Improved and Efficient Synthesis of Chromeno[4,3‐d]pyrazolo [3,4‐b]pyridin‐6(3H)‐ones and Their Fluorescence Properties

A series of chromeno[4,3‐d]pyrazolo[3,4‐b]pyridin‐6(3H)‐one derivatives was easily and efficiently synthesized by the reaction of 2H‐chromen‐2‐ones with pyrazol‐5‐amines catalyzed by CuCl₂?2H₂O in ethanol. This protocol has the advantages of mild reaction conditions, easy work‐up, and high yields. These compounds were showed to have high fluorescence quantum yields, which mentioned their value as luminescence or fluorescence probe.     

Krigings over space and time based on latent low-dimensional structures

We propose a new nonparametric approach to represent the linear dependence structure of a spatiotemporal process in terms of latent common factors.Though it is formally similar to the existing reduced rank approximation methods,the fundamental difference is that the low-dimensional structure is completely unknown in our setting,which is learned from the data collected irregularly over space but regularly in time.Furthermore,a graph Laplacian is incorporated in the learning in order to take the advantage of the continuity over space,and a new aggregation method via randomly partitioning space is introduced to improve the efficiency.We do not impose any stationarity conditions over space either,as the learning is facilitated by the stationarity in time.Krigings over space and time are carried out based on the learned low-dimensional structure,which is scalable to the cases when the data are taken over a large number of locations and/or over a long time period.Asymptotic properties of the proposed methods are established.An illustration with both simulated and real data sets is also reported.     

一种溶解氧敏感膜荧光发射效率光谱检测系统的研制

荧光猝灭法是快速测量污水、地表水以及渔业养殖水环境中溶解氧含量的先进技术之一,氧敏感膜是荧光猝灭法检测技术的核心,高荧光发射效率的氧敏感膜具有灵敏度高、特异性强、信噪比高的优点,检测结果更为准确。高效率是优选氧敏感膜的依据,也是溶解氧检测元器件、检测电路和检测光路优化设计的关键。现有溶解氧荧光检测装置中未有对氧敏感膜进行质量评估的标准方法,基于对已有传感器探头光路和电路的研究,该研究分析了全波段的荧光发射效率,选用大功率氙灯作为激发光源,基于连续单波长逐级扫描进行单色分光,构建了氧敏感膜的激发光-荧光光谱扫描装置,然后通过扫描测定氧敏感膜的激发光光谱和荧光光谱,提出并建立了荧光发射效率计算方法,提出的方法能客观地评估荧光发射能力,准确寻找最佳激发波长。为验证该方法的可行性,对来自国内外的多个氧敏感膜样品进行了实验测定,测试结果表明：单张氧敏感膜荧光发射效率随波长变化,呈多峰分布,同一型号的样品荧光效率曲线相似,但荧光发射效率差异较大,同一激发波长下荧光发射效率最大者较最小者高出14.5%,三张氧敏感膜的最大峰值波长均不同,分别为：401,543和435 nm,但发射峰值波长均为650 nm;不同型号的氧敏感膜相比较,最大荧光发射效率可相差1～2个数量级;实测传感器中使用的激发波长,其所选用的激发波长并非最大发射峰值波长,其荧光发射效率仅为最大荧光发射效率的1/2,表明传感器光源可以进一步优化选型。综上所述,本文建立了一种溶解氧敏感膜荧光发射效率检测系统,提出了以荧光发射效率评估氧敏感膜的方法,并开展了相关实验测定。本文工作可望用于新型氧敏感膜材料、工艺的研究及传感器优化设计与制造。     

An application of the monotone iterative method to a combustion problem in porous media

Problems related to combustion fronts in porous media have been studied by many authors recently, see e.g. [Y. Akkutlu, Y.C. Yortsos, The dynamics of in-situ combustion fronts in porous media, Combust. Flame 134 (2003) 239–247; J.C. da Mota, W. Dantas, D. Marchesin, Combustion fronts in porous media, SIAM J. Appl. Math. 62 (2002) 2175–2198; D.A. Schult, B.J. Matkowsky, V.A. Volpert, A.C. Fernandez-Pello, Forced forward smolder combustion, Combust. Flame 104 (1996) 1–26]. Most of this interest is due to the combustion process for oil recovery.In this paper we construct monotone iteractions for a Cauchy problem arising from a combustion model in a porous medium derived in [J.C. da Mota, S. Schecter, Combustion fronts in a porous medium with two layers, J. Dynam. Differential Equations 18 (3) (2006) 615–665]. We conclude that the monotone iteractions converge to a unique solution of this Cauchy problem, globally in time.     

Design of new highly luminescent Tb complexes using theoretical combinatorial chemistry

The relation between the structure and luminescent properties of Tb³⁺ complexes containing β-diketonate ligands has been investigated by means of theoretical combinatorial chemistry. The new hybrid method developed combines an empirical relation involving the energy of the lowest triplet state of Tb³⁺ complexes with extremely fast semiempirical quantum mechanical calculations. The concomitant use of phenyl groups attached at both extremities of the β-diketonate ligand has shown to give rise to complexes exhibiting theoretical emission quantum yields higher than 0.5. The results indicate that the proposed method may be used as a valuable tool for predicting luminescent properties of a large number of Tb³⁺ complexes in a relatively short computational time, therefore contributing to further developments in the field of theoretical combinatorial chemistry.     

Site‐Selective Late‐Stage Aromatic [18F]Fluorination via Aryl Sulfonium Salts

Site‐selective functionalization of C?H bonds in small complex molecules is a long‐standing challenge in organic chemistry. Herein, we report a broadly applicable and site‐selective aromatic C?H dibenzothiophenylation reaction. The conceptual advantage of this transformation is further demonstrated through the two‐step C?H [¹⁸F]fluorination of a series of marketed small‐molecule drugs.     

Whole‐Cell Photoenzymatic Cascades to Synthesize Long‐Chain Aliphatic Amines and Esters from Renewable Fatty Acids

Long‐chain aliphatic amines such as (S,Z)‐heptadec‐9‐en‐7‐amine and 9‐aminoheptadecane were synthesized from ricinoleic acid and oleic acid, respectively, by whole‐cell cascade reactions using the combination of an alcohol dehydrogenase (ADH) from Micrococcus luteus, an engineered amine transaminase from Vibrio fluvialis (Vf‐ATA), and a photoactivated decarboxylase from Chlorella variabilis NC64A (Cv‐FAP) in a one‐pot process. In addition, long chain aliphatic esters such as 10‐(heptanoyloxy)dec‐8‐ene and octylnonanoate were prepared from ricinoleic acid and oleic acid, respectively, by using the combination of the ADH, a Baeyer–Villiger monooxygenase variant from Pseudomonas putida KT2440, and the Cv‐FAP. The target compounds were produced at rates of up to 37 U g^?1 dry cells with conversions up to 90 %. Therefore, this study contributes to the preparation of industrially relevant long‐chain aliphatic chiral amines and esters from renewable fatty acid resources.     

An Order–Disorder Ferroelectric Host–Guest Inclusion Compound

The host–guest complex [(DIPA)([18]crown‐6)](ClO₄) ( 1 ; DIPA=2,6‐diisopropylanilinium) was constructed and found to undergo a sequence of phase transitions (Ibam–Pbcn–Pna2₁) at T₁=278 K and T₂=132 K, respectively. Systematic characterizations, such as differential scanning calorimetry, heat capacity, temperature‐dependent dielectric constant, and P–E hysteresis loop, reveal that the centrosymmetric‐to‐polar phase transition at T₂ is a paraelectric‐to‐ferroelectric transition. The symmetry breaking was also confirmed by temperature‐dependent second‐harmonic generation effect and X‐ray powder diffraction. The ferroelectric mechanism is attributable to the linear motion of the perchlorate counterions accompanied by the order–disorder transition of the [18]crown‐6 molecules and the anions.