Trifluoromethyl cationic carbyne (CF3C+:) possessing dual carbene‐carbocation behavior emulated as trifluoromethyl metal‐carbynoid (CF3C+=M) has not been explored yet, and its reaction ...characteristics are unknown. Herein, a novel α‐diazotrifluoroethyl sulfonium salt was prepared and used in Rh‐catalyzed three‐component 2+1+2 cycloadditions for the first time with commercially available N‐fused heteroarenes and nitriles, yielding a series of imidazo1,5‐a N‐heterocycles that are of interest in medicinal chemistry, in which the insertion of trifluoromethyl Rh‐carbynoid (CF3C+=Rh) into C=N bonds of N‐fused heteroarenes was involved. This strategy demonstrates synthetic applications in late‐stage modification of pharmaceuticals, construction of CD3‐containing N‐heterocycles, gram‐scale experiments, and synthesis of phosphodiesterase 10A inhibitor analog. These highly valuable and modifiable imidazo1,5‐a N‐heterocycles exhibit good antitumor activity in vitro, thus demonstrating their potential applications in medicinal chemistry.
A novel α‐diazotrifluoroethyl sulfonium salt was prepared, and it was applied in Rh‐catalyzed three‐component 2+1+2 cycloadditions for the first time, affording various imidazo1,5‐a N‐heterocycles under mild conditions. This strategy involved a unique trifluoromethyl Rh‐carbynoid (CF3C+=Rh), wherein three new chemical bonds were forged at the α‐carbon of trifluoromethyl in a single step.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
FZB42 is a plant growth-promoting rhizobacteria that stimulates plant growth, and enhances resistance to pathogens and tolerance of salt stress. Instead, the mechanistic basis of drought tolerance in
...induced by FZB42 remains unexplored. Here, we constructed an exopolysaccharide-deficient mutant
and determined the role of
in FZB42-induced drought tolerance in
. Results showed that FZB42 significantly enhanced growth and drought tolerance of
by increasing the survival rate, fresh and dry shoot weights, primary root length, root dry weight, lateral root number, and total lateral root length. Coordinated changes were also observed in cellular defense responses, including elevated concentrations of proline and activities of superoxide dismutase and peroxidase, decreased concentrations of malondialdehyde, and accumulation of hydrogen peroxide in plants treated with FZB42. The relative expression levels of drought defense-related marker genes, such as
,
,
, and
, were also increased in the leaves of FZB42-treated plants. In addition, FZB42 induced the drought tolerance in
by the action of both ethylene and jasmonate, but not abscisic acid. However, plants inoculated with mutant strain
were less able to resist drought stress with respect to each of these parameters, indicating that
are required for the full benefit of FZB42 inoculation to be gained. Moreover, the mutant strain was less capable of supporting the formation of a biofilm and of colonizing the
root. Therefore,
is an important factor that allows FZB42 to colonize the roots and induce systemic drought tolerance in
.
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IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
To determine whether supplementation with lutein and zeaxanthin improves macular pigment and visual function in patients with early age-related macular degeneration (AMD).
Randomized, double-masked, ...placebo-controlled trial.
Participants with probable AMD who were 50 to 79 years of age were screened for study eligibility from the local communities. One hundred eight subjects with early AMD were recruited.
Early AMD patients were assigned randomly to receive 10 mg/day lutein (n = 27), 20 mg/day lutein (n = 27), 10 mg/day lutein plus 10 mg/day zeaxanthin (n = 27); or placebo (n = 27) for 48 weeks. Macular pigment optical density (MPOD) and visual function variables were assessed at baseline, 24 weeks, and 48 weeks.
The primary outcome was MPOD. Secondary outcomes were visual function variables including best-corrected visual acuity (BCVA), contrast sensitivity (CS), photorecovery time, and Amsler grid testing results.
Macular pigment optical density increased significantly by a mean ± standard error of 0.076 ± 0.022 density unit in the 20-mg lutein group and 0.058 ± 0.027 density unit in the lutein and zeaxanthin group during 48 weeks. There was a significant dose-response effect for lutein supplementation, and the changes in MPOD from baseline to 48 weeks were correlated negatively with baseline MPOD in all active treatment groups (r = -0.56; P<0.001). At 48 weeks, a trend toward improvement was seen in BCVA, and there was a significant between-group difference in CS at 3 and 6 cycles/degree between the 20-mg lutein group and the placebo group. The increase in MPOD related positively to the reduction in the logarithm of the minimum angle of resolution BCVA (r = -0.31; P<0.01) and the increases in CS at 4 spatial frequencies (r ranging from 0.26 to 0.38; all P<0.05).
Among patients with early AMD, supplementation with lutein and zeaxanthin improved macular pigment, which played a causative role in boosting visual function and might prevent the progression of AMD. Future studies are required to evaluate the effect of these carotenoids on the incidence of late AMD.
We report the synthesis of five novel crystals (4-BrAni+)(DB18crown-6)2SMo12O402-·2CH3CN (1), (4-BrAni+)(B18crown-6)2SMo12O402-·CH3CN (2), (4-BrAni+)(B18crown-6)3PMo12O402-·2CH3CN (3), ...(3-AP+)3(B18crown-6)2PMo12O403- (4) and NBu4+(3-AP2+)(DB30crown-10)PMo12O403-·CH3CN (5) (4-BrAni+ = 4-bromoanilinium; B18crown-6 = benzo18-crown-6; DB18crown-6 = dibenzo18-crown-6; DB30crown-10 = dibenzo30-crown-10; 3-AP+ = 3-aminopyridinium; 3-AP2+ = 3-ammoniumpyridinium; NBu4+ = tetrabutylammonium). In order to construct non-centrosymmetric crystals, the five crystals were designed using a method to gradually introduce asymmetry into the building units. Crystal 1 was constructed with a symmetric supramolecular cation (SPC) (4-BrAni+)(DB18crown-6), resulting in a P21/n space group. The asymmetric SPC (4-BrAni+)(B18crown-6) was introduced into SMo12O402- to obtain crystal 2, which belongs to the symmetric P1combining macron space group. Introducing trivalent PMo12O403-, (4-BrAni+)(B18crown-6) produced crystal 3 with a non-centrosymmetric Pc space group. The asymmetric sandwich SPC (3-AP+)3(B18crown-6)2 was designed with multiple hydrogen bonding sites on the 3-AP+ cation, and crystal 4 was obtained with trivalent PMo12O403-. Crystal 4 has the properties of the chiral P1 space group. The distorted SPC (3-AP2+)(DB30crown-10) was constructed using flexible DB30crown-10, resulting in crystal 5 which matched the chiral P21 space group with trivalent PMo12O403-. This work focuses on strategies for the rational design of novel non-centrosymmetric crystals without a chiral synthon.
A Cu(II) coordination polymer with the composition of Cu
2
(L)
2
(4,4ʹ-bipy)
2
n
·2 n(ClO
4
) (1, HL = 4-methyl-L-phenylalanine and 4,4ʹ-bipy is 4,4ʹ-bipyridine), was successfully obtained by the ...reaction of the mixed ligand of HL and 4,4ʹ-bipy with Cu(ClO
4
)
2
· 6H
2
O under solvothermal condition. The as-synthesized compound not only has high thermal stability until 275°C but also excellent photocatalytic activity for the methyl blue solution degradation under the irradiation of ultraviolet light. Furthermore, the compound's treatment activity on the diabetes was determined and its relevant mechanism was also studied. The cytotoxicity or hemolysis toxicity (HC50) of the synthesized compound was also evaluated in this research.
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DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, UILJ, UKNU, UL, UM, UPUK
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•MIL-53(Al)-SO3H was post-synthesized without structural collapse.•MIL-53(Al)-SO3H preferentially adsorbed methanol over MTBE.•The membrane hydrophilicity and the free volume could be ...tuned effectively.•The membranes below 15 wt% loading exhibited anti-trade-off performance.•The as-prepared mixed matrix membranes showed encouraging long-term stability.
The post-synthetic MIL-53(Al)-SO3H was prepared and incorporated into sulfonated polyarylethersulfone with cardo (SPES-C) polymer matrix to form mixed matrix membranes (MMMs). The as-prepared MIL-53(Al)-SO3H was characterized by wide angle X-ray diffraction (WAXRD), fourier transform infrared spectroscopy (FTIR), dynamic light scattering (DLS), intelligent gravimetric analysis (IGA), scanning electron microscope (SEM) and elemental analysis. Positron annihilation lifetime spectroscopy (PALS), thermo gravimetric analysis (TGA), SEM, FTIR and water contact angle measurements were performed to investigate the properties and structure of MMMs. The results showed that MIL-53(Al)-SO3H was successfully synthesized without crystal structure collapse. The particle sizes were in nanometer scale. MIL-53(Al)-SO3H preferentially adsorbed methanol (MeOH) over methyl tert-butyl ether (MTBE). MIL-53(Al)-SO3H dispersed in SPES-C phase uniformly and no obvious interfacial defects could be observed. The membrane hydrophilicity, swelling behavior as well as free volume parameters could be effectively tuned by changing filler loading. The as-prepared MMMs demonstrated excellent separation performance and encouraging long-term stability for MeOH (15 wt%)/MTBE mixture. With increasing the filler loading, the permeation flux increased and the separation factor showed an up and down trend. When MIL-53(Al)-SO3H loading was below 15 wt%, an antitrade-off phenomenon was obtained. M-15 with 15 wt% loading exhibited the optimal separation performance (permeation flux of 0.368 kg·m−2·h−1 and separation factor of 1990).
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
A novel burdock fructooligosaccharide (BFO-1) was extracted from fresh burdock roots. In our study, we found that BFO-1 possessed immunoenhancing activity
in vitro
and
in vivo
. The proliferation ...activities of splenocytes were significantly stimulated at a BFO-1 dose of 1000 μg ml
−1
(
p
< 0.05), peritoneal macrophages showed increased activities of phagocytosis and acid phosphatase and increased production of NO at a BFO-1 dose of 1000 μg ml
−1
(
p
< 0.01)
in vitro
. In normal mice, BFO-1 promoted the activities of peritoneal macrophages at dosages of 250 and 500 mg per kg per day (
p
< 0.01). Similarly, in immunosuppressed mice, BFO-1 enhanced the activities of peritoneal macrophages at the dosage of 1000 mg per kg per day (
p
< 0.05). Furthermore, S180 tumor-bearing mice that were pre-administered BFO-1 solution showed improved immunological function and suppressed tumor growth. These data indicate that BFO-1 can improve the functioning of the immune system and has the potential to be developed as a dietary supplement and medicinal food.
Immunomodulatory activity of burdock fructooligosaccharide (BFO-1) on immune cells in
in vitro
normal mice, immunosuppressed mice treated with cyclophosphamide and S180 tumor-bearing mice.
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IJS, KILJ, NUK, UL, UM, UPUK
In sub-10 nm technology nodes, next generation lithography technologies are urgently required, and the diblock copolymer directed self-assembly (DSA) technology has shown its strong potential for ...contact/via layer fabrication. In addition, post-layout redundant via insertion has become a necessary step to guarantee sufficient yield and circuit reliability. However, existing redundant via insertion algorithms are not suitable for DSA since they could seriously deteriorate via manufacturability. In contrast, a sophisticated DSA-aware redundant via insertion algorithm may not only enhance circuit reliability but also improve DSA manufacturability. In this paper, we propose the first work of simultaneous guiding template optimization and redundant via insertion for DSA. Two integer linear programming (ILP)-based algorithms and an efficient graph-based approach are provided. The two ILP-based algorithms optimally maximize via manufacturability and the redundant via insertion rate. In addition, reduction techniques are presented to greatly improve the computational efficiency of ILP. For the graph-based approach, all feasible via patterns composed of original vias and redundant vias are identified. Then, the original problem is transformed into a graph formulation and efficiently optimized. Experimental results show that the ILP-based algorithms can find optimal solutions with reasonable computation time, and the graph-based algorithm can solve the problem much more efficiently and derive near-optimal solutions.
Both structural topology and composition strongly affect material properties and functionality, however, controlling both of them to achieve their synergic effects has been a long-sought goal. ...One-dimensional (1D) hollow structures have fantastic architectures and tunable physicochemical properties, but constructing them with desirable interiors and composition is extremely challenging. Here we report a facile and scalable approach, based on molecular self-assembly in water, for synthesizing hollow BCN microrods with hierarchical multichannel structure. The structural topology and composition of 1D hollow BCN are found to be easily tuned only by varying the annealing temperature. The multilevel interior structure and tunable composition make hollow BCN a multifunctional material, demonstrated by its impressive OER activity, high removal ability for heavy metals and organic pollutant. Specifically, its overpotential at a current density of 10 mAcm−2 is about 350 mV, outperforming the state-of-the-art precious-metal IrO2 catalyst, and its adsorption capacity for Cu2+ reaches up to a staggering 962.9 mg/g due to the synergistic effects of structural topology and composition. Our study provides an exceptionally simple strategy to tailor the structural topology and composition of materials, which are attractive for many applications.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP