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.     

Cryptanalysis of nonlinear confusion component based encryption algorithm

Recently many substitution box based encryption algorithms ensuring privacy have been proposed. Many, chaotic map based S-boxes have been generated posing high nonlinearity and strong cryptographic properties. Encryption schemes depending on the substitution box (S-box) only are weak and easily breakable with the help of chosen plaintext and ciphertext attacks. In this work, we have completely cryptanalyzed S-box based encryption scheme successfully by two types of attacks. Cryptanalysis in both types of attacks is performed by only one selected image. Moreover, we have suggested some improvements in the algorithm to defeat attacks.     

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.     

基于K-means和SOM的水下传感器数据采集方法

随着海洋资源勘探和海洋污染物监控工作的开展，水文数据的监测和采集等已经成为重要的研究方向。其中，水下无线传感器网络在水文数据采集过程中起着举足轻重的作用。本文研究的是水下无线传感器二维监测网络模型中，传感器节点数据采集的问题，其设计方法是通过自组织映射（Self-organizing mapping，SOM）对传感器节点进行路径最优化处理，结合优化的路径图形和K-means算法找到路径内部聚合点，利用聚合点和传感器的节点得到传感器通信半径内的数据采集点，最后通过SOM得到水下机器人（Autonomous underwater vehicle，AUV）到各个数据采集点采集数据的最优路径。经过实验验证，在水下1 200 m×1 750 m范围内布置52个传感器节点的情景下，数据采集点相比于传感器节点路径规划采用相同的采集顺序得到的路径优化了6.7%；对数据采集点重新进行自组织路径规划得到的路径比传感器结点路径的最优解提高了12.2%。增加传感器节点的数量，其结果也大致相同，因此采用该方法可以提高水下机器人采集数据的效率。     

Mechanical performance of ITO/Ag/ITO multilayer films deposited on glass substrate by RF and DC magnetron sputtering

ITO/Ag/ITO multilayer thin films have been a potential substitute of the conventional single-layer transparent conducting film. Nevertheless, the mechanical stability under preparation and in-service conditions still limits their applications and developments. In this paper, the influences of different structural properties as well as layer structure on both surface morphological properties and mechanical properties of the ITO/Ag/ITO multilayer thin films in comparison with commercial single-layer ITO thin film were systematically investigated. The results demonstrate that, i) the tri-layer composite has large impacts on the preferential orientation, and exhibits the decreased values of surface roughness, net lattice distortion and residual stress; ii) the increased hardness (H) and decreased Young's modulus (E) for full annealed ITO/Ag/ITO multilayer films indicate that it is possible to tailor mechanical properties of the materials by manufacturing multilayer composite; iii) the ITO/Ag/ITO multilayer thin film exhibits remarkable improvements in wear resistance with the increase of annealing temperature, which is mainly attributed to the increased ratios of H/E and H³/E².     

Optimizing the stability and electrical transport properties of CeNbO4+δ-based oxide ceramics by regulating oxygen ion content

CeNbO_4+δ ceramics have attracted extensive research interest because of their unique mixed ion-electron transport characteristics and interesting structure-functional characteristics caused by the difference in oxygen ion content. Although the change of oxygen ion content brings rich redox properties, it also causes serious crystal transformation and abnormal electrical transport properties. In order to obtain stable structure and excellent electrical transport properties, the directional regulation of the oxygen ion content has been realized through introducing Al₂O₃ and high temperature aging. After 600 h of aging at 1073 K, the prepared composite ceramics not only obtain a stable structure without crystal transformation, but also show good negative temperature coefficient (NTC) thermistor characteristics in the temperature range of 473 K–1273 K, in which the linear fitting maximum Pearson's r of the relationship between lnρ and 1000/T can reach 99.97%. The proposed method provides a new thought for the design and application of high-temperature electronic ceramics.     

Structural characteristics and high-temperature oxidation behaviour of nano-HfO2-doped thermal barrier coatings

The uneven growth of thermally grown oxides (TGOs) in thermal barrier coating systems is an important cause of cracking failure at the coating interface in high-temperature environments. The doping of rare earth elements in the bonding layer can effectively inhibit the formation of spinel oxides in the TGO and improve the high-temperature oxidation resistance of the coating. However, a single rare earth element has a limited effect on inhibiting TGO failure. In this study, a NiCoCrAlYHf coating was prepared using a supersonic flame spraying (HVOF) technique. The effects of HfO₂ doping on the high-temperature oxidation behaviour of the coatings and diffusion behaviour of metallic elements in the coatings were investigated at 1100 °C. The results showed that the nano-sized HfO₂ filled the pores between the powder particles and improved the hardness of the coating. During the high-temperature oxidation process, the oxides formed by Hf and Y had a large size and low solubility, which effectively blocked the diffusion of Al. This slowed the generation of spinel oxides, effectively inhibited the growth of the TGO, it inhibits the initiation and propagation of cracks within the coating, reduces damage to the coating from tensile and compressive stresses at the interface, and improved the high-temperature oxidation resistance of the coating.