Nonbiaryl N-C atropisomer is an important structural scaffold, which is present in natural products, medicines and chiral ligands. However the direct enantioselective C-H amination to access ...optically pure N-C atropisomer is still difficult and rare. Here we report a π-π interaction and dual H-bond concerted control strategy to develop the chiral phosphoric acids (CPAs) catalyzed direct intermolecular enantioselective C-H amination of N-aryl-2-naphthylamines with azodicarboxylates as amino sources for the construction of atroposelective naphthalene-1,2-diamines. This type of N-C atropisomers is stabilized by intramolecular hydrogen bond and the method features a broad range of substrates, high yields and ee values, providing a strategy to chirality transfer via the modification of N-C atropisomers.
•All-solid-state complementary ITO/WO3/Ta2O5/NiO/ITO ECD.•UV curing LiClO4+PC+UV as a solid electrolyte.•NiO is an auxiliary layer for a complementary ECD.•ECD deposited by ion-beam assisted ...electron-beam evaporation
This research investigates the optical, nanostructure, electrochemical, and binding-energy performances of a Nickel Oxide (NiO) auxiliary layer for a complementary ultraviolet (UV)-cured all-solid-state electrochromic device (ECD). The complementary ITO/WO3/Ta2O5/Electrolyte/NiO/ITO ECD was separated into two sub-modules, one being the colored NiO anode, the other being the colored WO3 cathode. These were combined using UV curing LiClO4+PC+UV glue as a solid electrolyte. The NiO film was deposited by ion-beam assisted (IAD) electron-beam evaporation under different oxygen flow rates ranging from 5 to 20 sccm, and the evaporation formed columnar nanostructures that allowed the Li+ ions to enter and leave. These experimental results exhibited location shifts for the binding-energy of Ni3d and O1s has the blue shift at the oxygen flow far away of 15 sccm. Depositing the NiO film under an oxygen flow of 15 sccm (111) showed the highest color/bleach variation of ΔT=45.9%@550nm, the greatest cyclic voltammetry (CV) cladding area of Q=31.39 mC, an alternating current (AC) impedance of 28 kΩ, and an ionic conduction rate of 4.46×10−7 S cm−1. The columnar NiO film deposited using IAD electron-beam evaporation has the potential to be used as an auxiliary layer for an all-solid-state ECD.
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In general, enantioselective C–H functionalization of N-monosubstituted anilines is a highly challenging task owing to the competitive chemoselective N–H bond insertion reactions. In this paper, we ...reported a direct highly chemo-, site-, and enantioselective para C–H aminoalkylation of N-monosubstituted aniline derivatives with isatin-derived ketimines in the presence of chiral phosphoric acids (CPAs) and offered a practical strategy for para asymmetric C–H functionalization of anilines containing N–H bonds.
Zymomonas mobilis is a gram-negative facultative anaerobic spore, which is generally recognized as a safe. As a promising ethanologenic organism for large-scale bio-ethanol production, Z. mobilis has ...also shown a good application prospect in food processing and food additive synthesis for its unique physiological characteristics and excellent industrial characteristics. It not only has obvious advantages in food processing and becomes the biorefinery chassis cell for food additives, but also has a certain healthcare effect on human health. Until to now, most of the research is still in theory and laboratory scale, and further research is also needed to achieve industrial production. This review summarized the physiological characteristics and advantages of Z. mobilis in food industry for the first time and further expounds its research status in food industry from three aspects of food additive synthesis, fermentation applications, and prebiotic efficacy, it will provide a theoretical basis for its development and applications in food industry. This review also discussed the shortcomings of its practical applications in the current food industry, and explored other ways to broaden the applications of Z. mobilis in the food industry, to promote its applications in food processing.
This research modified a porous titanium dioxide (TiO2) dye-sensitized solar cell (DSSC) with reduced graphene oxide (rGO) to improve efficiency. A secondary color selectivity effect was obtained by ...addition of an organic Fabry-Perot (F.P.) cavity. The TiO2 was doped with a variety of rGO including 0, 1, 5, and 10 wt%. Small molecule (McFarland and Tang, 2003; McFarland and Tang, 2003) 6,6-phenyl-C61-butyric acid methyl ester (PCBM) and polymer poly(3,4-ethylenedioxyselenophene): poly (styrene sulfonate) (PEDOS: PSS) were used to create the F.P. cavity. Such organic F.P. cavities on DSSCs can be produced by solution process which is economical, rapid, and produces a large surface area. The devices are suitable for use under low illumination indoor photovoltaic because there is light conversion current under low voltage. The solution process had three parts: (i) using a modified Hummers' method, the rGO was doped onto the porous TiO2 structure in different wt%, (ii) the polymer PEDOT: PSS and small molecule PCBM F.P cavities with different thicknesses were produced, as the thicknesses correspond to different color bands, and (iii) combine the F.P. cavity and rGO-TiO2 to produce a FTO/TiO2-rGO/Dye/Ag/F.P./Ag DSSC. Scanning electron microscope (SEM) images showed that 5 wt% rGO offered the best sheet nano-structure, and this increased the efficiency of DSSC by 28.1% when measured by power conversion efficiency (PCE). The color output advantages of F.P. cavity using PCBM and PEDOT materials are red and blue, respectively. The devices with PEDOT: PSS and PCBM saw a 9 and 12.5% gain compare to DSSC without F.P. cavity. However, two structures of TiO2 doped 5 wt% rGO and colorful PCBM F.P. cavity can increase the efficiency of DSSC by 44.1%.
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•DSSC can produce economical and large-area color solar cells through the solution process.•The porous TiO2 was doped with rGO to improve DSSC efficiency.•Color selection is thickness variation using organic F.P. cavity for colorful DSSC.•Color output advantages of F.P. cavity using PCBM and PEDOT are red and blue, respectively.
•V2O5 used as auxiliary electrochromic film deposited with RF magnetron sputtering.•V2O5 film has good electrochrism, valence, Raman red shift and stability potential.•V2O5 and WO3 films were ...sputtered for a complementary inorganic all-solid-state ECD.•The complementary all-solid-state ECD has low start voltage and fast response time.
Vanadium Pentoxide (V2O5) has good ion storage capacity and weak anodic electrochromism. Since the V2O5 and Tungsten Trioxide(WO3) films were used as the auxiliary and major color-changing layers, respectively, then they were combined with heat-cured gel (LiClO4 + PC) + PMMA electrolyte as an complementary all-solid-state electrochromic device (ECD). Also, the V2O5 films were prepared at different oxygen flows and annealing temperatures. These results exhibited that oxygen flow of 4 sccm and annealing temperature of 400 °C can enable the optimal optical contrast (ΔT) to reach 38.7%@550 nm. The response time of the coloring(tc) and the bleaching(tb) were 5 and 4 s, respectively. Raman spectrum showed the stable phase of V5+ and specific element ratio of 2.52 and X-ray photoelectron spectroscopy (XPS) had the red shift phenomenon. However, the performance of ITO/V2O5/gel-electrolyte/WO3/ITO device, the best working voltage was measured as ±2.5 V, the optical contrast was ΔT = 42% and the response time of tc and tb were 6.5 and 5.5 s, respectively. These results demonstrate that ECD has the advantages of fast response time and low voltage stable startup.
is an animal model for studying the reproduction and development of crustaceans. In this study, we knocked down the
gene by injecting dsRNA into
and inhibited
gene expression by injecting PLK1 ...inhibitor BI6727 into
. Then, the cell proliferation level, apoptosis level, and PI3K/AKT signaling expression level were detected. Our results showed that the proliferation level of spermatogenic cells decreased, while the apoptosis level increased after
knockdown or
inhibition. In order to verify whether these changes are caused by regulating the PI3K/AKT pathway, we detected the expression of PI3K and AKT proteins after
knockdown or
inhibition. Western Blot showed that in both the
knockdown group and the
inhibition group, the expression of PI3K and AKT proteins decreased. In addition, immunofluorescence showed that Es-KIF2A and Es-PLK1 proteins were co-localized during
spermatogenesis. To further explore the upstream and downstream relationship between Es-KIF2A and Es-PLK1, we detected the expression level of Es-PLK1 after
knockdown as well as the expression level of Es-KIF2A after
inhibition. Western Blot showed that the expression of Es-PLK1 decreased after
knockdown, while there was no significant change of Es-KIF2A after
inhibition, indicating that Es-PLK1 may be a downstream factor of Es-KIF2A. Taken together, these results suggest that Es-KIF2A upregulates the PI3K/AKT signaling pathway through Es-PLK1 during the spermatogenesis of
, thereby affecting the proliferation and apoptosis levels of spermatogenic cells.
Recent findings found that TiO2 nanoparticles (TiO2-NPs) have male reproductive toxicity. However, few reports have studied the toxicity of TiO2-NPs in crustaceans. In this study, we first chose the ...freshwater crustacean Eriocheir sinensis (E. sinensis) to explore the male toxicity of TiO2-NP exposure and the underlying mechanisms. Three nm and 25 nm TiO2-NPs at a dose of 30 mg/kg bw induced apoptosis and damaged the integrity of the haemolymph-testis-barrier (HTB, a structure similar to the blood-testis-barrier) and the structure of the seminiferous tubule. The 3-nm TiO2-NPs caused more severe spermatogenesis dysfunction than the 25-nm TiO2-NPs. We initially confirmed that TiO2-NP exposure affected the expression patterns of adherens junctions (α-catenin and β-catenin) and induced tubulin disorganization in the testis of E. sinensis. TiO2-NP exposure caused reactive oxygen species (ROS) generation and an imbalance of mTORC1-mTORC2 (mTORC1/rps6/Akt levels were increased, while mTORC2 activity was not changed). After using the ROS scavenger NAC to inhibit ROS generation, both the mTORC1-mTORC2 imbalance and alterations in AJs were rescued. More importantly, the mTORC1 inhibitor rapamycin abolished mTORC1/rps6/Akt hyperactivation and partially restored the alterations in AJs and tubulin. Collectively, the mTORC1-mTORC2 imbalance induced by TiO2-NPs was involved in the mechanism of AJ and HTB disruption, resulting in spermatogenesis in E. sinensis.
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•Exposure to TiO2-NPs disrupted the haemolymph-testis-barrier.•Exposure to TiO2-NPs changed the expression patterns of adhesion junctions.•ROS were the initiating factor of AJ and HTB impairment.•The mTORC1/rps6/Akt cascade signalling involved in AJ and HTB disruption.
β-CATENIN is an evolutionarily conserved multifunctional molecule that maintains cell adhesion as a cell junction protein to safeguard the integrity of the mammalian blood-testes barrier, and also ...regulates cell proliferation and apoptosis as a key signaling molecule in the WNT/β-CATENIN signaling pathway. In the crustacean Eriocheir sinensis, Es-β-CATENIN has been shown to be involved in spermatogenesis, but the testes of E. sinensis have large and well-defined structural differences from those of mammals, and the impact of Es-β-CATENIN in them is still unknown. In the present study, we found that Es-β-CATENIN, Es-α-CATENIN and Es-ZO-1 interact differently in the testes of the crab compared to mammals. In addition, defective Es-β-CATENIN resulted in increased Es-α-CATENIN protein expression levels, distorted and deformed F-ACTIN, and disturbed localization of Es-α-CATENIN and Es-ZO-1, leading to loss of hemolymph-testes barrier integrity and impaired sperm release. In addition to this, we also performed the first molecular cloning and bioinformatics analysis of Es-AXIN in the WNT/β-CATENIN pathway to exclude the effect of the WNT/β-CATENIN pathway on the cytoskeleton. In conclusion, Es-β-CATENIN participates in maintaining the hemolymph-testes barrier in the spermatogenesis of E. sinensis.
•We performed the first molecular cloning and bioinformatics analysis of Es-AXIN.•Es-β-CATENIN has an important role in maintaining the integrity of the HTB.•Defective Es-β-CATENIN leads to increased Es-α-CATENIN protein expression levels.•Es-α/β-CATENIN and ZO-1 interact differently in crab testes compared to mammals.
Aim： Many studies reveal an association between the acquired chemoresistant phenotype of cancer cells and tumor-initiating cell- like properties. The aim of this study was to determine the impact of ...c-Jun N-terminal kinase （JNK） on the tumor-initiating cell-like properties of acquired chemoresistant human cancer cells. Methods： Two well-established human acquired chemoresistant cancer cell lines K562/A02 and KB/VCR, as well as their respective parental counterparts K562 and KB were tested. The expression of relevant mRNAs and proteins was detected using qRT-PCR and Western blotting, respectively. Sphere formation and self-renewal assays were used to study the tumor-initiating cell-like properties. Soft agar and colony formation assays were used to investigate tumorigenic ability. Results： We observed that suppressing JNK activity by its specific small molecule inhibitor SP600125 or by limiting JNK1/2 expression with JNK1/2 shRNA lentiviruses inhibited the expression of pluripotent stem cell markers such as Oct4, Sox2, and Nanog in KB/VCR cells and K562/A02 cells as well as sphere formation and self-renewal abilities of K562/A02 cells. Additionally, inhibition of JNK activity significantly inhibited the in vitro and in vivo tumor-initiating abilities of KB/VCR cells. Furthermore, our data suggest that blocking JNK activity abundantly inhibited the Hedgehog （Hh） pathway activity, as reflected by reduction of Hedgehog （Hh） pathway target genes Gill and ptchl at the mRNA level as well as Gli-luciferase activity. Conclusion： JNK maintains the tumor-initiating cell-like properties of acquired chemoresistant K562/A02 and KB/VCR cells potentially through activating the Hedgehog pathway. Thus, disruption of tumor-initiating cell-like properties by targeting JNK may be a new approach to combating acquired chemoresistance.
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