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An enantioselective total synthesis of the polycyclic diterpene (+)-chatancin, a potent PAF antagonist, is reported. Proceeding in seven steps from dihydrofarnesal, this synthetic route was designed to circumvent macrocyclization-based strategies to complex, cyclized cembranoids. The described synthesis requires only six chromatographic purifications, is high yielding, and avoids protecting-group manipulations. An X-ray crystal structure of this fragile marine natural product was obtained. [ABSTRACT FROM AUTHOR]

As one of the best image clustering methods, fuzzy local information C-means is often used for image segmentation. The effects of noise are avoided by utilizing the spatial relationship among pixels, but it often generates boundary zones for the mix pixels around the edges. This letter presents an image spatial clustering method, called fuzzy C-means with edge and local information (FELICM), which reduces the edge degradation by introducing the weights of pixels within local neighbor windows. The edges are extracted at first by Canny edge detection. During detection, two adaptive thresholds obtained by multi-Otsu method are used. Then, different weights are set according to whether the window center and the local neighbors are separated by an edge or not. Pixels, together with different weighted local neighbors, are clustered iteratively, until the final clustering result is obtained. The method can be directly applied to the image without any filter preprocessing, and the experimental results over remote sensing images show that FELICM not only effectively solves the problem of isolated and random distribution of pixels inside regions but also obtains high edge accuracies. [ABSTRACT FROM PUBLISHER]

Herein, we present a unified chemical synthesis of three subgroups of cephalotaxus diterpenoids. Key to the success lies in adopting a synthetic strategy that is inspired by biosynthesis but is opposite in nature. By employing selective one‐carbon introduction and ring expansion operations, we have successfully converted cephalotane‐type C18 dinorditerpenoids (using cephanolide B as a starting material) into troponoid‐type C19 norditerpenoids and intact cephalotane‐type C20 diterpenoids. This synthetic approach has enabled us to synthesize cephinoid H, 13‐oxo‐cephinoid H, 7‐oxo‐cephinoid H, fortalpinoid C, 7‐epi‐fortalpinoid C, cephanolide E, and 13‐epi‐cephanolide E. Furthermore, through the development of an intermolecular asymmetric Michael reaction between β‐oxo esters and β‐substituted enones, we have achieved the enantioselective synthesis of advanced intermediates within our synthetic sequence, thus formally realizing the asymmetric total synthesis of the cephalotaxus diterpenoids family. [ABSTRACT FROM AUTHOR]

Secondary metabolites that have the same biological origin must share some relationship in their biosynthesis. Exploring this relationship has always been a significant task for synthetic biologists. However, from the perspective of synthetic chemists, it is equally important to propose, prove, or refute potential biosynthetic pathways in order to elucidate and understand the biosynthesis of homologous secondary metabolites. In this study, driven by the high structural similarity between the homologous Ganoderma meroterpenoids cochlearol B and ganocin B, two chemically synthetic strategies were designed and investigated sequentially for the synthesis of cochlearol B from ganocin B. These strategies include intramolecular metal‐catalyzed hydrogen atom transfer (MHAT) and intramolecular photochemical [2+2] cycloaddition. The aim was to reveal their potential biosynthetic conversion relationship using chemical synthesis methods. As a result, a highly efficient total synthesis of cochlearol B, cochlearol T, cochlearol F, as well as the formal total synthesis of ganocins A–B, and ganocochlearins C–D, has been achieved. Additionally, a novel synthetic approach for the synthesis of 6,6‐disubstituted 6H‐dibenzo[b,d]pyran and its analogues has been developed through palladium(II)‐catalyzed Wacker‐type/cross‐coupling cascade reactions. [ABSTRACT FROM AUTHOR]

Silicon oxide‐graphite (SiOx‐G) composites are promising anode materials for building practical high‐energy Li‐ion batteries. To acquire long and safe operation of battery, extensive efforts are made to maintain stable Li storage of SiOx‐G against materials aging and the accompanied performance fade. While previous studies mostly focus on the cycling aging, the calendar aging occurred during battery storage at a high state of charge or high temperature has not received sufficient attention. In this work, a mechanism study on the calendar aging chemistry of fully lithiated SiOx‐G electrodes in half‐cells both at ambient and high temperature (60 °C) is performed. Unmodified SiOx is employed as active materials to inspect the change of thermodynamics properties in the bulk and at interfaces. By excluding the interference from cathode, it is revealed that besides aggravated parasitic reactions happening at interface, Li migration from the lithiated graphite to the vicinal SiOx particles is also responsible for calendar aging of SiOx‐G electrodes, and high‐temperature storage notably accelerates the aging process. This work enriches the fundamental understandings about the multifactor‐coupled aging process of anode materials and sheds lights on rational materials design toward improved calendar life of a high‐energy rechargeable battery. [ABSTRACT FROM AUTHOR]

Herein, we report a concise and divergent synthesis of the complex hasubanan alkaloids metaphanine and oxoepistephamiersine from commercially available and inexpensive cyclohexanedione monoethylene acetal. Our synthesis features a palladium‐catalyzed cascade cyclization reaction to set the tricyclic carbon framework of the desired molecules, a regioselective Baeyer–Villiger oxidation followed by a MeNH2 triggered skeletal reorganization cascade to construct the benzannulated aza[4.4.3]propellane, and a strategically late‐stage regio‐/diastereoselective oxidative annulation of sp3 C−H bond to form the challenging THF ring system and hemiketal moiety in a single step. In addition, a highly enantioselective alkylation of cyclohexanedione monoethylene acetal paved the way for the asymmetric synthesis of target molecular. [ABSTRACT FROM AUTHOR]

The products are formed in very high yields and with very high enantioselectivities. [ABSTRACT FROM AUTHOR]

Ether solvents with superior reductive stability promise excellent interphasial stability with high‐capacity anodes while the limited oxidative resistance hinders their high‐voltage operation. Extending the intrinsic electrochemical stability of ether‐based electrolytes to construct stable‐cycling high‐energy‐density lithium‐ion batteries is challenging but rewarding. Herein, the anion‐solvent interactions were concerned as the key point to optimize the anodic stability of the ether‐based electrolytes and an optimized interphase was realized on both pure‐SiOx anodes and LiNi0.8Mn0.1Co0.1O2 cathodes. Specifically, the small‐anion‐size LiNO3 and tetrahydrofuran with high dipole moment to dielectric constant ratio realized strengthened anion‐solvent interactions, which enhance the oxidative stability of the electrolyte. The designed ether‐based electrolyte enabled a stable cycling performance over 500 cycles in pure‐SiOx||LiNi0.8Mn0.1Co0.1O2 full cell, demonstrating its superior practical prospects. This work provides new insight into the design of new electrolytes for emerging high‐energy density lithium‐ion batteries through the regulation of interactions between species in electrolytes. [ABSTRACT FROM AUTHOR]

Antiphospholipid antibodies are a family of closely related but heterogeneous autoantibodies that may have different biological and pathogenic properties. The article investigates the distribution of six kinds of Antiphospholipid antibodies (aPL) in the serum of healthy volunteers. Whole peripheral blood samples of 82 healthy volunteers were drawn from blood donors with median age of 39.3 years. The findings suggest that healthy volunteers possess aPL. Some aPL are natural autoantibodies that are present in healthy individuals. Other aPL present in sera from healthy individuals are those that may be uncovered by heating sera at 56 degrees Celsius for 30 minutes.

In this work, we present the details of the first unified chemical synthesis of cephalotaxus diterpenoids with three distinct carbon skeleton structures. Drawing on our previous synthesis of cephalotane-type C18 dinorditerpenoid and inspired by the proposed biosynthetic synthesis pathway, we formulated a biosynthetic reversed chemical synthetic strategy. This strategy facilitated the conversion of C18 dinorditerpenoid into troponoid-type C19 norditerpenoid and intact cephalotane-type C20 diterpenoid through pivotal one-carbon introduction and ring expansion reactions. In the synthesis of troponoid-type C19 norditerpenoid, we utilized TMSCHN 2 as one-carbon unit and meticulously examined the selective regulatory effect of halogen substituents in ring expansion and rearrangement reactions. This endeavor culminated in the successful synthesis of natural product molecules within this subclass, notably including cephinoid H and fortalpinoid C, marking the first chemical total synthesis in this line of research. In the investigation of intact cephalotane-type C20 diterpenoid synthesis, while adhering to the overall synthesis strategy, we initially pursued a ring expansion before carbon introduction approach, which proved unsuccessful. Subsequently, we explored a synthetic route of introducing carbon first and then expanding the ring, leading to a successful outcome and resulting in the first chemical total synthesis of the representative molecule cephanolide E within this subclass. Various challenges such as establishing crucial quaternary carbon stereocenters, selecting appropriate one-carbon units, and controlling ring expansion reactions were effectively addressed throughout this process. Moreover, enantioselective synthesis of natural products within this family was achieved through the development of asymmetric Michael reactions. A detailed research summary is presented for introducing the unified total synthesis of three subgroups of cephalotaxus diterpenoids, with a novel synthetic route possessing a reverse order with potential biosynthetic route. The troponoid-type C19 norditerpenoids cephinoid H and fortalpinoid C could be synthesized from cephalotane-type C18 dinorditerpenoid-cephanolide B through regioselective ring expansion modulated by introducing a chlorine atom at the C15 site. For intact cephalotane-type C20 diterpenoids, we develop two synthetic routes to explore their syntheses from cephalotane-type C18 dinorditerpenoid-cephanolide B, involving ring expansion/C17-introduction and its reverse process. The first synthetic route is unsuccessful due to the great difficulty of C17-introduction and the first total synthesis cephalotane-type C20 diterpenoid cephanolide E is finally realized via the second synthetic route. [Display omitted] [ABSTRACT FROM AUTHOR]

[Display omitted] • Poly (poly (ethylene glycol) methacrylate) (PPEGMA) was grafted onto PP separator by N-hydroxyphthalimide (NHPI) catalysis combined with ARGET-ATRP. • Electrolyte wettability of PPEGMA functionalized PP was enhanced evidently compared to that of pristine PP separator. • Rate performance and long cycle ability for cell with the modified PP separator was improved significantly. • The proposed strategy was also applied to modify other polyolefine membranes for advanced applications. Surface modification of polyolefine separators for high performance lithium-ion batteries has been a worthwhile research topic. In this work, poly (poly (ethylene glycol) methacrylate) (PPEGMA) was firstly grafted onto polypropylene (PP) separator based on N-hydroxyphthalimide (NHPI) catalysis and activators regenerated by electron transfer atom transfer radical polymerization (ARGET-ATRP). Bis(2,2,2-trichloroethyl) azodicarboxylate (BTCEAD) was anchored on the surface of PP separators in the presence of NHPI. Then BTCEAD functionalized PP separator initiated the polymerization of PEGMA by ARGET-ATRP. Thus, structure controllable PPEGMA was grafted on the surface of PP separators. The results of contact angle and electrolyte uptake tests demonstrated that electrolyte wettability of PPEGMA functionalized PP separator has been significantly improved. Electrochemical measurements indicated that the ionic conductivity and discharge capacity retention of cells assembled with PPEGMA functionalized PP separators were distinctly higher than that of cells with pristine PP separator. Herein, we presented a new methodology with high efficiency to modify PP separators under mild condition, which was also applied to other polyolefine separator for high performance lithium-ion batteries. The proposed approach might have many other potential applications in membrane modification field. [ABSTRACT FROM AUTHOR]

Two hole transporting materials (HTMs), SFX-PT1 and SFX-PT2 , were designed and synthesized by combing a spiro[fluorene-9, 9′-xanthene] (SFX) core with tetra- phenothiazine substituted at the 2,2′,7,7′- and 2,3′,6,′7-positions, respectively. As comparison, a HTM with tetra-phenothiazine substituted at the 2,2′,7,7′-positions of a 9, 9′-spirobifluorene core ( Spiro-PT ) was also synthesized. Their photophysical and electrochemical properties, thermal stability and hole mobility were investigated. It was demonstrated that SFX-centered HTMs exhibited superior Stokes shift, thermal stability and hole mobility than those of Spiro-PT . Combining with the substituted positions modification, SFX-PT1 has the largest Stokes shift of 197 nm, the highest decomposition temperature of 435 °C and hole mobility of 2.08 × 10 −3 cm 2 V −1 S −1 . Moreover, the energy levels of the HTMs were matched very well with that of CH 3 NH 3 PbI 3 . Our results indicated that SFX-centered, phenothiazole substituted HTMs might be potential candidates for efficient perovskite solar cells. [ABSTRACT FROM AUTHOR]

The inherently huge volume expansion during Li uptake has hindered the use of Si-based anodes in high-energy lithium-ion batteries. While some pore-forming and nano-architecting strategies show promises to effectively buffer the volume change, other parameters essential for practical electrode fabrication, such as compaction density, are often compromised. Here we propose a new in situ Mg doping strategy to form closed-nanopore structure into a micron-sized SiO x particle at a high bulk density. The doped Mg atoms promote the segregation of O, so that high-density magnesium silicates form to generate closed nanopores. By altering the mass content of Mg dopant, the average radii (ranged from 5.4 to 9.7 nm) and porosities (ranged from 1.4 % to 15.9 %) of the closed pores are precisely adjustable, which accounts for volume expansion of SiO x from 77.8 % to 22.2 % at the minimum. Benefited from the small volume variation, the Mg-doped micron-SiO x anode demonstrates improved Li storage performance towards realization of a 700-(dis)charge-cycle, 11-Ah-pouch-type cell at a capacity retention of >80 %. This work offers insights into reasonable design of the internal structure of micron-sized SiO x and other materials that undergo conversion or alloying reactions with drastic volume change, to enable high-energy batteries with stable electrochemistry., (© 2024 Wiley-VCH GmbH.)

Herein, we present the first racemic total synthesis of the structurally complex monoterpene indole alkaloids rhynchines A-E, starting from commercially available methyl nicotinate and 3-(2-bromoethyl)-1 H -indole. The success of our synthesis is attributed to the utilization of a bioinspired synthetic strategy, which facilitated the rapid construction of the pentacyclic core skeleton of the target molecules through biomimetic skeletal rearrangement and late-stage C-H oxidative cyclization. Additionally, silica-gel-promoted tautomerization played a crucial role as a strategic element in the chemical synthesis of rhynchines A and B.

Micron-sized Si anode promises a much higher theoretical capacity than the traditional graphite anode and more attractive application prospect compared to its nanoscale counterpart. However, its severe volume expansion during lithiation requires solid electrolyte interphase (SEI) with reinforced mechanical stability. Here, we propose a solvent-induced selective dissolution strategy to in situ regulate the mechanical properties of SEI. By introducing a high-donor-number solvent, gamma-butyrolactone, into conventional electrolytes, low-modulus components of the SEI, such as Li alkyl carbonates, can be selectively dissolved upon cycling, leaving a robust SEI mainly consisting of lithium fluoride and polycarbonates. With this strategy, raw micron-sized Si anode retains 87.5% capacity after 100 cycles at 0.5 C (1500 mA g -1 , 25°C), which can be improved to >300 cycles with carbon-coated micron-sized Si anode. Furthermore, the Si||LiNi 0.8 Co 0.1 Mn 0.1 O 2 battery using the raw micron-sized Si anode with the selectively dissolved SEI retains 83.7% capacity after 150 cycles at 0.5 C (90 mA g -1 ). The selective dissolution effect for tailoring the SEI, as well as the corresponding cycling life of the Si anodes, is positively related to the donor number of the solvents, which highlights designing high-donor-number electrolytes as a guideline to tailor the SEI for stabilizing volume-changing alloying-type anodes in high-energy rechargeable batteries., (© 2023. The Author(s).)

Ether solvents with superior reductive stability promise excellent interphasial stability with high-capacity anodes while the limited oxidative resistance hinders their high-voltage operation. Extending the intrinsic electrochemical stability of ether-based electrolytes to construct stable-cycling high-energy-density lithium-ion batteries is challenging but rewarding. Herein, the anion-solvent interactions were concerned as the key point to optimize the anodic stability of the ether-based electrolytes and an optimized interphase was realized on both pure-SiO x anodes and LiNi 0.8 Mn 0.1 Co 0.1 O 2 cathodes. Specifically, the small-anion-size LiNO 3 and tetrahydrofuran with high dipole moment to dielectric constant ratio realized strengthened anion-solvent interactions, which enhance the oxidative stability of the electrolyte. The designed ether-based electrolyte enabled a stable cycling performance over 500 cycles in pure-SiO x ||LiNi 0.8 Mn 0.1 Co 0.1 O 2 full cell, demonstrating its superior practical prospects. This work provides new insight into the design of new electrolytes for emerging high-energy density lithium-ion batteries through the regulation of interactions between species in electrolytes., (© 2023 Wiley-VCH GmbH.)

Herein, we report an efficient synthetic method for constructing the tetracyclic scaffold of sulfur-containing discorhabdin-type alkaloids. The key to success is the BF 3 •Et 2 O-promoted dienone-phenol-type rearrangement/sulfur insertion cascade reaction, which converts the common and readily available N,O -acetal-bridged tetracyclic framework to the labile and synthetically challenging N,S -acetal-bridged tetracyclic framework in a single step. Additionally, the hypervalent iodine promoted intramolecular oxidative dearomatization terminated with amide and indium(III) acetate-facilitated radical cyclization were also essential elements in this study.