2,2'-Biphenol-based Ultrathin Microporous Nanofilms for Highly Efficient Molecular Sieving Separation.

Organic solvent nanofiltration (OSN) is an emerging membrane separation technology, which urgently requires robust, easily processed, OSN membranes possessing high permeance and small solutes-selectivity to facilitate enhanced industrial uptake. Herein, we describe the use of two 2,2'-biphenol (BIPOL) derivatives to fabricate hyper-crosslinked, microporous polymer nanofilms through IP. Ultra-thin, defect-free polyesteramide/polyester nanofilms (≈5 nm) could be obtained readily due to the relatively large molecular size and ionized nature of the BIPOL monomers retarding the rate of the IP. The enhanced microporosity arises from the hyper-crosslinked network structure and monomer rigidity. Specifically, the amino-BIPOL/PAN membrane exhibits extraordinary permselectivity performances with molecular weight cut-off as low as 233 Da and MeOH permeance of ≈13 LMH/bar. Precise separation of small dye mixtures with similar M.W. based on both their charge and molecular size are achieved.

Insights into chromosomal evolution and sex determination of Pseudobagrus ussuriensis (Bagridae, Siluriformes) based on a chromosome-level genome.

Pseudobagrus ussuriensis is an aquaculture catfish with significant sexual dimorphism. In this study, a chromosome-level genome with a size of 741.97 Mb was assembled for female P. ussuriensis. A total of 26 chromosome-level contigs covering 97.34% of the whole-genome assembly were obtained with an N50 of 28.53 Mb and an L50 of 11. A total of 24,075 protein-coding genes were identified, with 91.54% (22,039) genes being functionally annotated. Based on the genome assembly, four chromosome evolution clusters of catfishes were identified and the formation process of P. ussuriensis chromosomes was predicted. A total of 55 sex-related quantitative trait loci (QTLs) with a phenotypic variance explained value of 100% were located on chromosome 8 (chr08). The QTLs and other previously identified sex-specific markers were located in a sex-determining region of 16.83 Mb (from 6.90 to 23.73 Mb) on chr08, which was predicted as the X chromosome. The sex-determining region comprised 554 genes, with 135 of which being differently expressed between males and females/pseudofemales, and 16 candidate sex-determining genes were screened out. The results of this study provided a useful chromosome-level genome for genetic, genomic and evolutionary studies of P. ussuriensis, and also be useful for further studies on sex-determination mechanism analysis and sex-control breeding of this fish.

Synthesis of silyl iron dinitrogen complexes for activation of dihydrogen and catalytic silylation of dinitrogen.

Three novel iron dinitrogen hydrides, [FeH(iPr-PSiMeP)(N2)(PMe3)] (1), [FeH(iPr-PSiPhP)(N2)(PMe3)] (2), and [FeH(iPr-PSiPh)(N2)(PMe3)] (3), supported by a silyl ligand are synthesized for the first time by changing the electronic effect and steric hindrance of the ligands through the reaction of ligands L1-L3 with Fe(PMe3)4 in a nitrogen atmosphere. The ligands containing an electron-donating group with large steric hindrance on the phosphorus atom are beneficial for the formation of dinitrogen complexes. A penta-coordinate iron hydride [FeH(iPr-PSiPh)(PMe3)2] (4) was formed through the reaction of ligand L3 with Fe(PMe3)4 in an argon atmosphere under the same conditions. The reactions between complexes 1-3 with an atmospheric pressure of dihydrogen gas resulted in Fe(II) dihydrides, [(iPr-PSiMe(µ-H)P)Fe(H)2(PMe3)] (5), [(iPr-PSiPh(µ-H)P)Fe(H)2(PMe3)] (6) and [(iPr-PSiPh(µ-H))Fe(H)2(PMe3)2] (7), with an η2-(Si-H) coordination. The isolation of dihydrides 5-7 demonstrates the ability of the dinitrogen complexes 1-3 to realize the activation of dihydrogen under ambient temperature and pressure. The molecular structures of complexes 1-7 were elucidated by single crystal X-ray diffraction analysis. The iron dinitrogen hydrides 1-3 are effective catalysts for the silylation of dinitrogen under ambient conditions and among them 3 is the best catalyst.

[Analysis of Spatial-Temporal Variation Characteristics of Potential Non-point Source Pollution Risks in the Upper Beiyun River Basin Using Different Weighting Methods].

Non-point source pollution has become an important factor affecting the aquatic ecological environment and human health, and the analysis of spatial-temporal variations in non-point source pollution risks is an important prerequisite for pollution control. Based on land-use and land-cover data from 1980 to 2020, the potential non-point source pollution index (PNPI) model was applied in the upper Beiyun River Basin using different weighting methods. The results showed that:① The potential risk of non-point source pollution is high in the southeast and low in the northwest of the basin. Between 1980 and 2020, the total area of extremely high-risk and high-risk non-point source pollution regions showed a decreasing trend, and the main types of land use for extremely high-risk and high-risk regions gradually evolved from paddy fields, drylands, and orchards to urban and rural residential land; ② The weighting of the land use index determined by the mean-square deviation decision, entropy, coefficient of variation, and expert scoring methods was largest among the three PNPI indices, with average weightings of 0.46, 0.53, 0.45, and 0.48, respectively. However, the weightings for runoff and distance indices determined by different weighting methods were notably different, and the proportions of regions with different levels of non-point source pollution risk also varied; ③ The exponential function method, which describes the relationship between source factors and transport factors by constructing the exponential functions of land use, runoff, and distance indices, provided results that are more consistent with the spatial distribution characteristics of non-point source pollution risk in the basin. The proportions of extremely low-risk and extremely high-risk regions are 54.22% and 6.23%, respectively. These results provide scientific reference for risk analysis and the control of non-point source pollution in this basin.

Differential expression analysis and identification of sex-related genes by gonad transcriptome sequencing in estradiol-treated and non-treated Ussuri catfish Pseudobagrus ussuriensis.

The Ussuri catfish (Pseudobagrus ussuriensis) has an XX/XY sex determination system but its sex determination gene(s) remain unknown. To better understand the molecular sex determination mechanism, transcriptome analysis was conducted to obtain sex-related gene expression profiles. Transcriptome analyses were made of male and female developing/differentiating gonads by high-throughput RNA sequencing, including gonads from fish given an estradiol-induced sex reversal treatment. A total of 81,569 unigenes were assembled and 39,904 were significantly matched to known unique proteins by comparison with public databases. Twenty specifically expressed and 142 differentially expressed sex-related genes were extracted from annotated data by comparing the treatment groups. These genes are involved in spermatogenesis (e.g., Dnali1, nectin3, klhl10, mybl1, Katnal1, Eno4, Mns1, Spag6, Tsga10, Septin7), oogenesis (e.g., Lagr5, Fmn2, Npm2, zar1, Fbxo5, Fbxo43, Prdx4, Nrip1, Lfng, Atrip), gonadal development/differentiation (e.g., Cxcr4b, Hmgb2, Cftr, Ch25h, brip1, Prdm9, Tdrd1, Star, dmrt1, Tut4, Hsd17b12a, gdf9, dnd, arf1, Spata22), and estradiol response (e.g., Mmp14, Lhcgr, vtg1, vtg2, esr2b, Piwil1, Aifm1, Hsf1, gdf9). Dmrt1 and gdf9 may play an essential role in sex determination in P. ussuriensis. The expression patterns of six random genes were validated by quantitative real-time PCR, which confirmed the reliability and accuracy of the RNA-seq results. These data provide a valuable resource for future studies of gene expression and for understanding the molecular mechanism of sex determination/differentiation and gonadal development/differentiation (including hormone-induced sexual reversal) in Ussuri catfish. This has the potential to assist in producing monosex Ussuri catfish to increase aquacultural productivity.

BDE-47 induced apoptosis in zebrafish embryos through mitochondrial ROS-mediated JNK signaling.

2,2,4,4-tetrabromodiphenyl ether (BDE-47) has received considerable attention because of its high detection level in biological samples and potential developmental toxicity. Here, using zebrafish (Danio rerio) as the experimental animal, we investigated developmental effects of BDE-47 and explored the potential mechanism. Zebrafish embryos at 4 h post-fertilization (hpf) were exposed to 0.312, 0.625 and 1.25 mg/L BDE-47 to 74-120 hpf. We found that BDE-47 instigated a dose-related developmental toxicity, evidenced by reduced embryonic survival and hatching rate, shortened body length and increased aberration rate. Meanwhile, higher doses of BDE-47 reduced mitochondrial membrane potential and ATP production but increased apoptosis in zebrafish embryos. Expression of genes involved in mitochondrial oxidative phosphorylation (OXPHOS) (ndufb8, sdha, uqcrc1, cox5ab and atp5fal) were negatively related to BDE-47 doses in zebrafish embryos. Moreover, exposure to BDE-47 at 0.625 or 1.25 mg/L impaired mitochondrial biogenesis and mitochondrial dynamics. Our data further showed that BDE- 47 exposure induced excessive reactive oxygen species (ROS) and oxidative stress, which was accompanied by the activation of c-Jun N-terminal Kinase (JNK). Antioxidant NAC and JNK inhibition could mitigate apoptosis in embryos and improve embryonic development in BDE-47-treated zebrafish, suggesting the involvement of ROS/JNK pathway in embryonic developmental changes induced by BDE-47. Altogether, our data suggest here that developmental toxicity of BDE-47 may be associated with mitochondrial ROS-mediated JNK signaling in zebrafish embryo.

Polymorphisms of the growth hormone gene and their association with growth traits and sex in Sarcocheilichthys sinensis.

The growth hormone gene (gh) of Sarcocheilichthys sinensis was cloned and characterized in this study. The cDNA length of gh was 973 bp, containing a 5'-UTR of 15 bp, a 3'-UTR of 325 bp and an open reading frame of 633 bp. The genomic DNA of gh was 2135 bp in length containing five exons and four introns. The precursor peptide of gh contained 210 amino acids (aa), including a signal peptide of 22 aa (Met1-Ala22) and a mature region of 188 aa (Ser23-Leu210). The similarity and identity ranges of the gh precursor peptide with those of other cyprinids were 88.6%-99.0% and 84.8%-98.6%, respectively. The gh of S. sinensis expressed at the highest level in the pituitary, and its expression was also detected in muscle and brain. Six polymorphic sites were detected in intron 1 (g.51InDel, g.64InDel and g.242InDel), intron 2 (g.864T>C), intron 3 (g.1017InDel) and intron 4 (g.1541A>G). Among these sites, g.242InDel was significantly associated with condition factor, g.1541A>G was associated with all six growth traits, while g.864T>C was associated with sex. The data obtained herein provide useful information for further studies on the regulation mechanisms of growth and sexual growth differences in S. sinensis.

Correction: Pyridine N-oxide promoted hydrosilylation of carbonyl compounds catalyzed by [PSiP]-pincer iron hydrides.

Correction for 'Pyridine N-oxide promoted hydrosilylation of carbonyl compounds catalyzed by [PSiP]-pincer iron hydrides' by Guoliang Chang et al., Dalton Trans., 2020, 49, 9349-9354, DOI: 10.1039/D0DT00392A.

Pyridine N-oxide promoted hydrosilylation of carbonyl compounds catalyzed by [PSiP]-pincer iron hydrides.

Five [PSiP]-pincer iron hydrides 1-5, [(2-Ph2PC6H4)2HSiFe(H)(PMe3)2 (1), (2-Ph2PC6H4)2MeSiFe(H)(PMe3)2 (2), (2-Ph2PC6H4)2PhSiFe(H)(PMe3)2 (3), (2-(iPr)2PC6H4)2HSiFe(H)(PMe3) (4), and (2-(iPr)2PC6H4)2MeSiFe(H)(PMe3)2 (5)], were used as catalysts to study the effects of pyridine N-oxide and the electronic properties of [PSiP]-ligands on the catalytic hydrosilylation of carbonyl compounds. It was proved for the first time that this catalytic process could be promoted with pyridine N-oxide as the initiator at 30 °C because the addition of pyridine N-oxide is beneficial for the formation of an unsaturated hydrido iron complex, which is the key intermediate in the catalytic mechanism. Complex 4 as the best catalyst shows excellent catalytic performance. Among the five complexes, complex 3 was new and the molecular structure of complex 3 was determined by single crystal X-ray diffraction. A proposed mechanism was discussed.

Genetic diversity analysis of Asian clam Corbicula fluminea in the Hongze Lake based on mitochondrial cytochrome b gene.

The Asian clam Corbicula fluminea is a small bivalve with high nutritional and medical values. However, natural resources of C. fluminea have declined in many areas of China including the Hongze Lake. In this study, 119 individuals from 10 sites of this lake and 2 outgroups were analyzed using a 456 bp mitochondrial cytochrome b (cytb) gene segment. Totally, 19 polymorphic sites were detected, which defined 16 haplotypes. Polymorphism varied among the 10 populations with those at the water inlet being more polymorphic. Most FST values among these populations were below 0.15 with the overall value of 0.060 (p < .05), meanwhile, the overall gene flow was 7.67, both of which indicated the low level of population differentiation in this lake. Neutrality test and mismatch analyses indicated that population explosion may have occurred in this lake. The results obtained in this study will provide useful information for artificial breeding and resource protection of this species in the Hongze Lake.

De novo assembly, characterization and annotation for the transcriptome of Sarcocheilichthys sinensis.

The Chinese lake gudgeon Sarcocheilichthys sinensis is a small cyprinid fish with great aquaculture potential both for its edible and ornamental values. Nevertheless, available genomic and transcriptomic information for this fish is extremely deficient. In this study, a normalized cDNA library was constructed using 13 mixed tissues of an adult male S. sinensis, and was sequenced by the Illumina HiSeq2500 platform. De novo assembly was performed using 38,911,511 obtained clean reads, and a total of 147,282 unigenes with an average length of 900 bp were finally achieved. 96.2% of these unigenes were annotated in 9 public databases, and 16 segments of growth-related genes were identified for future studies. In addition, 28,493 unigenes were assigned to 61 subcategories of Gene Ontology (GO), and 10,483 unigenes were assigned to 25 categories of Cluster of Orthologous Group (COG). Moreover, 14,943 unigenes were classified into 225 pathways of the Kyoto Encyclopedia of Genes and Genomes (KEGG) database. A total of 30,666 microsatellites were detected from 17,627 unigenes with an average distribution density of 1:2405 bp. This transcriptome data set will be valuable for researches on discovery, expression and evolution on genes of interest. Meanwhile, the identified microsatellites would be useful tools for genetic and genomic studies in S. sinensis.

Cu(II), Ni(II) complexes derived from chiral Schiff-base ligands: Synthesis, characterization, cytotoxicity, protein and DNA-binding properties.

A series of novel copper (II) and nickel (II) complexes derived from chiral Schiff-base ligands [(R)/(S)-H2L(1)=(R)/(S)-2-[(1-Hydroxymethyl-propylimino)-methyl]-5-methoxy-phenol and (R)/(S)-H2L(2)=(R)/(S)-2-[(1-Hydroxymethyl-2-phenyl-ethylimino)-methyl]-5-methoxy-phenol], were synthesized and characterized by elemental analyses, (1)H NMR spectra, FT-IR spectrum. The crystal structures of complexes 1-5 were determined through single crystal X-ray diffraction (SXRD). The structures showed the ligands coordinated to the Cu/Ni (II) ion in a neutral manner via ONO donor atoms, and oxygen atoms of solvent molecules occupy the axial positions in Ni (II) complexes 3 and 4. The complexes interactions with BSA and CT-DNA were investigated by various spectroscopic methods (UV-Visible, circular dichroism spectrum, fluorescence spectroscopic and synchronous fluorescence spectra). Interactions of chiral copper (II) complexes are stronger than nickel (II) complexes. Further, the cytotoxicities of the complexes 1-6 towards three kinds of cancerous cell lines, were human lung adenocarcinoma (A549), human cervical carcinoma cell (HeLa) and human breast cancer cell (MCF-7) respectively, were evaluated by MTT assay. All complexes exhibited good cytotoxic activity. Furthermore, Cu (II) complex 5 derived from (R)-Schiff-base ligand was found to be more effective towards HeLa cancerous cell. The results showed that chirality and metal ion have important influence on their anticancer activities and interactions with DNA/BSA.

Hierarchical three-dimensional branched hematite nanorod arrays with enhanced mid-visible light absorption for high-efficiency photoelectrochemical water splitting.

Herein, we presented hierarchical three-dimensional (3D) branched hematite nanorod arrays (NAs) on transparent fluorine-doped tin oxide (FTO) conductive glass substrates, which exhibited high PEC water splitting performance due to the enhancement of mid-visible light harvesting as well as charge separation and transfer. The introduction of a TiO2 underlayer made the as-prepared 3D branched hematite NAs achieve a photocurrent density of 0.61 mA cm(-2) at 1.23 V vs. reversible hydrogen electrode (RHE) without high-temperature activation.

Chiral manganese (IV) complexes derived from Schiff base ligands: Synthesis, characterization, in vitro cytotoxicity and DNA/BSA interaction.

Two new couples of chiral manganese (IV) complexes with Schiff-base ligands, Λ-[Mn(R-L(1))2]·2(CH3OH) (Λ-1) and Δ-[Mn(S-L(1))2]·2(CH3OH) (Δ-1), Λ-[Mn(R-L(2))2]·(H2O)2 (Λ-2) and Δ-[Mn(S-L(2))2]·(H2O)2 (Δ-2), {H2L(1)=(R/S)-(±)-1-[(1-hydroxymethyl-propylimino)-methyl]-naphthalen-2-ol, H2L(2)=(R/S)-(±)-1-[(1-Hydroxymethyl-2-phenyl-ethylimino)-methyl]-naphthalen-2-ol} have been synthesized, and fully characterized by elemental analyses, UV-Vis spectrum, circular dichroism spectrum, FT-IR spectrum, mass spectrum, and single crystal X-ray diffraction (SXRD). The interaction of the four chiral Mn (IV) complexes with CT-DNA and BSA were also investigated by various spectroscopic techniques (UV-visible, fluorescence spectroscopic). The results show that the Δ-complexes exhibit more efficient CT-DNA interaction with respect to the Λ-complexes. All the complexes could quench the intrinsic fluorescence of BSA by a static quenching process. In addition, the vitro cytotoxicity of these complexes toward four kinds of cancerous cell lines (A549, HeLa, HL-60, and Caco-2) was assayed by the MTT method, which exhibited to be selectively active against certain cell lines.

Crystal Structure, Cytotoxicity and Interaction with DNA of Zinc (II) Complexes with o-Vanillin Schiff Base Ligands.

Two new zinc complexes, Zn(HL1)2 (1) and [Zn2(H2L2)(OAc)2]2 (2) [H2L1 = Schiff base derived from o-vanillin and (R)-(+)-2-amino-3-phenyl-1-propanol, H3L2 = Schiff base derived from o-vanillin and 2-amino-2-ethyl-1,3-propanediol], have been synthesized and characterized by single crystal X-ray diffraction, elemental analyses, TG analyses, solid fluorescence, IR, UV-Vis and circular dichroism spectra. The structural analysis shows that complex 1 has a right-handed double helical chain along the crystallographic b axis. A homochiral 3D supramolecular architecture has been further constructed by intermolecular C-H··· π, O-H···O and C-H···O interactions. Complex 2 includes two crystallographically independent binuclear zinc molecules. The two binuclear zinc molecules are isostructural. The 2-D sheet supramolecular structure was formed by intermolecular hydrogen bonding interaction. The fluorescence of ligands and complexes in DMF at room temperature are studied. The interactions of two complexes with calf thymus DNA (CT-DNA) are investigated using UV-Vis, CD and fluorescence spectroscopy. The results show that complex 1 exhibits higher interaction with CT-DNA than complex 2. In addition, in vitro cytotoxicity of the complexes towards four kinds of cancerous cell lines (A549, HeLa, HL-60 and K562) were assayed by the MTT method. Investigations on the structures indicated that the chirality and nuclearity of zinc complexes play an important role on cytotoxic activity.

Uniform Doping of Titanium in Hematite Nanorods for Efficient Photoelectrochemical Water Splitting.

Doping elements in hematite nanostructures is a promising approach to improve the photoelectrochemical (PEC) water-splitting performance of hematite photoanodes. However, uniform doping with precise control on doping amount and morphology is the major challenge for quantitatively investigating the PEC water-splitting enhancement. Here, we report on the design and synthesis of uniform titanium (Ti)-doped hematite nanorods with precise control of the Ti amount and morphology for highly effective PEC water splitting using an atomic layer deposition assisted solid-state diffusion method. We found that Ti doping promoted band bending and increased the carrier density as well as the surface state. Remarkably, these uniformly doped hematite nanorods exhibited high PEC performance with a pronounced photocurrent density of 2.28 mA/cm(2) at 1.23 V vs reversible hydrogen electrode (RHE) and 4.18 mA/cm(2) at 1.70 V vs RHE, respectively. Furthermore, as-prepared Ti-doping hematite nanorods performed excellent repeatability and durability; over 80% of the as-fabricated photoanodes reproduced the steady photocurrent density of 1.9-2.2 mA/cm(2) at 1.23 V vs RHE at least 3 h in a strong alkaline electrolyte solution.

A comparative study of cytotoxicity and interaction with DNA/protein of five transition metal complexes with Schiff base ligands.

Five transition metal complexes NiL(1)2 (1), CuL(1)2 (2), ZnL(1)2 (3), [MnL(1)2(N3)]n·nCH2Cl2 (4), CuL(2)2 (5) {HL(1)=3-{[2-(2-hydroxy-ethoxy)-ethylimino]-methyl}-naphthalen-2-ol, HL(2)=2-{[2-(2-hydroxy-ethoxy)-ethylimino]-methyl}-phenol} have been synthesized and fully characterized. In all of the complexes, the ligands coordinated to the metal ion in a negative fashion via O and N donor atoms. The X-ray structures of nickel complex 1 and copper complexes 2 and 5 are four-coordinated monomers and show slightly distorted square-planar geometry in the vicinity of the central metal atom. Zinc complex 3 exhibits a four-coordinated tetrahedral structure. Differently, manganese complex 4 reveals a six-coordinated octahedral structure, one-dimensional chain is linked by azide in the end-to-end mode. In vitro cytotoxicity of these complexes to various tumor cell lines was assayed by the MTT method. The results showed that most of these metal-Schiff base complexes exhibited enhanced cytotoxicity than Schiff base ligands, which clearly implied a positive synergistic effect. Moreover, these complexes appeared to be selectively active against certain cell lines. The interactions of these metal complexes with CT-DNA were investigated by UV-vis, fluorescence and CD spectroscopy, the results indicated that these complexes are metallointercalators and can interact with CT-DNA. The study of interaction between complexes and BSA indicated that all of the complexes could quench the intrinsic fluorescence of BSA in a static quenching process.