A Ligand-Controlled Approach Enabling Gold(I)-Catalyzed Stereoinvertive Glycosylation with Primal Glycosyl ortho-Alkynylbenzoate Donors.

A diarylurea-containing phosphine ligand-modulated stereoinvertive O-glycosylation with primal furanosyl and pyranosyl ortho-alkynylbenzoate (ABz) donors under gold(I) catalysis is disclosed. Both α- and ß-configured glycosides could be obtained from the corresponding stereochemically pure ß- and α-glycosyl donors with high yields and good to excellent stereoselectivities, respectively. This method accommodates a variety of glycosyl donors and alcoholic acceptors, leading to both 1,2-cis and 1,2-trans glycosidic linkages, and has been applied to the convenient preparation of a series of linear arabinan glycans. Mechanistic investigations reveal that the counteranion could bridge the diarylurea residue on the phosphine ligand with the alcoholic acceptor via hydrogen bond interactions, thereby permitting stereoinvertive displacement at the anomeric position.

Convergent Synthesis of the Nonreducing Hexasaccharide Fragment and the Dodecasaccharide Scaffold of Marine Lipopolysaccharide Axinelloside A.

A convergent synthesis of the dodecasaccharide scaffold of axinelloside A was achieved through Au(I)-catalyzed [6+6] glycosylation. The initially devised [3+1+2] assembly of the nonreducing hexasaccharide fragment was low-yielding, whereas a convergent [3+3] glycosylation under Au(I) catalysis was proven feasible, allowing for a semi-gram scale preparation of the wanted hexasaccharide. The requisite 1,2-cis glycosidic bonds were forged in a highly stereoselective fashion by virtue of remote acetyl group participation, and judicious manipulation of protecting groups. The synthetic dodecasaccharide has been properly protected for the downstream elaboration toward its natural form.

Synthesis of the Reducing-end Hexasaccharide Fragment of Marine Lipopolysaccharide Axinelloside A.

Chemical synthesis of an orthogonally protected hexasaccharide relevant to the reducing-end half of axinelloside A, a highly sulfated marine lipopolysaccharide, is disclosed. The synthesis features preparation of the scyllo-inositol unit via a Ferrier-type-II rearrangement, construction of the 1,2-cis-glycosidic bonds via remote participation, and concise [2+2+2] assembly via Au(I)-catalyzed glycosylation.

Dzyaloshinskii-Moriya-Interaction-Like Behavior in Confined Permalloy Nanostructures via Coupled Magnetic Vortices.

Dzyaloshinskii-Moriya interaction (DMI), one of antisymmetric exchanges, originates from the combination of low structural symmetry and large spin-orbit coupling and favors magnetization rotations with fixed chirality. Herein, this work reports a DMI-like behavior in permalloy via coupled vortices in confined structures. Under the in-plane magnetic fields, continuous reversals of different coupled vortices are directly observed by in situ Lorentz transmission electron microscopy, and reproduced by complementary micromagnetic simulations. The statistical results show that coupled vortices with opposite chirality appear more frequently with the frequency up to about 60%. Such an asymmetric phenomenon mainly arises from a DMI-like behavior, associated with the increased total energy difference between different ground-state coupled vortices. Moreover, in the reversal process, the junction between disks accelerates the annihilation of vortices moving toward it and is also the starting point of vortex nucleation. These results provide an effective method to generate a DMI-like behavior in magnetic systems with symmetry breaking surface and benefit the future development of vortex-based spintronic devices.

Nonreciprocal Transport in a Bilayer of MnBi2Te4 and Pt.

MnBi2Te4 (MBT) is the first intrinsic magnetic topological insulator with the interaction of spin-momentum locked surface electrons and intrinsic magnetism, and it exhibits novel magnetic and topological phenomena. Recent studies suggested that the interaction of electrons and magnetism can be affected by the Mn-doped Bi2Te3 phase at the surface due to inevitable structural defects. Here, we report an observation of nonreciprocal transport, that is, current-direction-dependent resistance, in a bilayer composed of antiferromagnetic MBT and nonmagnetic Pt. The emergence of the nonreciprocal response below the Néel temperature confirms a correlation between nonreciprocity and intrinsic magnetism in the surface state of MBT. The angular dependence of the nonreciprocal transport indicates that nonreciprocal response originates from the asymmetry scattering of electrons at the surface of MBT mediated by magnon. Our work provides an insight into nonreciprocity arising from the correlation between magnetism and Dirac surface electrons in intrinsic magnetic topological insulators.

Sign Change of Spin-Orbit Torque in Pt/NiO/CoFeB Structures.

Antiferromagnetic insulators have recently been proved to support spin current efficiently. Here, we report the dampinglike spin-orbit torque (SOT) in Pt/NiO/CoFeB has a strong temperature dependence and reverses the sign below certain temperatures, which is different from the slight variation with temperature in the Pt/CoFeB bilayer. The negative dampinglike SOT at low temperatures is proposed to be mediated by the magnetic interactions that tie with the "exchange bias" in Pt/NiO/CoFeB, in contrast to the thermal-magnon-mediated scenario at high temperatures. Our results highlight the promise to control the SOT through tuning the magnetic structure in multilayers.

A Stereoselective Glycosylation Approach to the Construction of 1,2-trans-ß-d-Glycosidic Linkages and Convergent Synthesis of Saponins.

Conventional syntheses of 1,2-trans-ß-d- or α-l-glycosidic linkages rely mainly on neighboring group participation in the glycosylation reactions. The requirement for a neighboring participation group (NPG) excludes direct glycosylation with (1→2)-linked glycan donors, thus only allowing stepwise assembly of glycans and glycoconjugates containing this type of common motif. Here, a robust glycosylation protocol for the synthesis of 1,2-trans-ß-d- or α-l-glycosidic linkages without resorting to NPG is disclosed; it employs an optimal combination of glycosyl N-phenyltrifluroacetimidates as donors, FeCl3 as promoter, and CH2 Cl2 /nitrile as solvent. A broad substrate scope has been demonstrated by glycosylations with 12 (1→2)-linked di- and trisaccharide donors and 13 alcoholic acceptors including eight complex triterpene derivatives. Most of the glycosylation reactions are high yielding and exclusively 1,2-trans selective. Ten representative, naturally occurring triterpene saponins were thus synthesized in a convergent manner after deprotection of the coupled glycosides. Intensive mechanistic studies indicated that this glycosylation proceeds by SN 2-type substitution of the glycosyl α-nitrilium intermediates. Importantly, FeCl3 dissociates and coordinates with nitrile into [Fe(RCN)n Cl2 ]+ and [FeCl4 ]- , and the ferric cationic species coordinates with the alcoholic acceptor to provide a protic species that activates the imidate, meanwhile the poor nucleophilicity of [FeCl4 ]- ensures an uninterruptive role for the glycosidation.

Total Synthesis of Starfish Cyclic Steroid Glycosides.

Starfishes have evolved with a special type of secondary metabolites, namely starfish saponins, to ward off various predators and parasites; among them, the starfish cyclic steroid glycosides stand out structurally, featuring a unique 16-membered ring formed by bridging the steroidal C3 and C6 with a trisaccharide. The rigid cyclic scaffold and the congested and vulnerable steroid-sugar etherate linkage present an unprecedented synthetic challenge. Here we report a collective total synthesis of the major starfish cyclic steroid glycosides, namely luzonicosides A (1) and D (2) and sepositoside A (3), with an innovative approach, which entails a de novo construction of the ether-linked hexopyranosyl units, use of olefinic pyranoses as sugar precursors, and a decisive ring-closing glycosylation under the mild gold(I)-catalyzed conditions.

Chemical synthesis of marine saponins.

Covering: 1989-2017 Saponins are characteristic metabolites of starfish and sea cucumbers, and occasionally are also found in sponges, soft coral, and small fish. These steroid or triterpenoid glycosides often show remarkable biological and pharmacological activities, such as antifungal, antifouling, shark repellent, antitumor and anti-inflammatory activities. Over one thousand marine saponins have been characterized; the majority of them can be categorized into three major structural types, i.e., asterosaponins, polyhydroxysteroid glycosides, and holostane glycosides. Thus far, only 12 marine saponins have been synthesized; those representing the major types were successfully synthesized recently. The syntheses involve preparation of the aglycones from the terrestrial steroid or triterpene materials, installation of the carbohydrate units, and manipulation of the protecting groups. Herein, we provide a comprehensive review on these syntheses.

Nonlinear Planar Hall Effect.

An intriguing property of a three-dimensional (3D) topological insulator (TI) is the existence of surface states with spin-momentum locking, which offers a new frontier of exploration in spintronics. Here, we report the observation of a new type of Hall effect in a 3D TI Bi_{2}Se_{3} film. The Hall resistance scales linearly with both the applied electric and magnetic fields and exhibits a π/2 angle offset with respect to its longitudinal counterpart, in contrast to the usual angle offset of π/4 between the linear planar Hall effect and the anisotropic magnetoresistance. This novel nonlinear planar Hall effect originates from the conversion of a nonlinear transverse spin current to a charge current due to the concerted actions of spin-momentum locking and time-reversal symmetry breaking, which also exists in a wide class of noncentrosymmetric materials with a large span of magnitude. It provides a new way to characterize and utilize the nonlinear spin-to-charge conversion in a variety of topological quantum materials.

MST1 suppresses viability and promotes apoptosis of glioma cells via upregulating SIRT6 expression.

It has been well established that mammalian sterile 20-like 1 (MST1) functions as a suppressor via regulating cell progression in many tumors. However, the molecular mechanism of MST1 on regulating glioma progression remains unclear. Here, we discovered that MST1 was robustly down-regulated in glioma tissues and cells. Functional analysis showed that over-expression of MST1 downregulated viability and colony formation and promoted apoptosis of glioma cells. Our results also identified that MST1 positively regulated expression of SIRT6 (Sirtuin 6) via transcriptional factor FOXO3a (Forkhead box O3a). Furthermore, the functional role of MST1 in glioma cell viability (or apoptosis) were significantly reversed after knocking down of SIRT6. Our research indicates that MST1 is a potential biomarker for the prognosis and diagnosis of glioma and provides new direction on the molecular mechanism of glioma progression and development.

Room-Temperature Giant Charge-to-Spin Conversion at the SrTiO3-LaAlO3 Oxide Interface.

The two-dimensional electron gas (2DEG) formed at the interface between SrTiO3 (STO) and LaAlO3 (LAO) insulating layer is supposed to possess strong Rashba spin-orbit coupling. To date, the inverse Edelstein effect (i.e., spin-to-charge conversion) in the 2DEG layer is reported. However, the direct effect of charge-to-spin conversion, an essential ingredient for spintronic devices in a current-induced spin-orbit torque scheme, has not been demonstrated yet. Here we show, for the first time, a highly efficient spin generation with the efficiency of ∼6.3 in the STO/LAO/CoFeB structure at room temperature by using spin torque ferromagnetic resonance. In addition, we suggest that the spin transmission through the LAO layer at a high temperature range is attributed to the inelastic tunneling via localized states in the LAO band gap. Our findings may lead to potential applications in the oxide insulator based spintronic devices.

Total Synthesis of Linckosides A and B, the Representative Starfish Polyhydroxysteroid Glycosides with Neuritogenic Activities.

Linckosides A and B, two starfish metabolites with promising neuritogenic activities, are synthesized in a longest linear sequence of 32 steps and 0.5% overall yield; this represents the first synthesis of members of the polyhydroxysteroid glycoside family, which occur widely in starfishes.

The Relationship Between Negotiable Fate and Life Satisfaction: The Serial Mediation by Self-Esteem and Positive Psychological Capital.

Purpose: Negotiable fate as a belief in coping with the difficulties and uncertainties of life has an impact on people's mental health. This study aims to understand the influence of negotiate fate on college students' life satisfaction and its underlying mechanism. Methods: A cross-sectional study was conducted with the participation of 1523 students from six universities across China. The study aimed to measure the variables of negotiable fate, self-esteem, positive psychological capital, and life satisfaction of all participants. To investigate the effect of negotiable fate on college students' life satisfaction and the mediating roles of self-esteem and positive psychological capital in this relationship, a serial mediation effects model using Hayes' PROCESS was employed. Results: The results suggest that negotiable fate has a positive predictive effect on college students' life satisfaction. The impact of negotiable fate on college students' life satisfaction was mediated by self-esteem and positive psychological capital, and the chained mediation of self-esteem and positive psychological capital. Conclusion: To summarize, the belief of negotiable fate has practical significance for the enhancement of college student's mental health and quality of life, and the cultivation of college students' belief of negotiable fate can be actively promoted in the future to help them better cope with the uncertainties and challenges in their lives to improve their life satisfaction.

Expeditious chemical synthesis of xylomannans disproves the proposed antifreeze activities.

Cold-adapted species are able to generate cryoprotective proteins and glycoproteins to prevent freezing damage. The [→4)-ß-D-Manp-(1→4)-ß-D-Xylp-(1→] n xylomannan from the Alaska beetle Upis ceramboides was disclosed by Walters and co-workers in 2009 as the first glycan-based antifreeze agent, which was later reported to be found in diverse taxa. Here, we report the rapid synthesis of four types of xylomannans, including the proposed antifreeze xylomannan up to a 64-mer (Type I), the regioisomeric [→3)-ß-D-Manp-(1→4)-ß-D-Xylp-(1→] n 16-mer (Type II), the diastereomeric [→4)-ß-L-Manp-(1→4)-ß-D-Xylp-(1→] n 16-mer (Type III) and the block-wise [→4)-ß-D-Manp-(1→] m [→4)-ß-D-Xylp-(1→] n 32-mer (Type IV), by employing a strategic iterative exponential glycan growth (IEGG) process. The nuclear magnetic resonance spectral data of the alleged natural xylomannan are in accordance only to those of the block-wise Type IV glycan and none of these synthetic xylomannans has been found to be capable of inducing thermal hysteresis. These results disprove the previous reports about the natural occurrence of antifreeze xylomannans.

Synthesis of C-Oligosaccharides via Ni-Catalyzed Reductive Hydroglycosylation.

C-Oligosaccharides are metabolically stable surrogates of native glycans containing O/N/S-glycosidic linkages and thus have therapeutic potential. Here we report a straightforward approach to the synthesis of vinyl C-linked oligosaccharides via the Ni-catalyzed reductive hydroglycosylation of alkynyl glycosides with glycosyl bromides.

Stereoselective Synthesis of ß-glycosyl Esters via 1-Hydroxybenzotriazole Mediated Acylation of Glycosyl Hemiacetals.

Highly stereoselective access to ß-glycosyl esters was disclosed, employing 1-hydroxybenzotriazole (HOBt) mediated esterification of glycosyl hemiacetals in the presence of EDCI and 1,4-diazabicyclo[2.2.2]octane (DABCO). Mechanistic studies indicated a dynamic kinetic acylation pathway. In addition, a stereoretentive esterification of glycosyl hemiacetals with tert-butyloxycarbonyl ortho-hexynylbenzoate and DMAP was also reported.

Synthesis of 2-Indolyl C-Glycoside Neopetrosins A and C and Congeners via Ni-Catalyzed Photoreductive Cross-Coupling.

The synthesis of neopetrosins A and C, two 2-indolyl C-α-d-mannopyranosides, and their congeners has been realized via a direct Ni/photoredox-catalyzed reductive coupling of 3-methoxycarbonyl-2-iodo-1H-indoles with pyranosyl bromides.

A Cu(OTf)2-Catalyzed Glycosylation with Glycosyl ortho-N-Phthalimidoylpropynyl Benzoates as Donors.

A Cu(OTf)2-catalyzed glycosylation protocol using glycosyl ortho-N-phthalimidoylpropynyl benzoates (NPPBs) as donors was disclosed, which features an inexpensive copper catalyst, operationally convenient conditions, high to excellent yields, and a broad substrate scope. Mechanistic studies indicated an isochromen-4-yl copper(II) intermediate arising from the departure of the leaving group.

Characterizing the Gut Microbiota of Eurasian Otter (Lutra lutra chinensis) and Snub-Nosed Monkey (Rhinopithecus roxellana) to Enhance Conservation Practices in the Foping National Nature Reserve of China.

Understanding the interaction between the microbial composition in the habitat and the gut of wildlife will contribute to conservation efforts since changes in the gut microbiome have been proven to influence the healthy and nutritional status of the host. This study analyzed the relationship between soil microbes and the microbial diversity and structure of the distal gut of the terrestrial golden snub-nosed monkey and Eurasian otter in the Foping National Nature Reserve (FNNR). A total of 15 otter fecal samples and 18 monkey fecal samples were collected from which 5 and 6 samples, respectively, were randomly selected for microbiome analysis. The remaining samples were used for fecal short-chain fatty acids (SCFAs) analysis. Soil samples from the otter and monkey habitats at each sampling point (eight in total) were also collected for microbiome analysis. The microbial phyla with the greatest relative abundance in soil or animal samples were Proteobacteria (41.2, 32.7, and 73.3% for soil, otters, and monkeys, respectively), Firmicutes (0.4% soil, 30.1% otters, and 14.4% monkeys), Bacteroidota (5.6% soil, 17.0% otters, and 8.3% monkeys), and Acidobacteriota (24.6% soil, 1.7% otters, and 0.1% monkeys). The estimation of alpha diversity indices revealed that the feature, Chao1, and Shannon indices of the soil microbiome were the greatest (p < 0.01) among the three groups, followed by those of the otter microbiome and those of the monkey microbiome (p < 0.01). Beta diversity analyses confirmed differences in the microbiota of the three types of samples. The determination of SCFA concentration in feces revealed that total volatile fatty acids, acetic acid, and isovaleric acid were greater (p < 0.05) in otters than in monkeys, while propionic acid followed the opposite pattern (p < 0.05). Correlation analysis of the microbiome and SCFA contents showed that propionic acid was positively correlated with significantly different bacterial groups, while acetic and butyric acid and total volatile acids were negatively correlated. This study confirmed that the fecal microbes of Eurasian otters and golden snub-nosed monkeys in the reserve are related to the soil microbial communities of their habitats, but they have different bacterial community structures and compositions, and there are different SCFA metabolic patterns in the gut of the two animals. The present study will help to improve wildlife protection in the FNNR.