A general approach to cyathin diterpenes. Total synthesis of allocyathin B(3)

[reaction: see text] The synthesis of allocyathin B(3) from an advanced intermediate possessing the ring system and relative stereochemistry but lacking the isopropyl and hydroxymethyl groups is reported. The isopropyl group was introduced by radical cyclization of a methyl propargyl acetal of an alpha-bromo ketone, and the hydroxymethyl group was generated by Pd-catalyzed carbonylation of a vinyl triflate. The route provides functionalized intermediates that could allow access to more complex members of the cyathin family of diterpenes.     

Characterization of Roasting Time on Sensory Quality,Color, Taste,and Nonvolatile Compounds of Yuan An Yellow Tea

Roasting is crucial for producing Yuan An yellow tea (YAYT) as it substantially affects sensory quality. However, the effect of roasting time on YAYT flavor quality is not clear. To investigate the effect of roasting time on the sensory qualities, chemical components, odor profiles, and metabolic profile of YAYTs produced with 13 min roasting, 16 min roasting, 19 min roasting, 22 min roasting, and 25 min roasting were determined. The YAYTs roasted for 22 min got higher sensory scores and better chemical qualities, such as the content of gallocatechin (GC), gallocatechin gallate (GCG), free amino acids, solutable sugar, meanwhile the lightness decreased, the hue of tea brew color (b) increased, which meant the tea brew got darker and yellower. YAYTs roasted for 22 min also increased the contents of key odorants, such as benzaldehyde, nonanal, β-cyclocitral, linalool, nerol, α-cedrol, β-ionone, limonene, 2-methylfuran, indole, and longiborneol. Moreover, non-targeted metabolomics identified up to 14 differentially expressed metabolites through pair-wise comparisons, such as flavonoids, phenolic acids, sucrose, and critical metabolites, which were the main components corresponding to YAYT roasted for 22 min. In summary, the current results provide scientific guidance for the production of high quality YAYT.     

Determination of 241Am in Environmental Samples: A Review

The determination of ²⁴¹Am in the environment is of importance in monitoring its release and assessing its environmental impact and radiological risk. This paper aims to give an overview about the recent developments and the state-of-art analytical methods for ²⁴¹Am determination in environmental samples. Thorough discussions are given in this paper covering a wide range of aspects, including sample pre-treatment and pre-concentration methods, chemical separation techniques, source preparation, radiometric and mass spectrometric measurement techniques, speciation analyses, and tracer applications. The paper focuses on some hyphenated separation methods based on different chromatographic resins, which have been developed to achieve high analytical efficiency and sample throughput for the determination of ²⁴¹Am. The performances of different radiometric and mass spectrometric measurement techniques for ²⁴¹Am are evaluated and compared. Tracer applications of ²⁴¹Am in the environment, including speciation analyses of ²⁴¹Am, and applications in nuclear forensics are also discussed.     

Spectroscopic fingerprints of valence and spin states in manganese oxides and fluorides

We performed a systematic study of soft X-ray absorption spectroscopy in various manganese oxides and fluorides. Both Mn L-edges and ligand (O and F) K-edges are presented and compared with each other. Despite the distinct crystal structure and covalent/ionic nature in different systems, the Mn-L spectra fingerprint the Mn valence and spin states through spectral lineshape and energy position consistently and evidently. The clear O- and F-K pre-edge features in our high resolution spectra enable a quantitative definition of the molecular orbital diagram with different Mn valence. In addition, while the binding energy difference of the O-1s core electrons leads to a small shift of the O-K leading edges between trivalent and quadrivalent manganese oxides, a significant edge shift, with an order of magnitude larger in energy, was found between divalent and trivalent compounds, which is attributed to the spin exchange stabilization of half-filled 3d system. This shift is much enhanced in the ionic fluoride system. This work provides the spectroscopic foundation for further studies of complicated Mn compounds.     

The effect of water molecule on the thermal stability of lanthanide compounds with 1,3-benzeneditetrazol-5-yl

Six lanthanide compounds [Ln(H₂O)₉](m-BDTH)₃·9(H₂O) where Ln = La (1), and [Ln(H₂O)₈](m-BDTH)₃·9(H₂O) (m-BDTH₂ = 1,3-benzeneditetrazol-5-yl) where Ln = Lu (2), Yb (3), Er (4), Ho (5) and Y (6) were hydrothermally synthesized and characterized by elemental analyses, infrared spectra, powder X-ray diffraction (PXRD) and X-ray single crystal diffraction. PXRD indicates that 2–6 are isomorphous. Structural analyses reveal that 1 is coordinated by nine water molecules forming a capped-square antiprism, while 2–6 are coordinated by eight water molecules forming a simple square antiprismatic geometry. Effects of water molecules on thermal stability were also discussed by thermogravimetric (TG), DSC, and PXRD under different temperatures. TG analyses suggest that 1 loses lattice and coordinated water molecules with no diacritical boundary, and 6 removes lattice water molecules first and then coordinated water molecules. DSC and PXRD further confirm the consequence.     

Solubility of methane in octane + ethanol at temperatures from 303.15 K to 333.15 K and pressures up to 12.01 MPa

Solubility of methane in octane + ethanol was measured at temperatures ranging from 303.15 K to 333.15 K and pressures ranging from 2.60 MPa to 12.01 MPa. Experimental data were analyzed using the Soave-Redlich-Kwong equation of state with three types of mixing rules, and the estimated average deviation from the experimental solubility data was less than 3.5 %.     

基于跨文化视角的旅游地视觉表征差异分析——以中美游客镜头下的西藏为例

旅游地摄影是旅游者自身对目的地的视觉表征,通过潜在游客对目的地的形象感知影响其旅游决策.旅游地摄影被旅游企业视为旅游地视觉营销的重要策略.基于跨文化视角,以中美旅游者拍摄且上传网络的西藏旅游照片为研究对象,采用内容分析法、卡方检验、社会网络分析法和空间分析法,借助NVivo11.0、SPSS22.0、Ucinet6和ArcGIS10.2软件,探寻中美游客摄影图片对西藏视觉表征的差异,以期为旅游目的地定向营销提供参考依据.研究发现：（1）从照片编码树状节点频数来看,雄壮瑰丽的自然景观、虔诚的佛教信徒、神秘的民族非物质文化是西藏旅游形象的核心要素和符号.（2）从照片树状节点类目间差异分析来看,两组照片在自然景观、民族非物质文化、户外活动、舞台化表演和衣饰6个类目上存在统计学差异.中国旅游者的照片更倾向于表征自然景观、当地人生活细节、户外活动和精心设计的舞台化表演.美国游客的照片则更侧重于对原真性的民族非物质文化和绚丽多彩、独特别致的民族服饰的表征.（3）从照片"聚合形象地图"来看,美国样本的聚合形象地图较为复杂和多样化,而中国样本则相对简单有条理.（4）从中美游客地理摄影偏好来看,游客最爱拉萨.除此之外,中国游客更为偏爱那曲地区,而美国游客却更倾向于山南和日喀则地区.     

CCD对高空间分辨率波前干涉检测的影响

推导并用实验验证了光强与入射波前在单位像元面积里成近似线性关系,从而得到入射波前经CCD采样后的功率谱密度（PSD）公式.根据该公式,模拟分析了影响CCD采集系统的系统传递函数的各个因素：入射波前、CCD的填充因子及CCD的曝光时间,得出了他们与系统传递函数的定性关系,并且通过实验明确CCD曝光时间对高空间分辨率波前检测不确定度的影响,为高空间分辨率干涉设计提供了理论依据.     

Nonequilibrium thermodynamics and fluctuation relations for small systems

In this review, we give a retrospect of the recent progress in nonequilibrium statistical mechanics and thermodynamics in small dynamical systems. For systems with only a few number of particles, fluctuations and nonlinearity become significant and contribute to the nonequilibrium behaviors of the systems, hence the statistical properties and thermodynamics should be carefully studied. We review recent developments of this topic by starting from the Gallavotti–Cohen fluctuation theorem, and then to the Evans–Searles transient fluctuation theorem, Jarzynski free-energy equality, and the Crooks fluctuation relation. We also investigate the nonequilibrium free energy theorem for trajectories involving changes of the heat bath temperature and propose a generalized free-energy relation. It should be noticed that the non-Markovian property of the heat bath may lead to the violation of the free-energy relation.