₂) and deuterated X‐anilines (XC₆H₄ND₂) were investigated kinetically in acetonitrile at 55.0°C. The free energy relationship with X in the anilines looked biphasic concave upwards with a break region between X = H and X = 3‐MeO, giving large negative ρ_X and small positive β_X values. The deuterium kinetic isotope effects were secondary inverse (k_H/k_D < 1: 0.789‐0.995) and the magnitudes, (k_H/k_D), increased when the nucleophiles were changed from weakly basic to strongly basic anilines. A concerted S_N2 mechanism is proposed on the basis of the selectivity parameters and the variation trend of the deuterium kinetic isotope effects with X.