Asymmetric Synthesis of Indoline from Achiral Phthalimide Involving Crystallization-Induced Deracemization

Asymmetric synthesis was performed by combining the photochemical reaction of an achiral substrate followed by crystallization-induced deracemization. The results indicated that a fused indoline produced by photochemical intramolecular δ-hydrogen abstraction and cyclization of N-(5-chloro-2-methylphenyl)phthalimide crystallized as a racemic conglomerate. Since this substrate has an aminal skeleton, racemization involving a ring-opening and ring-closing equilibrium process occurred under suitable conditions. Efficient racemization was observed in acetone containing a catalytic base, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Crystallization-induced dynamic deracemization by Viedma ripening from racemic indoline was performed with an excellent enantioselectivity of 99 % ee. Furthermore, one-pot asymmetric synthesis of the indoline was achieved by the photochemical reaction of achiral phthalimide followed by continuous attrition-enhanced deracemization converging to 99 % ee of enantiomeric crystals. This is the first example of asymmetric expression and amplification by photochemical hydrogen abstraction and crystallization-induced dynamic deracemization.     

Evolution of an Adenine–Copper Cluster to a Highly Porous Cuboidal Framework: Solution‐Phase Ripening and Gas‐Adsorption Properties

The synthesis and directed evolution of a tetranuclear copper cluster, supported by 8‐mercapto‐N9‐propyladenine ligand, to a highly porous three‐dimensional cubic framework in the solid state is reported. The structure of this porous framework was unambiguously characterized by X‐ray crystallography. The framework contains about 62 % solvent‐accessible void; the presence of a free exocyclic amino group in the porous framework facilitates reversible adsorption of gas and solvent molecules. Oriented growth of framework in solution was also tracked by force and scanning electron microscopy studies, leading to identification of an intriguing ripening process, over a period of 30 days, which also revealed formation of cuboidal aggregates in solution. The elemental composition of these cuboidal aggregates was ascertained by EDAX analysis.     

利用Ostwald熟化作用合成空心碳纳米材料

以淀粉等易获得的生物质为碳前驱物, 亚铁盐为添加剂, 采用水热法制备了碳材料. 实验发现, 在反应过程中, 首先生成了被无定形碳包裹的铁氧化物纳米棒, 形成碳/铁氧化物的核/壳结构. 在进一步的反应中, 铁氧化物核自发溶解, 最终得到了空心的碳纳米棒. 讨论了铁氧化物自发溶解的原因, 认为空心碳纳米棒的形成是由Ostwald熟化现象造成的. 当以葡萄糖或环糊精为碳前驱物时, 得到的是空心碳球, 这可能与各种碳前驱物不同的表面活性剂作用有关.     

Post-Harvest Use of Ultraviolet Light (UV) and Light Emitting Diode (LED) to Enhance Bioactive Compounds in Refrigerated Tomatoes

Different strategies have been developed to increase the concentration of bioactive compounds in tomatoes during post-harvest, with ultraviolet light (UV) and light emitting diodes (LEDs) being interesting tools. The aim of this study was to evaluate the effect of ultraviolet (UVA at 366 nm and UVC at 254 nm) pre-treatment (1 kJ/m²) and red–blue LED light (25.4 µmol/m²/s) on the concentration of carotenoids, (poly)phenols and hydrophilic/lipophilic antioxidant capacity during 7 days of refrigeration storage of green tomatoes (Solanum lycopersicum L.) cultivar “Raf”. In addition, special attention was paid to quality parameters (weight loss, colour, acidity, soluble solids and ripening index). Tomatoes exposed to LED light at 6 °C for 7 days increased up to three times the total carotenoids content (mainly β-carotene and E-lycopene) compared to tomatoes refrigerated in the dark, while UV treatments alone did not significantly affect the carotenoid content. Besides, exposure to LEDs increased the hydrophilic and lipophilic antioxidant capacity of tomatoes by 30%, without affecting phenolic contents. Thus, LED treatments alone during refrigerated storage fostered ripening and improved the nutritional value of tomatoes, without compromising quality parameters. Further studies must be carried out to evaluate the impact on sensory attributes and consumer acceptance.     

Compositional Changes in Grapes and Leaves as a Consequence of Smoke Exposure of Vineyards from Multiple Bushfires across a Ripening Season

The negative effects of smoke exposure of grapes in vineyards that are close to harvest are well documented. Volatile phenols in smoke from forest and grass fires can contaminate berries and, upon uptake, are readily converted into a range of glycosylated grape metabolites. These phenolic glycosides and corresponding volatile phenols are extracted into the must and carried through the winemaking process, leading to wines with overtly smoky aromas and flavours. As a result, smoke exposure of grapes can cause significant quality defects in wine, and may render grapes and wine unfit for sale, with substantial negative economic impacts. Until now, however, very little has been known about the impact on grape composition of smoke exposure very early in the season, when grapes are small, hard and green, as occurred with many fires in the 2019–20 Australian grapegrowing season. This research summarises the compositional consequences of cumulative bushfire smoke exposure of grapes and leaves, it establishes detailed profiles of volatile phenols and phenolic glycosides in samples from six commercial Chardonnay and Shiraz blocks throughout berry ripening and examines the observed effects in the context of vineyard location and timing of smoke exposure. In addition, we demonstrate the potential of some phenolic glycosides in leaves to serve as additional biomarkers for smoke exposure of vineyards.     

Qualitative evaluation of the effect of morphology,spatial distribution and coherent interfaces on the coarsening kinetics and size distribution of particles during Ostwald ripening

ABSTRACT

By exploiting the simple structure of the recently developed Multi-Particle model of Ostwald ripening based on pairwise interactions, the effect of extra factors affecting the coarsening process, such as the morphology of particles, the topology of their spatial distribution and the presence of elastic fields surrounding coherent precipitates, is analysed from a qualitative viewpoint.

Two observables disclose the presence of deviations with respect to the behaviour of a system of spherical and incoherent precipitates: the absolute value of the kinetic coarsening constant, together with its evolution with the volume fraction, and the shape of the asymptotic particle size distribution (PSD) for a given volume fraction of second phase.

By using a parametrised ‘rounded cube’ ideal solid it is shown that, as the shape of precipitates flattens, the coarsening constant decreases reaching in some condition values as low as about 20% that of a system of spheres with the same fraction.

Consequently, the curve of the relative kinetic constant with the volume fraction has a slower increase above 0.7 compared to spherical particles and this permits to explain accurately the experimental data on dense systems in the whole range of volume fractions.

It is also shown how the shape of the PSD is influenced by regular arrangements of particles in the space and by interfacial stresses in the matrix surrounding coherent precipitates. In both cases the model predicts a sharpening of the PSD, whose shape tends to become more symmetrical and somehow similar to that of the classical LSW theory.     

Thermally stimulated depolarization measurements on NaF:02-, NaCI:S2-.and KC1:S2-

In NaCl:S^2-, KC1:S² and NaF:0^2-(i) optical absorption and emission spectra and (ii) electric conductivity measurements show that after suitable heat treatment the bivalent anion impurities are paired with anion vacancies. Conventional dielectric absorption measurements and sensitive measurements of thermally stimulated depolarizing (t. s. d.) currents (ionic thermocurrent) have failed to detect the presence of bivalent anion-anion vacancy dipoles in these crystals. We suggest that derealization or sharing of the electron of the bivalent impurity ion, possibly with the vacancy, considerably reduces the dipole moment.     

锰的硅化物薄膜在Si(100)-2×1表面生长的STM研究

锰的硅化物在微电子器件、自旋电子学器件等领域具有良好的应用前景, 了解锰的硅化物薄膜在硅表面的生长规律是其走向实际应用的关键步骤之一. 本文采用分子束外延方法在Si(100)-2× 1表面沉积了约4个原子层的锰薄膜, 并利用超高真空扫描隧道显微镜研究了该薄膜与硅衬底之间在250-750℃范围内的固相反应情况. 室温下沉积在硅衬底表面的锰原子与衬底不发生反应, 薄膜由无序的锰团簇构成; 当退火温度高于290℃时, 锰原子与衬底开始发生反应, 生成外形不规则的枝晶状锰硅化物和富锰的三维小岛; 325℃时, 衬底上开始形成平板状的MnSi小岛; 525℃时, 枝晶状锰硅化物完全消失, 出现平板状的MnSi_1.7大岛; 高于600℃时, 富锰的三维小岛和平板状的MnSi小岛全部消失, 仅剩下平板状的MnSi_1.7大岛. 这些结果说明退火温度决定了薄膜的形态和结构. 在大约600℃退火时岛的尺寸随着退火时间的延长而逐渐增大, 表明岛的生长遵从扩散限制的Ostwald熟化机理.     

Distribution of Triterpenoids and Steroids in Developing Rugosa Rose (Rosa rugosa Thunb.) Accessory Fruit

Triterpenoids and steroids are considered to be important for the fruit quality and health-promoting properties for the consumers. The aim of the study was the determination of the changes in triterpenoid and steroid biosynthesis and the accumulation in hypanthium and achenes of rugosa rose (Rosa rugosa Thunb.) hip during fruit development and ripening at three different phenological stages (young fruits, fully developed unripe fruits, and matured fruits). Triterpenoids and steroids were also determined in the peel and the pulp of the matured hips. The obtained results indicated that the distribution of the analyzed compounds in different fruit tissues is a selective process. The increased rate of hydroxylation of triterpenoids, the deposition of hydroxylated acids in fruit surface layer, and the continuous biosynthesis of phytosterols in achenes versus its gradual repression in hypanthium accompanied by the accumulation of their biosynthetic intermediates and ketone derivatives seem to be characteristic metabolic features of maturation of rugosa rose accessory fruit. These observations, apart from providing the important data on metabolic modifications occurring in developing fruits, might have a practical application in defining fruit parts, particularly rich in bioactive constituents, to enable the development of novel functional products.     

Label-free and rapid spectroscopic evaluation of ripening of Syzygium cumini fruit

In the present investigation, attempts have been made to obtain the spectral signature of the fruit jamun and to estimate the changes in biochemical composition that take place in the process of ripening of the fruits. The changes in exocarp, mesocarp, and seed of the fruit in raw and ripe stages have been investigated with the help of label-free, nondestructive, and rapid techniques: laser-induced fluorescence and attenuated total reflectance Fourier transform infrared spectroscopy. For this, the fluorescence spectra of the different parts (exocarp, mesocarp, and seed) of the raw and ripe fruits of jamun excited by 405?nm violet diode laser have been recorded in the spectral region 400–900?nm. The spectrum shows the spectral signature of anthocyanin, flavonoids, carotenoid, and chlorophyll. The observed decrease in the intensity of chlorophyll bands and simultaneous increase in the intensity of anthocyanin and carotenoid bands is regarded as indicator of the ripening of the fruit of jamun. Also, attenuated total reflectance Fourier transform infrared spectra have been recorded in the spectral region 4000–485?cm^?1 for the identification of functional groups associated with different biochemical altered during ripening process of the fruits of jamun. The analyses of the recorded infrared spectra show the presence of carbohydrates, cell wall components, phenolic compounds, nucleic acid, and amide. The quantitative estimation of the biochemical content in the different parts of jamun fruit during the ripening process has been done through calculating the area of the band by curve fitting. The determined spectral signatures can be utilized for the effective monitoring of jamun fruit.