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Phosphate transporters (PHTs) are well-known for their roles in phosphate uptake in plants. However, their actions in imparting plant growth in plants are still not so clear. In our previous study, we observed that maize PHT1 gene ZmPt9 plays a significant role in phosphate uptake. In this study, we further characterized ZmPt9 in response to low phosphate condition through ZmPt9 promoter inductive analysis by GUS staining and quantification. To elucidate the function of ZmPt9, we generated overexpression plant in Arabidopsis. ZmPt9 overexpressing Arabidopsis plants conferred small leaves and early flowering compared with the wild-type plants. In addition, ZmPt9 can complement the late flowering phenotype of Arabidopsis mutant pht1;2. The qRT-PCR analysis revealed that overexpression of ZmPt9 in Arabidopsis changed expression levels of some flowering-related genes. Further expressed detection of hormone related genes revealed that GA and auxin maybe the main determinant for growth influences of ZmPt9. In conclusion, these results suggest that apart from phosphate transport activity, ZmPt9 can be further exploited for improving crops growth.

Tian-Yong Hu,1,* Hua Zhang,1,* Yan-Yan Chen,1 Wei-Hua Jiao,2 Jun-Ting Fan,3 Zhi-Qiang Liu,1 Hou-Wen Lin,2 Bao-Hui Cheng1 1Shenzhen Key Laboratory of ENT, Institute of ENT and Longgang ENT Hospital, Shenzhen, 518172, People’s Republic of China; 2Research Center for Marine Drugs, State Key Laboratory of Oncogene and Related Genes, Department of Pharmacy, Ren Ji Hospital, School of Medicine, Shanghai Jiao Tong University, Shanghai, 200127, People’s Republic of China; 3Department of Pharmaceutical Analysis, School of Pharmacy, Nanjing Medical University, Nanjing, 211166, People’s Republic of China*These authors contributed equally to this workCorrespondence: Hou-Wen LinShanghai Jiao Tong University, 160 Pujian Road, Shanghai, 200127, People’s Republic of ChinaEmail franklin67@126.comBao-Hui ChengShenzhen Key Laboratory of ENT, Institute of ENT and Longgang ENT Hospital, 3004, Longgang Avenue, Longgang District, Shenzhen, 518172, People’s Republic of ChinaEmail chengbaohui@sina.comBackground: Marine natural products harbor a variety of pharmacological activities, and the sea species have been becoming a main source of new drug candidate. In pursuit of safer and more effective anti-inflammation drug, the anti-inflammatory activities, anti-oxygenation effects and underlying molecular mechanisms of compound dysiarenone from Dysidea arenaria were investigated via LPS-induced RAW 264.7 cell model.Methods: Firstly, RAW 264.7 cells have been stimulated with LPS and treated with dysiarenone, and the cell viability of the LPS-treated RAW 264.7 cells was examined. One-step method, DCFH-DA fluorescence probe method was used to detect reactive oxygen species (ROS). The modulation of dysiarenone on anti-inflammation was detected by enzyme-linked immunosorbent assay by measuring the release of inflammatory cytokines (TNF-α and IL-6), and inflammatory mediators (LTB4). Further, the underlying anti-inflammatory mechanism of dysiarenone was explored by determining the expression of inducible 5-LOX, MAPKs, p-Akt, and p-NF-κB p65. Oxidative stress is tightly connected with inflammation, which was also evaluated through nuclear factor erythroid 2-related factor 2 (Nrf2)/heme oxygenase-1 (OH-1) signaling pathway.Results: Our study unraveled that dysiarenone between 2 and 8 μM reduces the inflammation responses via suppressing the production of inflammatory cytokines (TNF-α and IL-6) and inflammatory mediators (LTB4). Dysiarenone down-regulated the protein levels of inducible 5-LOX via the inhibition of phosphorylation of MAPKs (including p38, ERK), Akt and NF-κB p65. Additionally, dysiarenone decreases ROS accumulation by upregulating HO-1 expression via nuclear translocation of Nrf2.Conclusion: In conclusion, we demonstrated that dysiarenone possesses anti-inflammation and anti-oxidation activity via inhibiting 5-LOX/NF-κB/MAPK and Nrf2/HO-1 signaling pathway. Dysiarenone might be a promising lead compound for inflammatory diseases.Keywords: dysiarenone, Dysidea arenaria, Nrf2, HO-1, NF-κB

Aerobic photo-oxidation of sulfide into sulfoxide in water is of great interest in green chemistry. In this study, three highly stable Ir(III)–Zr(IV) metal–organic frameworks (Ir–Zr MOFs), namely Z...

Recombinant protein biopharmaceuticals comprise a significant portion of the current drug development landscape. The glycosylation profile of these proteins is a key quality parameter as it can affect their safety, efficacy, and stability. However, glycan analysis is challenging because of the complexity of their structures. To overcome this challenge in achieving accurate glycan identification, cross-identification of N-Glycans by CE-LIF method using two capillary coatings and three labeling dyes was developed in this work. This work explored whether complementary separation capabilities can be achieved using homemade polyvinyl alcohol (PVA) coating and commercial Guarant™ (Guarant) coating in the analysis of N-glycans. Similar separation profiles were observed using the two capillary coatings, and hence the N-glycan GU databases generated by these coatings were comparable and complementary. The performance of cross-validation by labeling with three fluorescent dyes indicated that low covariance of APTS and Turquoise™ labeling can be obtained, and hence these two labeling mechanisms provided better accuracy for the identification of glycans. Superior reproducibility with RSDs less than 1% for all target glycan standards was achieved by the internal standards (IS) method using maltodextrin ladders as additives in the separation buffer. The developed CE-LIF analysis method was applied to the identification of N-glycans in IgG samples.

The chiral-recognition processes of homoproline (hpro) and [Ir(pq)2(MeCN)2](PF6) (pq is 2-phenylquinoline; MeCN is acetonitrile) are investigated, in favor of formation of the thermodynamically stable diastereomers Λ-[Ir(pq)2(d-hpro)] and Δ-[Ir(pq)2(l-hpro)]. Moreover, the diastereoselective photoreactions of Δ-[Ir(pq)2(d-hpro)] and Δ-[Ir(pq)2(l-hpro)] are reported in the presence of O2 at room temperature. Diastereomer Δ-[Ir(pq)2(l-hpro)] is dehydrogenatively oxidized into imino acid complex Δ-[Ir(pq)2(hpro-2H2)] (hpro-2H2 is 3,4,5,6-tetrahydropicalinate), while diastereomer Δ-[Ir(pq)2(d-hpro)] occurs by interligand C-N cross-coupling and dehydrogenative oxidation reactions, affording three products: Δ-[Ir(pq)(d-pqh)] [pqh is N-(2-phenylquinolin-8-yl)homoproline], Δ-[Ir(pq)2(hpro-2H2)], and Δ-[Ir(pq)2(d-hpro-2H6)] [hpro-2H6 is 2,3,4,5-tetrahydropicalinate]. The C-N cross-coupling and dehydrogenative oxidation reactions are competitive, and the dehydrogenative oxidation reactions are regioselective. By optimization of the photoreaction parameters such as the diastereomeric substrate, solvent, and temperature as well as base, each possible competitive product is selectively controlled. In addition, density functional theory calculations are performed to elucidate the distinctly chiral recognition between proline and hpro with an iridium(III) complex.

Enantiopure Λ-[Ir(dfppy)2(MeCN)2](PF6) and Δ-[Ir(dfppy)2(MeCN)2](PF6) (where dfppy is (4,6-difluoropheny)pyridine) were demonstrated to preferentially react with (S,S)-1,2-bis(arylsulfinyl)ethane and (R,R)-1,2-bis(arylsulfinyl)ethane, respectively, under thermodynamic equilibrium. Sequential treatment of Λ-[Ir(dfppy)2(MeCN)2](PF6) and Δ-[Ir(dfppy)2(MeCN)2](PF6) with C2-symmetric bis-sulfoxides led to diastereoselective formation of the corresponding diastereomers Λ-[Ir(dfppy)2(R,R)-bis-sulfoxide)](PF6) in 90-92% and Δ-[Ir(dfppy)2(S,S)-bis-sulfoxide)](PF6) in 88-90%, respectively. The uncoordinated (R,S)-bis-sulfoxides were afforded in 45% with >97% de values. Enantiopure (S,S)-bis-sulfoxides and (R,R)-bis-sulfoxides were respectively obtained by the release of sulfoxide ligands from the corresponding complexes in the presence of glycine in yields of 20-21% with 97-99% ee values. The enantioreceptors Λ-[Ir(dfppy)2(MeCN)2](PF6) and Δ-[Ir(dfppy)2(MeCN)2](PF6) can be recycled and reused in the next reaction cycle. Moreover, a protocol for asymmetric oxidation of prochiral bis-sulfide into enantiopure C2 symmetric bis-sulfoxide was also developed in a high enantioselectivity. The absolute configurations at the metal centers and sulfur atoms were determined by X-ray crystallography.

We design a series of expanded porphyrins which are incorporated of dithienothiophene (DTT), 2,2′-bithiophene, inverted thiophene ring or selenophene ring and substituted of the pyrrole NH groups by S and Se heteroatoms. The molecule with 2,2′-bithiophene is more stable than the molecule with DTT. The expanded porphyrins with a thiophene or selenophene ring are more stable than the expanded porphyrins with an inverted thiophene or inverted selenophene ring. 6 shows special features due to its increased HOMO-LUMO gap, planar geometry, and strengthened aromaticity. We expect that this work can provide help to design and synthesize stable molecular materials.

Carbazole is an important compound in pharmaceuticals and functional materials. A new Pd(II) supramolecular cage-catalyzed protocol for the synthesis of multifunctional carbazoles from indoles is described through regioselective successive oxidative Heck reactions. This new protocol is highly efficient, with a low Pd (2.4 mol%) catalyst loading and good compatibility for both N-H free and N-protected indole substrates. Moreover, it can be used to synthesize carbazoles with various functional groups by a one-pot two-step procedure. The excellent catalytic activity can be attributed to the distinct properties of the supramolecular cage structure in uniformly distributive and well-defined Pd(II) active centers on the cage surfaces.

The assembly of mixed [1,1';3',1'']terphenyl-4,5',4''-tricarboxylic acid (H3TPTC) and [1,1'-biphenyl]-4,4'-dicarboxylic acid (H2BPDC), 2,2'-diamino-[1,1'-biphenyl]-4,4'-dicarboxylic acid (H2BPDC-NH2), or 6-oxo-6,7-dihydro-5H-dibenzo[ d, f][1,3]diazepine-3,9-dicarboxylic acid (H2BPDC-Urea) with Cu2+ ion generated the corresponding copper-paddlewheel-based metal-organic framework (MOF) [Cu5(TPTC)3(BPDC)0.5(H2O)5] (1), [Cu5(TPTC)3(BPDC-NH2)0.5(H2O)5] (1-NH2), or [Cu5(TPTC)3(BPDC-Urea)0.5(H2O)5] (1-Urea). They are isostructural with hierarchical porosity, consisting of zero-dimensional cage (19.2 A × 18.9 A) and one-dimensional pillar channel (29.7 A × 15.1 A) in a manner of face sharing. Platon analyses revealed the porous volume ratios are 80.2%, 80.0%, and 77.8% for 1, 1-NH2, and for 1-Urea, respectively. Thermogravimetric measurements suggested 53, 51, and 48 wt % guest molecules in 1, 1-NH2, and 1-Urea, respectively. 1-NH2 and 1-Urea were precisely functionalized via the introduction of amino and urea functional groups into the pillar channels. The constructed MOF 1-Urea, incorporating both exposed copper active sites and accessible urea functional groups to substrates, presents high efficiency on catalytic CO2 cycloaddition with propene oxide to produce cyclic carbonate in the yield of 98% with a TOF value of 136 h-1 at 1 atm and room temperature. This synergic effect provides a new strategy for designing high-efficient catalysts for CO2 chemical conversion under ambient conditions.

A diastereoselective photooxidation of α-amino acid (AA) complexes into imino acid complexes using a chiral iridium(III) complex as a photosensitizer and stereo-controller under visible light irradiation and oxygen was developed. It was found that the oxidative rate of Δ-[Ir(pq)2(L-AA)] (pq is 2-phenylquinoline) diastereomer is significantly higher than that of the corresponding Δ-[Ir(pq)2(D-AA)] diastereomer, providing a new protocol for kinetic resolution of AAs via a nonenzymatic pathway. Moreover, the thermodynamic controlled strategy offered a complemental method for the diastereoselective hydrogenation of imine bonds using NaBH4 as a reductant under the chiral Ir(III) complex as a stereo-controller. The combination of diastereoselective photooxidation and reduction processes results in a new protocol for deracemization of α-amino acids under mild conditions. Mechanism study strongly indicates that singlet oxygen is a key participant in the reaction and the α-C–H bond cleavage of AAs is the rate-dete...

A new chiral sensor assembly with enantiomeric Ir(III) complex Δ-[Ir(ppy)2(MeCN)2](PF6) (ppy is 2-phenylpyridine) and 3-hydroxypyridine-2-carboxaldehyde as anxiliaries for chiral amines and amino derivatives, including α-amines, α-amino alcohols, α-amino esters, β-amines and β-amino alcohols as well as amino ether, was developed on the basis of 1H NMR spectroscopy. The assembly reaction is rapid and quantitative in equivalent under mild conditions, generating the corresponding diastereomers that are applied to discriminate the absolute configuration and quantitatively determine the enantiomeric excess (ee) directly without physical separation. The chelating coordination to Ir(III) ion much enhances the stability of the formed Schiff base ligand. Furthermore, more than one pair of diastereotopic resonances in wide detection regions ensures a convenient and high degree of accuracy in quantifying the ee value of chiral amines and amino derivatives. The absolute errors of the ee determinations by 1H NMR spectroscopy in different detection windows are within 1.9%. The linear relationship between the experimentally measured ee values and the gravimetrically prepared samples is found to be excellent.

Ganoderma fungi have long been used as a famous traditional medicine and food in country of East Asia. In this work, two new farnesyl phenolic compounds, ganoduriporols A and B (1 and 2), were isolated from the fruiting bodies of Ganoderma duripora, and their structures were elucidated using various spectroscopic methods. Anti-inflammatory activities were assayed and evaluated for the two compounds. Ganoduriporols A and B exhibited dose-dependent anti-inflammatory effects in RAW 264.7 cells. Furthermore, ganoduriporol A was demonstrated to inhibit the production of tumor necrosis factor-α (TNF-α), interleukin-1β (IL-1β), interleukin-6 (IL-6) and prostaglandin E2 (PGE2) through the suppression of COX-2, MAPK and NF-κB signaling pathway in LPS-induced macrophage cells. These results suggested that these two new farnesyl phenolic compounds and the fruiting body of G. duripora could serve as anti-inflammatory agents for medicinal use or functional food.

On the basis of hard soft acid base theory, two neutral heterometallic M2Pd3 supramolecular cages, [Al2Pd3(L)6Cl6] (1) and [Fe2Pd3(L)6Cl6] (2) (where HL is 1-(4-(1H-imidazol-1-yl)phenyl)butane-1,3-dione), have been constructed by using the tripodal M(L)3 as metalloligands in combination with PdCl2 or Pd(MeCN)2Cl2. The supramolecular cage can be described as a trigonal bipyramid with two M3+ ions occupying at the two axial sites in ΔΔ or ΛΛ configurations and three Pd2+ ions sitting in the three equatorial positions with square planar geometry in trans configuration. The supramolecular cages exhibit high catalytic activity for the Suzuki–Miyaura coupling with arylbromide or arylchrolide and phenylboronic acid in biorenewable solvent glycerol under mild conditions. Moreover, the catalyst can be readily recycled and reused at least five times without loss of catalytic activity. The high catalytic performance may be attributed to the distinct properties of the cage structure with uniformly distributive and well-defined Pd active centres on the cage surfaces. The high stability in the cage structure also prevents Pd leaching out and agglomeration.

The postcoordinated interligand-coupling strategy provides a useful and complementary protocol for synthesizing polydentate ligands. Herein, diastereoselective photoreactions of Λ-[Ir(pq)2(d-AA)] (Λ-d) and Λ-[Ir(pq)2(l-AA)] (Λ-l, where pq is 2-phenylquinoline and AA is an amino acid) are reported in the presence of O2 under mild conditions. Diastereomer Λ-d is dehydrogenatively oxidized into an imino acid complex, while diastereomer Λ-l mainly occurs via interligand C-N cross-dehydrogenative coupling between quinoline at the C8 position and AA ligands at room temperature, affording Λ-[Ir(pq)(l-pq-AA)]. Furthermore, the photoreaction of diastereomer Λ-l is temperature-dependent. Mechanistic experiments reveal the ligand-radical intermediates may be involved in the reaction. Density functional theory calculations were used to eluciate the origin of diastereoselectivity and temperature dependence. This will provide a new protocol for the amination of quinoline at the C8 position via the postcoordinated interligand C-N cross-coupling strategy under mild conditions.

A method for mercury high throughput rapid speciation analysis was developed by short column capillary electrophoresis (SC-CE) coupled with inductively coupled plasma mass spectrometry (ICP-MS). A MicroMist nebulizer was employed to increase the nebulization efficiency and a laboratory-made removable SC-CE-ICP-MS interface on the basis of cross design was applied to alleviate buffer contamination of ICP-MS. In less than 60 s, methylmercury (MeHg(i)) and inorganic mercury (Hg(ii)) were separated in a 16 × 75 μm i.d. short fused-silica capillary at 21 kV, while a mixture of 30 mmol L-1 boric acid + 5% (v/v) CH3OH (pH = 8.60) acted as running electrolyte. The precisions (RSD, n = 5) of migration time and peak area for MeHg(i) and Hg(ii) were in the range of 1.4-2.6% and 3.3-3.4%, respectively. The limits of detection (3σ) mercury species were 9.7 μg L-1 and 12.0 μg L-1, respectively. The recoveries for Hg(ii) and MeHg(i) were in the range of 96-107% and 99-105%.

Background Yan Hou Qing (YHQ) is a Chinese medicinal formula designed to alleviate sore throat symptoms, but underlying mechanism of YHQ treatment for pharyngitis is poorly defined up to now. Methods In this study, the modulation of YHQ on pharyngitis is investigated in ammonia-induced acute pharyngitis rat models. After treatment with YHQ or dexamethasone respectively for five consecutive days, all rats were sacrificed for biomolecular and histopathologic study. Protein expressions of MAPKs, NF-κB, COX-2 and 5-LOX in pharyngitis tissue were evaluated by western blot analysis and the levels of TNF-α, IL-6, prostaglandin (PG) E2, leukotrienes (LT)-B4 and LT-D4 in pharyngeal tissue were measured via ELISA assay. Evans blue (EB) dye exudation test was performed parallelly to assess the integrity of pharyngeal tissue. Results Compared with normal control group, EB dye exudation, and inflammatory cytokines in the model group were significantly increased, and the pharynx tissue was obviously infiltrated by inflammatory cells. YHQ treatment improved the inflammatory infiltrate in pharyngeal tissue, and reduced EB dye exudation in AP rat models. The up-regulated TNF-α and IL-6 in pharyngeal tissue of AP were significantly reduced by YHQ through inhibition of phosphorylation of p38, Erk and NF-κB. YHQ treatment also reversed the increased level of PGE2 through down-regulation of COX-2. Conclusions YHQ formula attenuated the pharyngitis related symptoms via suppression of COX-2 and phosphorylation of p38, Erk and NF-κB (p65).

The macrocyclic molecules with terthiophene (TTH) isomers unit exhibit intriguing properties in terms of aromaticity, stability, and absorption. In this work, we theoretically designed a series of macrocyclic molecules featured with TTH and dithienothiophene (DTT) π-conjugated building units, which are used to permute pyrrole unit in porphyrin skeleton. Density functional theory and time-dependent DFT methods are used to evaluate the performance of the designed molecules. Our simulations show that molecules 1-3 exhibit excellent optoelectronic performance. Specifically, the molecule with the DTT unit is more stable than the one with TTH unit in terms of aromaticity and aromatic stabilization energy. This is because DTT unit enhances the coplanarity of the molecular material, facilitating electronic communication. Calculation of vertical electronic excitations suggests the absorption feature of these molecules is mainly contributed by the electronic excitations of higher occupied molecular orbital (HOMO) → lowest unoccupied molecular orbital (LUMO)+1 and HOMO-1 → LUMO. Judging from the key parameters determining the overall performance, 3 stands out because of its good planarity, large HOMO-LUMO gap, and strong aromaticity among all molecules. Interestingly, molecule 1 has the current density flow distributes around the outer section of TTH unit; in contrast, molecule 3 with DTT unit has the current density flow located at the inner section of DTT, which is beneficial for stability and aromaticity. Second-order perturbation energies are calculated to rationalize this observation. We expect that these research results can provide valuable insights into the rational design of novel molecular materials for a variety of applications.

Dihydrofisetin is a flavanonol derived from some edible wild herbs and traditional Chinese medicines. It has been found to possess many biological activities. However, the anti-inflammatory potential of Dihydrofisetin remains uncharacterized. The aim of the present study was to investigate the anti-inflammatory activity of Dihydrofisetin and its underlying mechanisms. We found that Dihydrofisetin dose-dependently inhibited lipopolysaccharide-induced productions of nitric oxide (NO) and prostaglandin E2 (PGE2) in RAW 264.7 macrophages, probably through suppressing the protein expressions of inducible nitric oxide synthase (iNOS) and cyclooxygenase-2 (COX-2). The expressions of pro-inflammatory cytokines, such as tumor necrosis factor-α (TNF-α), interleukin-1β (IL-1β), interleukin-6 (IL-6) and monocyte chemotactic protein (MCP-1) were also suppressed. We further demonstrated that Dihydrofisetin inhibited the activation of mitogen-activated protein kinases (MAPKs) pathway and phosphorylation of IκB-α whereas upregulated the expression of heme oxygenase-1 (HO-1). The in vivo carrageenan-induced mice paw edema study also indicated that treatment with 100 mg/kg of Dihydrofisetin could significantly inhibit carrageenan induced paw edema, decrease the levels of TNF-α, IL-6 and MDA, and increase the activity of GSH-Px in paw tissues. Taken together, Dihydrofisetin may act as a natural agent for treating inflammatory diseases by targeting MAPK, NF-κB and HO-1 pathways.

Five new benzopyran derivatives (2–6) and a new natural product (1) were isolated from endophytic Daldinia eschscholzii in Dendrobium chrysotoxum and determined as (R)-2,3-dihydro-2,5-dihydroxy-2-methylchromen-4-one (1), (2R, 4S)-2,3-dihydro-2-methyl-benzopyran-4,5-diol (2), (R)-3-methoxyl-1-(2,6-dihydroxy phenyl)-butan-1-one (3), 7-O-α-d-ribosyl-5-hydroxy-2-methyl-4H-chromen-4-one (4), 7-O-α-d-ribosyl-2,3-dihydro-5-hydroxy-2-methyl-chromen-4-one (5), daldinium A (6). These compounds were evaluated for their antimicrobial activity, anti-acetylcholinesterase, nitric oxide inhibition, anticoagulant, photodynamic antimicrobial activities and glucose uptake of adipocytes. Some compounds showed photoactive antimicrobial activities and glucose uptake stimulating activities.

Perovskite solar cells (PSCs) are currently under both of intense academic and industrial investigations. Here, two dimethoxyphenylamine-substituted carbazole derivatives (SYN1 and PARA1), as hole-transporting materials (HTMs) for PSCs, have been synthesized via two-step synthesis with low cost and simple operation. PSCs devices based on SYN1 and PARA1 showed power conversion efficiencies (PCE) of 11.4% and 13.1%, respectively, outperforming that of Spiro-OMeTAD (12.0%), demonstrating the dimethoxyphenylamine-substituted carbazole derivatives are good candidates as HTMs for perovskite solar cells. Time-resolved photoluminescence (TRPL) and J-V test under dark indicate that the hole injecting efficiency and dark current affect the cell performance seriously.

A new coordination polymer, {[Cd(BIPA)(1,3-bdc)](DMF)} n , based on bis(4-(1H-imidazol-1- yl)phenyl)amine (BIPA) and 1,3-dicarboxybenzene (1,3-H2bdc) was synthesized and showing 2D → 3D structure via π-π* interaction of BIPA molecules in the nearby networks in the complex. Investigation of photophysical properties showed that the complex exhibits a strong emission in the range of 350–425 nm (λmax = 375 nm upon excitation at 327 nm).

Diastereoselective synthesis of bis-cyclometalated Ir(III) stereoisomers Δ/Λ-[Ir(C∧N)2(d-pro)] and Δ/Λ-[Ir(C∧N)2(l-pro)] (where C∧N is 2-phenylpyridine (Hppy), (4,6-difluorophenyl)pyridine (Hdfppy), and 2-phenylquinoline (Hpq) and pro is proline) with dual stereogenic centers at the metal and auxiliary ligand has been developed. The diastereomers Λ-l and Λ-d, and Δ-l and Δ-d exhibit distinguishable photophysical properties in both solution and the solid state. The thermodynamically stable diastereomers Λ-[Ir(ppy)2(l-pro)], Λ-[Ir(dfppy)2(l-pro)], and Λ-[Ir(pq)2(l-pro)] emit a green emission at 524 nm (Φ = 3.5% and τ = 35 ns), a blue-green emission at 480 nm (Φ = 4.5% and τ = 59 ns), and a red emission at 588 nm (Φ = 6.5% and τ = 200 ns) in DCM solution, respectively, which are blue-shifted accompanied by a large quantum yield and long lifetime relative to the corresponding unstable diastereomers Δ-[Ir(ppy)2(l-pro)] at 537 nm (Φ = 2.3% and τ = 29 ns), Δ-[Ir(dfppy)2(l-pro)] at 489 nm (Φ = 2.8% and τ = 43 ns)...

A new natural mycotoxin was isolated from the fermentation broth of Trichoderma sp. Jing-8 and the structure was determined as alternariol 1′-hydroxy-9-methyl ether (1), together with twelve known compounds. The structures were elucidated on the basis of their 1D, 2D NMR spectra and mass spectrometric data. Compounds 1, 8 and 9 indicated inhibitions against germination of the seeds of cabbage with MICs 1 showed the antibacterial activity against Bacillus subtilis and Staphylococcus aureus with MICs at 64 μg/mL. Compound 1 and 3 showed significant DPPH radical-scavenging activities with IC50 at 12 μg/mL, respectively. The OH at C-1′ in compound 1 decreased the cytotoxicity of these mycotoxins. A primary structure–activity relationship about the alternariol derivatives was discussed. Compounds 2–7 and 8 were the first time to be isolated from the Trichoderma.

The optically active Ir(III) complex Λ-[Ir(ppy)2(MeCN)2](PF6) (ppy is 2-phenylpyridine) with a chiral-at-metal was first demonstrated to preferentially react with (R)-configuration sulfoxides 2-(alkylsulfinyl)phenol (HLO-R, R = Me, Et, iPr, and Bn) rather than (S)-configuration sulfoxides under thermodynamic equilibrium due to the hydrogen-bonding interaction and the differences in the steric interference, and thus act as a highly efficient enantioreceptor for resolution of sulfoxide enatiomers. Treatment of Λ-[Ir(ppy)2(MeCN)2](PF6) with 2 equiv of rac-HLO-R offered (S)-HLO-R in yields of 46–47% with 97–99% enantiomeric excess (ee) values and Λ-[Ir(ppy)2{(S)-LO-R}] complex in yields of 89–93% with 98% diastereomeric excess (de). The (R)-HLO-R chiral sulfoxides were obtained by the acidolysis of Λ-[Ir(ppy)2{(S)-LO-R}] complexes with trifluoroacetic acid (TFA) in the presence of coordinated solvent MeCN in yields of 45–47% with 98–99% ee values. Moreover, the enantioreceptor Λ-[Ir(ppy)2(MeCN)2](PF6) can be ...

With the idea of supramolecular hosts encircling monoanions, a series of urea-containing trinuclear cationic copper complexes were designed, prepared and structurally analyzed. Copper(I) acetylides [Cu3(μ-dppm)3(μ3-η1-CCC6H4-4-NHC(O)NHC6H4-4-R)2]+ (dppm = bis(diphenylphosphino)methane; R = NO2 (1), CF3 (2), Cl (3), H (4), tBu (5), and OCH3 (6)) were prepared with F−, BF4−, or NO3− present as the anion. Eight 1-D anion coordination polymers (ACPs), 1·F, 2·F, 3·BF4, 4·F, 5·F, 5·BF4, 5·NO3 and 6·0.5F·0.5BF4, were clearly determined by X-ray diffraction. Diversity in the polymeric architecture is generated by both the choice of R-group used and anion present. 2·F, 3·BF4, 4·F, and 5·F show linear 1-D structures; 5·BF4 and 5·NO3 feature single-stranded helical structures; 1·F and 6·0.5F·0.5BF4 exhibit meso-helical structures. Solid state UV-vis absorption and luminescence properties are also discussed.

A method was built to separate three kinds of enantiomers of non-natural carboxyl amino acid with CE while CM-β-CDacted as chiral selective reagent. Several different β-CD derivatives were used as the chiral separation agent, and it was proved that CM-β-CDhad the advantage of chiral selectivity for carboxyl amino acids. Three kinds of enantiomers of carboxyl amino acids were separated by CE in a 50 μm i.d.×60 cm (effective length 45 cm) fused-silica capillary at 20 kV voltages and 10 mM NaH2PO4 solution served as running buffer solution with 10 mM CM-β-CDserving as selective reagent. The optimum detection wavelength was 214nm.

The etched stainless steel wire was prepared and explored as sorbent material for solid-phase micro extraction (SPME) coupled with gas chromatography (GC) and flame ionization detection (FID) for the trace polycyclic aromatic hydrocarbons (PAHs) determination in water. This paper explored different factors that affected the extraction efficiency of etched stainless steel wire, including the extraction time, the thermal desorption time and the thermal desorption temperature. Under the optimal conditions, six kinds of analytes, including trace biphenyl, acenaphthylene, fluorene, phenanthrene, fluoranthene and pyrene were extracted by etched stainless wire with high concentration efficiency and separated by GC-FID. In view of the high selectivity of the etched stainless steel wires for PAHs, a new SPME method was developed with the detection limits of 0.05-0.53 μg/L. The precision for the six kinds of analytes ranged from 2.6% to 8.8%. The developed etched stainless steel wires were very stable, highly selective, and reproducible for the SPME of PAHs.

Summary Camellia kucha, a wild tea plant with potent antioxidant potential, has been consumed as local beverage for a long history. It is featured for the presence of theacrine and low content of caffeine. Interestingly, compared with caffeine showed strong stimulant effect, theacrine showed sedation, hypnoses and promoting memory function. In this study, the anti-adipogenic ability of Kucha tea (KT) and its main components were evaluated in mouse 3T3-L1 cells. The results indicated that KT acted significantly to decrease lipid droplet accumulation. Moreover, KT decreased the expression of major transcription factors of adipogenesis pathway, such as PPAR γ and C/EBP α. KT also decreased the mRNA and protein levels of fatty acid synthase, fatty acid translocase, steroylcoenzyme A desaturase-1, lipoprotein lipase and acetyl-CoA carboxylase-1. Furthermore, KT suppressed the activation of ERK, p38 and JNK.

With 2-phenylquinoline (pq) as a cyclometalated ligand, a series of cationic Ir(III) complexes [Ir(pq)2(L1)2](PF6) (L1 is pyridine (1a), 4-methoxypyridine (1b), 4-dimethylaminopyridine (1c), and 4-...

Objective: Reactive oxygen species (ROS) are involved in a variety of biological phenomena and serve both deleterious and beneficial roles. ROS quantification and assessment of reaction networks are desirable but difficult because of their short half-life and high reactivity. Here, we describe a pro-oxidative model in a single human lung carcinoma SPC-A-1 cell that was created by application of extracellular H(2)O(2) stimuli. Methods: Modified microfluidics and imaging techniques were used to determine O(2) (•−) levels and construct an O(2) (•−) reaction network. To elucidate the consequences of increased O(2) (•−) input, the mitochondria were given a central role in the oxidative stress mode, by manipulating mitochondria-interrelated cytosolic Ca(2+) levels, mitochondrial Ca(2+) uptake, auto-amplification of intracellular ROS and the intrinsic apoptotic pathway. Results and conclusions: Results from a modified microchip demonstrated that 1 mmol/L H(2)O(2) induced a rapid increase in cellular O(2) (•−) levels (>27 vs. >406 amol in 20 min), leading to increased cellular oxidizing power (evaluated by ROS levels) and decreased reducing power (evaluated by glutathione (GSH) levels). In addition, we examined the dynamics of cytosolic Ca(2+) and mitochondrial Ca(2+) by confocal laser scanning microscopy and confirmed that Ca(2+) stores in the endoplasmic reticulum were the primary source of H(2)O(2)-induced cytosolic Ca(2+) bursts. It is clear that mitochondria have pivotal roles in determining how exogenous oxidative stress affects cell fate. The stress response involves the transfer of Ca(2+) signals between organelles, ROS auto-amplification, mitochondrial dysfunction, and a caspase-dependent apoptotic pathway.

Aerobic oxidation of amino acid complexes is an important process for the functionalization of amino acids. However, the reaction mechanism is still uncertain. Two enantiopure imino acid complexes Δ-[Ir(pq)2(ala-2H)] and Δ-[Ir(ppy)2(ala-2H)] (where pq is 2-phenylquinoline, ppy is 2-phenylpyridine and ala is alanine) have been synthesized respectively via the dehydrogenated oxidation reaction of the corresponding amino acid complexes Δ-[Ir(pq)2( l -ala)] and Δ-[Ir(ppy)2( l -ala)] in EtOH using visible light as the driving force and oxygen as an oxidant under mild conditions. The imino acid complexes have been fully characterized by NMR and MS techniques as well as X-ray single-crystal determination. The mechanism studies show singlet oxygen (1O2) is the main reactive oxygen species (ROS) and the carbon radical intermediate may involve in the reaction process. Therefore, a reaction mechanism involving the formation of a ligand-radical intermediate rather than the higher oxidation state of the metal center was proposed.

Research thus far has ascertained the potential of glycans as biomarkers of disease. Recent developments in glycan analysis also suggests connections between glycosylation traits and physiological states as well as lifestyle habits. The trends in recent reports thus allowed us to discern the applicability of harvesting glycomic information from one of the most common crime scene evidence – blood. In particular, the glycomic information could serve as forensic evidence to profile suspected candidates or persons-of-interest, by estimating characteristics such as age, gender, smoking status, chronic alcohol consumption, disease or risks of diseases, and even possibly ethnicity. In this review, we discuss the current limitations in obtaining relevant “human profiling” information through analysis of blood samples, specifically in DNA-based techniques. This forms the premise which necessitates the development of alternative glycan-based methods. In that regard, we summarise recent evidence from the past 10 years indicating that glycans are biomarkers of the various determinable physiological/lifestyle parameters for forensic applications. This also includes brief biological explanations for the interconnections between glycosylation and these parameters. Through reviewing works studying the stability of glycans in dried blood stains left in various conditions, the utility of glycan analysis as a novel forensic tool and as corroborative evidence to DNA-based tools is further demonstrated. Together with future directions needed to realise such a potential of glycan markers, we conclude that the development of a possible glycan analysis framework, aided by bioinformatics experts or data scientists, may be the rising star for forensic analytical chemistry.

An efficient approach for direct carbamoylation of terminal alkynes with formamides affording propiolamides has been developed by copper-catalyzed oxidative cross coupling of C(sp)-H and C(sp2)-H bonds in the presence of a pincer ligand with two imidazolyl groups. The catalytic reaction is compatible with diverse functional groups but sensitive to the electronic effect of terminal alkyne and the steric effect of formamides. KIE study indicates the cleavage of the carbamoyl C–H bond affording formamide radical is the rate-determining step.

The enantioselective oxidation synthesis of chiral modafinil acid and its analogues with high enantiomeric excess has been developed by means of a chiral-at-metal strategy. Treatment of ruthenium complexes cis-[Ru(bpy)2Cl2] or Δ/Λ-[Ru(bpy)2(MeCN)2](PF6)2 (bpy is 2,2′-bipyridine) with the appropriate prochiral thioether ligands afforded thioether complexes rac-1, Δ/Λ-1, rac-2, Δ/Λ-2, rac-3, and Δ/Λ-3. Diastereoselective oxidation of the thioether complexes in situ produced the corresponding sulfoxide complexes rac-1a, Δ/Λ-1a, rac-2a, Δ/Λ-2a, rac-3a, and Δ/Λ-3a. The configuration at the metal center in each case is stable during the coordination and oxidation reactions, and dictates the chirality of the sulfoxide ligand in the oxidation process. The chiral modafinil acids were obtained with ee values greater than 98 % upon their removal from the corresponding sulfoxide complexes in the presence of TFA/MeCN. Moreover, the chiral ruthenium precursors Δ/Λ-[Ru(bpy)2(MeCN)2](PF6)2 are recyclable and reusable with complete retention of the configurations.

Intermolecular interaction of mononitrotoluenes (MNs) plasticizer with 2,4,6-trinitrotoluene (TNT) and 1,3,5-trinitrohexahydro-1,3,5-triazine (RDX) was experimentally and theoretically investigated. The basis set superposition error (BSSE) and interaction energy of TNT, RDX and plasticizers were computed at MP2/6-311++G** levels. Compared with the weak Einterbetween RDX and TNT (−1.586 kJ/mol), Einterbetween the o-nitrotoluene and TNT and RDX can increase to −131.557 kJ/mol and −48.487 kJ/mol, indicating there is strong intermolecular-interaction. SEM imagines also show that mononitrotoluene could form layered deposits in TNT and closely surround RDX crystalline. MD simulation results indicate that tensile modulus of (100) TNT and (100) RDX increases when introducing mononitrotoluene plasticizers separately, which agree with the experimental phenomenon of Brazilian disk test.

The toluene being removed by dielectric barrier discharge (DBD) combined with modified photocatalyst was studied in the paper. Transition metal manganese was doped into crystal lattice of TiO2 in order to improve the activity of photocatalyst, and the optimal doping ratio was confirmed in the study. As one of main factors, the influence on toluene removal efficiency of gas flow rate, initial concentration and electric field intensity was analyzed in the study. Furthermore, the energy efficiency was another important index which had been compared amongγ-Al2O3, TiO2/γ-Al2O3 and Mn-TiO2/γ-Al2O3. The result of study showed that DBD combined with Mn-TiO2/γ-Al2O3 had the best buffer action against increasing of gas flow rate and initial concentration, the energy efficiency had the tendency as Mn-TiO2/γ-Al2O3 > TiO2/γ-Al2O3>γ-Al2O3, and the optimal doping ratio of manganese was 0.01.

The etched stainless steel powder was prepared and explored as sorbent material for solid-phase extraction coupled with high-performance liquid chromatography (HPLC) for determination of trace polycyclic aromatic hydrocarbons (PAHs) in environmental matrices. The etched stainless steel powder was shown to be promising for solid-phase extraction of PAHs in environmental samples with subsequent HPLC separation and UV detection. This paper explored different factors that affected the adsorption efficiency of etched stainless steel powder, including the etched time of stainless steel powder, the mass of sorbent, and the volume of water sample, and so on. In the optimum conditions, nine kinds of PAHs, including trace naphthalene, acenaphthylene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzanthracene and benzopyrene, were extracted by etched stainless powder and the extraction efficiency is satisfactory.

A palladium-catalyzed asymmetric [3+2] cycloaddition reaction of vinylaziridines with alpha,beta-unsaturated ketones, wherein the alkenes have a single activator, is realized in high diastereo- and enantioselectivity, thus affording 3,4-disubstituted pyrrolidines in high yields with excellent ee values. The introduction of a methyl group at C1 of the vinyl group the vinylaziridines greatly improves the stereochemistry of the reaction. A plausible transition state is proposed.

Magnetic coordination polymers have attracted considerable interest due to their novel structures and potential applications. In this paper, one new 2D magnetic manganese coordination polymer {[Mn(bimb)(OBA)]}n (1) was synthesized under solvothermal conditions based on 4,4′-bis(1H-imidazol-1-yl-methyl)biphenyl (bimb) and 4,4′-oxybis(benzoate) (H2OBA). Complex 1 contains [Mn(CO2)]n 1D chains and magnetic susceptibility measurements indicate that compound 1 exhibits an antiferromagnetic coupling interaction. In addition, complex 1 exhibits solid-state photoluminescence and high thermal stability.

Four anionic maleic monoester carboxylate polymeric surfactants were synthesized by the reaction of maleic anhydride with linear alcohols of different chain length in the ratio of 1:1.1 under 80 °C. Then the intermediate products were neutralized by sodium hydroxide at 60 °C to produce the final monomers. The structures of products were confirmed by FTIR. The surface tension was measured at 45 °C and the thermodynamic parameters were calculated. The results show that the polymeric surfactants possess low critical micelle concentration (CMC), high adsorption affinities and good surface and interfacial activity.

The synthesis of 3-picoline from the liquid-phase condensation of acrolein and ammonium acetate under atmospheric pressure was conducted by first dissolving ammonium acetate in a C 2 C 6 carboxyl acid medium in the presence of solid acid catalyst, and then, feeding gradually a solution of acrolein in a C 2 C 6 carboxyl acid solvent. It was found that the employment of acetic acid, among various carboxyl acids tested, as both the reaction medium and solvent of acrolein, was most favorable, due to the obvious promotion to the formation of 3-picolind in liquid phase and retarding to the side reaction of acrolein polymerization in gas phase. The SO 4 2− /ZrO 2 -FeZSM-5 catalyst possesses the largest acid acidity and thus exhibited the largest yield of 3-picoline, among various solid acid catalysts. By employing the SO 4 2− /ZrO 2 -FeZSM-5 catalyst and acetic acid as both the reaction medium and solvent of acrolein, the influencing factors, including reaction temperature, molar ratio of ammonium acetate/acrolein/acetic acid, concentration and feeding rate of acrolein solution as well as usage of catalyst, were systematically investigated. The results indicated that an as high as 60% yield of 3-picoline could be achieved from a batch with molar ratio composition acrolein/ammonium acetate/acetic acid = 0.025/0.125/1.8, under the conditions of reaction temperature = 130 °C, concentration of acrolein solution = 14 wt%, feeding speed of acrolein solution = 12 mL/h and catalyst usage = 0.7 g/g (acrolein).

Two new oxidation products-related aureonitol and cytochalasan were isolated from Chaetomium globosum fermented in Chinese yam (Dioscorea opposita) and determined as 10,11-dihydroxyl- aureonitol (1) and yamchaetoglobosin A (2). Compound 2 indicated significant inhibitory effect on nitric oxide production in LPS-activated macrophages, anti-acetylcholinesterase activity with the inhibition ratios of 92.5, 38.2% at 50 μM, and cytotoxicity to HL-60, A-549, SMMC-7721, MCF-7 and SW480 with the range of inhibition ratio at 51–96% for a concentration of 40 μM. Compounds 1, 2 showed weak anticoagulant activity with PT at 16.8 s. Few work was reported on the anti-acetylcholinesterase, and anticoagulant activities of aureonitol, and cytochalasan derivatives. The preliminary structure–activity relationship stated that the oxidation ring-opening in yamchaetoglobosin A can retain the inhibitory effect against NO production and tumor cell.

A three-component protocol involving enantiopure Δ-[Ir(ppy)2(MeCN)2](PF6) (ppy is 2-phenylpyridine) and salicylaldehyde as chiral auxiliaries was successfully applied to discriminate the absolute configuration and determine the enantiopurity of primary amines and amine alcohols via 1H NMR spectroscopy. The assembly reaction is rapid and quantitative, generating a pair of diastereomers that can be determined directly without physical separation. Single crystal structural analyses indicate that the shielding effects on the ligands imposed by a pair of diastereomers are different and generate sufficient resolution NMR signals for identification. The enhancement of stability via chelating coordination to Ir(III) ion and more than one pair of diastereotopic resonances in different detection regions of the three-component protocol ensure a high degree of accuracy in quantifying the ee value of chiral amines. The absolute errors in the ee determinations by 1H NMR spectroscopy in different detection windows are w...

The effects of sample injection time, pH of the buffer solution, micelles concentration and micelles standing time on the peak splitting in MEKC were explored respectively in the research. 4- methyl phenethyl alcohol, 4- methoxy phenethyl alcohol, 4- nitro phenethyl alcohol, benzyl alcohol and phenethyl alcohol were selected as analytes and were separated by CE in a 50 μm i.d. × 60 cm (effective length 45 cm) fused-silica capillary at 20.0 kV. The buffer solution in MEKC consisted of 15.0 mM Na2B4O7, 10.0 mM NaH2PO4 and specific concentration of SDS. Suggestions to avoid the peak splitting were given.

Hipposponlachnins A (1) and B (2), possessing an unprecedented tetracyclo [9.3.0.02,8.03,7] tetradecane ring system, and the probable biogenetic precursor [3, (1R*,2E,4R*,7E,10S*,11S*,12R*)-10, 18-diacetoxydolabella-2,7-dien-6-one] of 1‒2 were isolated from the South China Sea marine sponge Hippospongia lachne. The structures of the novel compounds were determined using integrated spectroscopic methods in combination with single-crystal X-ray diffraction analysis. Compounds 1‒2 showed potent inhibitory activity on the release of β-hexosaminidase, a biomarker for degranulation, as well as the production of pro-inflammatory cytokine IL-4 and lipid mediator LTB4 in DNP-IgE-stimulated RBL-2H3 cells.

Treatment of cis-[Ru(bpy)2Cl2]⋅2 H2O or Δ/Λ-[Ru(bpy)2(py)2]2+ (bpy=2,2′-bipyridine, py=pyridine) with the prochiral thioether ligands 2-alkylthiobenzoic acid (HOSR) produces the corresponding thioether complexes rac-[Ru(bpy)2(OSR)](PF6) (R=Me (rac-1), iPr (rac-2), 2-benzylthiobenzonate (Bn) (rac-3)) and Δ/Λ-[Ru(bpy)2(OSR)](PF6) (R=Me (Δ-1/Λ-1), iPr (Δ-2/Λ-2), Bn (Δ-3/Λ-3)) with retention of the configurations at chiral metal centers. In situ oxidation of the thioether complexes by meta-chloroperoxybenzoic acid provides the corresponding sulfoxide complexes rac-[Ru(bpy)2(OSOR)](PF6) (OSOR is 2-alkylsulfinylbenzonate, R=Me (rac-1 a), iPr (rac-2 a), Bn (rac-3 a)), Δ-[Ru(bpy)2{(R)-OSOR}](PF6) (R=Me (Δ-1 a), iPr (Δ-2 a), Bn (Δ-3 a)), and Λ-[Ru(bpy)2{(S)-OSOR}](PF6) (R=Me (Λ-1 a), iPr (Λ-2 a), Bn (Λ-3 a)) in yields of 95 % with 98 % ee values. The absolute configurations at the metal centers and sulfur atoms were determined by means of X-ray crystallography. The results indicate that the configurations of the metal centers are retained and have the function of controlling sulfoxide chirality during the oxidation process. The Δ metal-centered configuration enantioselectively generates an R-configuration sulfoxide, and the Λ configuration enantioselectively forms an S-configuration sulfoxide in the course of the in situ oxidation reaction, thereby resulting in a predetermined chirality of the sulfoxide ligands. The predetermined chirality of sulfoxides (S)-HOSOR and (R)-HOSOR were obtained by the treatments of the corresponding sulfoxide complexes Δ-[Ru(bpy)2{(R)-OSOR}](PF6) and Λ-[Ru(bpy)2{(S)-OSOR}](PF6) with trifluoroacetic acid in yields of 90 % with 83.5–92.9 % ee values.

Entangled coordination polymers have attracted considerable interest due to their novel structures and potential applications. In this paper, one new 2D → 3D porous zinc coordination polymer {[Zn2(DPDBT)2(OBA)2](H2O)3}n (1) with parallel polycatenation was synthesized under solvothermal conditions based on 2,8-di(pyridin-4-yl)dibenzo[b,d]thiophene (DPDBT) ligand. In addition, complex 1 exhibits interesting solid-state photoluminescence and high thermal stability.