Lactones in the Synthesis of Prostaglandins and Prostaglandin Analogs

In the total stereo-controlled synthesis of natural prostaglandins (PGs) and their structural analogs, a vast class of compounds and drugs, known as the lactones, are encountered in a few key steps to build the final molecule, as: δ-lactones, γ-lactones, and 1,9-, 1,11-, and 1,15-macrolactones. After the synthesis of 1,9-PGF_2α and 1,15-PGF_2α lactones, many 1,15-lactones of E₂, E₃, F₂, F₃, A₂, and A₃ were found in the marine mollusc Tethys fimbria and the quest for understanding their biological role stimulated the research on their synthesis. Then 1,9-, 1,11-, and 1,15-PG lactones of the drugs were synthesized as an alternative to the corresponding esters, and the first part of the paper describes the methods used for their synthesis. The efficient Corey procedure for the synthesis of prostaglandins uses the key δ-lactone and γ-lactone intermediates with three or four stereocenters on the cyclopentane fragment to link the PG side chains. The paper describes the most used procedures for the synthesis of the milestone δ-Corey-lactones and γ-Corey-lactones, their improvements, and some new promising methods, such as interesting, new stereo-controlled and catalyzed enantioselective reactions, and methods based on the chemical/enzymatic resolution of the compounds in different steps of the sequences. The many uses of δ-lactones not only for the synthesis of γ-lactones, but also for obtaining 9β-halogen-PGs and halogen-substituted cyclopentane intermediates, as synthons for new 9β-PG analogs and future applications, are also discussed.     

Heteroalleles in Common Wheat: Multiple Differences between Allelic Variants of the Gli-B1 Locus

The Gli-B1-encoded γ-gliadins and non-coding γ-gliadin DNA sequences for 15 different alleles of common wheat have been compared using seven tests: electrophoretic mobility (EM) and molecular weight (MW) of the encoded major γ-gliadin, restriction fragment length polymorphism patterns (RFLPs) (three different markers), Gli-B1-γ-gliadin-pseudogene known SNP markers (Single nucleotide polymorphisms) and sequencing the pseudogene GAG56B. It was discovered that encoded γ-gliadins, with contrasting EM, had similar MWs. However, seven allelic variants (designated from I to VII) differed among them in the other six tests: I (alleles Gli-B1i, k, m, o), II (Gli-B1n, q, s), III (Gli-B1b), IV (Gli-B1e, f, g), V (Gli-B1h), VI (Gli-B1d) and VII (Gli-B1a). Allele Gli-B1c (variant VIII) was identical to the alleles from group IV in four of the tests. Some tests might show a fine difference between alleles belonging to the same variant. Our results attest in favor of the independent origin of at least seven variants at the Gli-B1 locus that might originate from deeply diverged genotypes of the donor(s) of the B genome in hexaploid wheat and therefore might be called “heteroallelic”. The donor’s particularities at the Gli-B1 locus might be conserved since that time and decisively contribute to the current high genetic diversity of common wheat.     

给水管道腐蚀原因及防护措施探讨

给水管道在使用过程中很容易受到人为外力、管道材质、地下水、周围空气、土壤等因素的影响而腐蚀,影响了管道的使用质量和寿命,也带来较大的安全隐患。本文主要是从给水管道腐蚀原因出发,并探讨防护措施。     

Matrix Manipulation of Directly-Synthesized PbS Quantum Dot Inks Enabled by Coordination Engineering

The direct-synthesis of conductive PbS quantum dot (QD) ink is facile, scalable, and low-cost, boosting the future commercialization of optoelectronics based on colloidal QDs. However, manipulating the QD matrix structures still is a challenge, which limits the corresponding QD solar cell performance. Here, for the first time a coordination-engineering strategy to finely adjust the matrix thickness around the QDs is presented, in which halogen salts are introduced into the reaction to convert the excessive insulating lead iodide into soluble iodoplumbate species. As a result, the obtained QD film exhibits shrunk insulating shells, leading to higher charge carrier transport and superior surface passivation compared to the control devices. A significantly improved power-conversion efficiency from 10.52% to 12.12% can be achieved after the matrix engineering. Therefore, the work shows high significance in promoting the practical application of directly synthesized PbS QD inks in large-area low-cost optoelectronic devices.     

Intrinsic Defect Limit to the Growth of Orthorhombic HfO2 and (Hf,Zr)O2 with Strong Ferroelectricity: First-Principles Insights

It is believed that promoting the fraction of ferroelectric orthorhombic phase (o-phase) through O-poor growth conditions can increase the spontaneous polarization of HfO₂ and (Hf,Zr)O₂ thin films. However, the first-principles calculations show that the growth may be limited by the easy formation of point defects in the orthorhombic and tetragonal phases of HfO₂, ZrO₂, and (Hf,Zr)O₂. Their dominant defects, O interstitial (O_i) under O-rich conditions and O vacancy (V_O) under O-poor condition, have low formation energies and quite high density (10¹⁶–10¹⁹ cm⁻³ for 800–1400 K growth temperature). Especially, O_i has negative formation energy in tetragonal HfO₂ under O-rich condition, causing non-stoichiometry and limiting the crystalline-seed formation during o-phase growth. High-density defects can cause disordering of dipole moments and increase leakage current, both diminishing the polarization. These results explain the experimental puzzle that the measured polarization is much lower than the ideal value even in O-poor thin films and highlight that controlling defects is as important as promoting the o-phase fraction for enhancing ferroelectricity. The O-intermediate condition (average of O-rich and O-poor conditions) and low growth temperature are proposed for fabricating HfO₂ and (Hf,Zr)O₂ with fewer defects, lower leakage current, and stronger ferroelectricity, which challenges the belief that O-poor condition is optimal.     

Transglycosylation Activity of Engineered Bifidobacterium Lacto-N-Biosidase Mutants at Donor Subsites for Lacto-N-Tetraose Synthesis

The health benefits of human milk oligosaccharides (HMOs) make them attractive targets as supplements for infant formula milks. However, HMO synthesis is still challenging and only two HMOs have been marketed. Engineering glycoside hydrolases into transglycosylases may provide biocatalytic routes to the synthesis of complex oligosaccharides. Lacto-N-biosidase from Bifidobacterium bifidum (LnbB) is a GH20 enzyme present in the gut microbiota of breast-fed infants that hydrolyzes lacto-N-tetraose (LNT), the core structure of the most abundant type I HMOs. Here we report a mutational study in the donor subsites of the substrate binding cleft with the aim of reducing hydrolytic activity and conferring transglycosylation activity for the synthesis of LNT from p-nitrophenyl β-lacto-N-bioside and lactose. As compared with the wt enzyme with negligible transglycosylation activity, mutants with residual hydrolase activity within 0.05% to 1.6% of the wild-type enzyme result in transglycosylating enzymes with LNT yields in the range of 10–30%. Mutations of Trp394, located in subsite -1 next to the catalytic residues, have a large impact on the transglycosylation/hydrolysis ratio, with W394F being the best mutant as a biocatalyst producing LNT at 32% yield. It is the first reported transglycosylating LnbB enzyme variant, amenable to further engineering for practical enzymatic synthesis of LNT.     

Braking behaviours of C/C–SiC mated with iron/copper-based PM in dry,wet and salt fog conditions

C/C–SiC composites have enormous potential as a new generation of brake materials. It is worth studying the friction and wear behaviours of these materials in special environments to ensure the safe and effective braking of trains in practical applications. In this study, the braking behaviours and wear mechanisms of C/C–SiC mating with iron/copper-based PM in dry, wet and salt fog conditions are compared in detail. The results show that the coefficient of friction (COF) in the wet condition is reduced by 14.13% compared with that under the dry condition. The COF value of the first braking under salt fog condition is increased by 12.27% and 30.75% compared to the dry and wet conditions, respectively. Additionally, the tail warping phenomenon of the braking curve disappears in wet condition, which is attributed to the weak adhesion of friction interfaces and the lubrication of the water film. The main wear mechanisms of C/C–SiC mating with iron/copper-based PM under dry condition are adhesive, fatigue and oxidation wear. However, the dominant wear in wet condition is abrasive wear. The cooling and lubrication of water reduce the tendency of thermal stress, and weaken adhesive and fatigue wear. Furthermore, salt fog can accelerate the corrosion of alloy friction film, leading to the damage of friction film. Meanwhile, the third body particles formed in salt fog condition participate in the braking process. The wear mechanisms in salt fog condition are dominated by abrasive and delamination wear.     

Meticulously tailoring phase boundary in KNN-based ceramics to enhance piezoelectricity and temperature stability

Although KNN-based ceramics with high electrical properties are obtained through a variety of strategies, the temperature sensitivity is still one of the key technical bottlenecks hindering practical applications. Here, we use a new strategy, meticulously tailoring phase boundary, to refine the ferroelectric boundary of KNN-based ceramics, leading to high piezoelectricity companied with improving temperature stability. The highest d₃₃ value in this system reaches 501 pC/N with a T_C ∼ 240°C, whereas a large strain of ∼0.134% can be kept with 10% lower deterioration until 100°C. The origin of high piezoelectricity is mainly attributed to the well-preserved multiphase coexistence and the appearance of nanodomains, which greatly facilitate the polarization rotation. Instead of the changed intrinsic thermal insensitivity, the precision phase boundary engineering plays an important role in strengthening the temperature stability of electric-induced strain. This work provides a simple and effective method to obtain both high electrical properties and excellent thermal stability in KNN-based ceramics, which is expected to promote the practical applications in the future.     

基于归一化水体指数及其阈值自适应算法的水体遥感反演效果分析

归一化水体指数（NDWI）是水体遥感反演的一种重要指标，其阈值及修正直接影响反演结果的精度。基于Landsat-8与GF-1光学多光谱影像，使用归一化水体指数法阈值0（TH₀）、最大类间方差法（OTSU）自适应阈值（TH_otsu）与均值漂移聚类算法（Mean-Shift）自适应阈值（TH_MS）分别对典型正常水体、云雾覆盖水体、富营养化水体、高含泥沙水体进行水体遥感提取与效果分析，结果表明：正常水体以TH₀为阈值提取精度最高，THMS提取精度次之，TH_otsu提取精度最差；而云雾覆盖水体、富营养化水体以及含泥沙水体使用THMS提取精度最高，尤其少量云雾覆盖下的水体，TH_MS具有更明显的优势，TH₀提取精度次之，TH_otsu提取精度最差；对于不同的阈值，Land?sat-8比GF-1总体表现出更高的水体提取精度。Mean-Shift算法应用于NDWI阈值修正与水体遥感反演具有快速、水质适应性强、效果稳定的优势，对尤其是复杂条件下的水体信息遥感反演具有较好的提取效果。     

阳泉地区“老窑水”现状及治理对策探究

阳泉地区的“老窑水”目前已在部分区域出露,对区域地表水和喀斯特地下水水质造成了一定的影响。因此,本文在充分了解“老窑水”成因及对阳泉地区的影响的基础上,针对区域现状,按照分类制定、综合施策的原则,系统探究了“源头控、末端治”有效结合的治理方案,可为当地“老窑水”治理提供参考,以期为其他类似地区的“老窑水”治理提供借鉴。