Ring-Opening Metathesis Polymerization of the Dewar Isomer of 1,2-Azaborinine, a B-N Isostere of Benzene.

The successful polymerization of the Dewar isomer of an azaborinine heterocycle is reported. Controlled ring-opening metathesis polymerization was accomplished with Grubbs and Hoveya-Grubbs second generation catalysts (G2, HG2), as well as a Z-selective Ru catalyst (HGM2001). The structure of the polymers containing 4-membered B-N heterocycles was verified by GPC and multinuclear and 2D NMR. Differences in stereochemistry of polymers derived from G2/HG2 versus the Z-selective catalyst HGM2001 were substantiated by 2D NOESY, FT-IR, and Raman analyses. The incorporation of B-N heterocycles into these polymer structures is promising as a route to functional polymers that contain polar side groups.

Theoretical Examination of the Hydroxide Transport in Cobaltocenium-Containing Polyelectrolytes.

Polymers incorporating cobaltocenium groups have received attention as promising components of anion-exchange membranes (AEMs), exhibiting a good balance of chemical stability and high ionic conductivity. In this work, we analyze the hydroxide diffusion in the presence of cobaltocenium cations in an aqueous environment based on the molecular dynamics of model systems confined in one dimension to mimic the AEM channels. In order to describe the proton hopping mechanism, the forces are obtained from the electronic structure computed at the density-functional tight-binding level. We find that the hydroxide diffusion depends on the channel size, modulation of the electrostatic interactions by the solvation shell, and its rearrangement ability. Hydroxide diffusion proceeds via both the vehicular and structural diffusion mechanisms with the latter playing a larger role at low diffusion coefficients. The highest diffusion coefficient is observed under moderate water densities (around half the density of liquid water) when there are enough water molecules to form the solvation shell, reducing the electrostatic interaction between ions, yet there is enough space for the water rearrangements during the proton hopping. The effects of cobaltocenium separation, orientation, chemical modifications, and the role of nuclear quantum effects are also discussed.

Stability Analysis of Substituted Cobaltocenium [Bis(cyclopentadienyl)cobalt(III)] Employing Chemistry-Informed Neural Networks.

Cationic cobaltocenium derivatives are promising components of the anion exchange membranes because of their excellent thermal and alkaline stability under the operating conditions of a fuel cell. Here, we present an efficient modeling approach to assessing the chemical stability of substituted cobaltocenium CoCp2+, based on the computed electronic structure enhanced by machine learning techniques. Within the aqueous environment, the positive charge of the metal cation is balanced by the hydroxide anion through formation of the CoCp2+OH- complexes, whose dissociation is studied within the implicit solvent employing the density functional theory. The data set of about 118 the CoCp2+OH- complexes based on 42 substituent groups characterized by a range of electron-donating (ED) and electron-withdrawing (EW) properties is constructed and analyzed. Given 12 carefully chosen chemistry-informed descriptors of the complexes and relevant fragments, the stability of the complexes is found to strongly correlate with the energies of the highest occupied and lowest unoccupied molecular orbitals, modulated by a switching function of the Hirshfeld charge. The latter is used as a measure of the electron-withdrawing-donating character of the substituents. On the basis of this observation from the conventional regression analysis, two fully connected, feed-forward neural network (FNN) models with different unit structures, called the chemistry-informed (CINN) and the quadratic (QNN) neural networks, together with a support vector regression (SVR) model are developed. Both deep neural network models predict the bond dissociation energies of the cobaltocenium complexes with mean relative errors less than 10.56% and average absolute errors less than 1.63 kcal/mol, superior to the conventional regression and the SVR model prediction. The results show the potential of QNN to efficiently capture more complex relationships. The concept of incorporating the domain (chemical) knowledge/insight into the neural network structure paves the way to applications of machine learning techniques with small data sets, ultimately leading to better predictive models compared to the classical machine learning method SVR and conventional regression analysis.

Correlation between the Stability of Substituted Cobaltocenium and Molecular Descriptors.

Metallocenium cations, used as a component in an anion exchange membrane of a fuel cell, demonstrate excellent thermal and alkaline stability, which can be improved by the chemical modification of the cyclopentadienyl rings with substituent groups. In this work, the relation between the bond dissociation energy (BDE) of the cobaltocenium (CoCp2+) derivatives, used as a measure of the cation stability, and chemistry-informed descriptors obtained from the electronic structural calculations is established. The analysis of 12 molecular descriptors for 118 derivatives reveals a nonlinear dependence of the BDE on the electron donating-withdrawing character of the substituent groups coupled to the energy of the frontier molecular orbitals. A chemistry-informed feed-forward neural network trained using k-fold cross-validation over the modest data set is able to predict the BDE from the molecular descriptors with the mean absolute error of about 1 kcal/mol. The theoretical analysis suggests some promising modifications of cobaltocenium for experimental research. The results demonstrate that even for modest data sets the incorporation of the chemistry knowledge into the neural network architecture, e.g., through mindful selection and screening of the descriptors and their interactions, paves the way to gain new insight into molecular properties.

Mechanochemistry of Cationic Cobaltocenium Mechanophore.

Recent research on the mechanochemistry of metallocene mechanophores has shed light on the force-responsiveness of these thermally and chemically stable organometallic compounds. In this work, we report a combination of experimental and computational studies on the mechanochemistry of main-chain cobaltocenium-containing polymers. Ester derivatives of the cationic cobaltocenium, though isoelectronic to neutral ferrocene, are unstable in the nonmechanical control experimental conditions that were accommodated by their ferrocene analogs. Replacing the electron withdrawing C-ester linkages with electron-donating C-alkyls conferred the necessary stability and enabled the mechanochemistry of the cobaltocenium to be assessed. Despite their high bond dissociation energy, cobaltocenium mechanophores are found to be selective sites of main chain scission under sonomechanical activation. Computational CoGEF calculations suggest that the presence of a counterion to cobaltocenium plays a vital role by promoting a peeling mechanism of dissociation in conjunction with the initial slipping.

Allelopathic inhibitory effect of the macroalga Pyropia haitanensis (Rhodophyta) on harmful bloom-forming Pseudo-nitzschia species.

The blooms of harmful microalgae represent a prominent threat to fisheries, public health, and economies throughout the world. Recent studies have shown that certain macroalgae release allelochemicals that can inhibit the growth of bloom-forming microalgae. In this study, we found that the macroalga Pyropia haitanensis significantly inhibited growth of the harmful bloom-forming microalgae Pseudo-nitzschia pungens and Pseudo-nitzschia multiseries. The inhibitory-effect of the live thali of P. haitanensis was highest, followed by that of dry powder, water-soluble extract, and culture medium filtrate. The Pseudo-nitzschia species died 96 h after exposure to 5-10 g fresh-weight L-1 of P. haitanensis live thalli. Furthermore, an aqueous extract of P. haitanensis suppressed the growth of P. pungens and P. multiseries, thereby indicating that P. haitanensis contains stable allelopathic substances that cause the observed inhibitory-effects. On the basis of these findings, we conclude that the macroalga P. haitanensis would have potential utility in controlling the blooms of Pseudo-nitzschia species.

Polysiloxane/Polystyrene Thermo-Responsive and Self-Healing Polymer Network via Lewis Acid-Lewis Base Pair Formation.

The use of thermo-reversible Lewis Pair (LP) interactions in the formation of transient polymer networks is still greatly underexplored. In this work, we describe the synthesis and characterization of polydimethylsiloxane/polystyrene (PDMS/PS) blends that form dynamic Lewis acid-Lewis base adducts resulting in reversible crosslinks. Linear PS containing 10 mol % of di-2-thienylboryl pendant groups randomly distributed was obtained in a two-step one-pot functionalization reaction from silyl-functionalized PS, while ditelechelic PDMS with pyridyl groups at the chain-termini was directly obtained via thiol-ene "click" chemistry from commercially available vinyl-terminated PDMS. The resulting soft gels, formed after mixing solutions containing the PDMS and PS polymers, behave at room temperature as elastomeric solid-like materials with very high viscosity (47,300 Pa·s). We applied rheological measurements to study the thermal and time dependence of the viscoelastic moduli, and also assessed the reprocessability and self-healing behavior of the dry gel.

Correction: Synthesis by free radical polymerization and properties of BN-polystyrene and BN-poly(vinylbiphenyl).

Correction for 'Synthesis by free radical polymerization and properties of BN-polystyrene and BN-poly(vinylbiphenyl)' by Wen-Ming Wan et al., Chem. Commun., 2016, 52, 13616-13619.

Biological and Chemical Diversity of Bacteria Associated with a Marine Flatworm.

The aim of this research is to explore the biological and chemical diversity of bacteria associated with a marine flatworm Paraplanocera sp., and to discover the bioactive metabolites from culturable strains. A total of 141 strains of bacteria including 45 strains of actinomycetes and 96 strains of other bacteria were isolated, identified and fermented on a small scale. Bioactive screening (antibacterial and cytotoxic activities) and chemical screening (ultra-performance liquid chromatography-mass spectrometry (UPLC-MS)) yielded several target bacterial strains. Among these strains, the ethyl acetate (EA) crude extract of Streptomyces sp. XY-FW47 fermentation broth showed strong antibacterial activity against methicillin-resistant Staphylococcus aureus ATCC43300 (MRSA ATCC43300) and potent cytotoxic effects on HeLa cells. The UPLC-MS spectral analysis of the crude extract indicated that the strain XY-FW47 could produce a series of geldanamycins (GMs). One new geldanamycin (GM) analog, 4,5-dihydro-17-O-demethylgeldanamycin (1), and three known GMs (2-4) were obtained. All of these compounds were tested for antibacterial, cytotoxic, and antifungal activities, yet only GM (3) showed potent cytotoxic (HeLa cells, EC50 = 1.12 µg/mL) and antifungal (Setosphaeria turcica MIC = 2.40 µg/mL) activities. Their structure-activity relationship (SAR) was also preliminarily discussed in this study.

Deinococcus planocerae sp. nov., isolated from a marine flatworm.

A Gram-positive, non-motile and coccoid strain, designated XY-FW106T, was isolated from a marine flatworm identified to be Planocera sp. The 16S rRNA gene sequence of this pink organism was consistent with membership of the genus Deinococcus, with high sequence similarity to Deinococcus aetherius ST0316T (94.7%). The optimum growth temperature range of the strain XY-FW106T was found to be 25-30 °C and optimum growth occurs at pH 7.2-7.4 without NaCl. The strain XY-FW106T was found to contain unidentified glycolipids, unidentified phosphoglycolipids, unidentified phospholipids and unidentified lipids, which differed from those of closely related species. Menaquinone MK-8 was identified as the major respiratory quinone and the predominant cellular fatty acids were found to be Summed Feature 3 (C16:1 ω7c/C16:1 ω6c), C16:0, iso-C15:0, and Summed Feature 8 (C18:1 ω7c/C18:1 ω6c). The DNA G+C content was determined to be 70.2 mol%. The biochemical and chemotaxonomic data together suggest that the strain represents a new species for which the name Deinococcus planocerae sp. nov. is proposed. The type strain is XY-FW106T (=MCCC 1K01499T=KCTC 33809T).

Altererythrobacter salegens sp. nov., a slightly halophilic bacterium isolated from surface sediment.

A Gram-negative, rod-shaped and slightly halophilic bacterium, strain XY-R17T, was isolated from the surface sediment of Mai Po Inner Deep Bay Ramsar Site birdwatch in Hong Kong. The 16S rRNA gene sequence of strain XY-R17T exhibited 96.5 % similarity to that of the type strain of Altererythrobacter atlanticus. Optimal growth occurred at pH 7.0-7.5, 3-8 % (w/v) NaCl and at 30 °C. The major respiratory quinone was ubiquinone-10. The principal fatty acids were summed feature 8 (C18 : 1ω7c and/or C18 : 1ω6c), summed feature 3 (C16 : 1ω7c and/or C16 : 1ω6c), 11-methyl C18 : 1ω7c and C17 : 1ω6c .The polar lipid profile consisted of the major compounds sphingoglycolipid, phosphatidylethanolamine, phosphatidylglycerol, diphosphatidylglycerol, phosphatidylcholine and two unknown lipids. The DNA G+C content was 64.7 mol%. Based on its phenotypic properties, chemotaxonomic characteristics and phylogenetic distinctiveness, strain XY-R17T should be designated as a novel species of the genus Altererythrobacter. Therefore, the name Altererythrobacter salegens sp. nov. (type strain XY-R17T=KCTC 52267T=MCCC 1K01500T) is proposed.

Synthesis by free radical polymerization and properties of BN-polystyrene and BN-poly(vinylbiphenyl).

Free radical polymerization of B-vinyl- and B-styryl-functionalized azaborinine monomers gives well-defined hybrid polymers that were fully characterized by multinuclear NMR and GPC analysis; their solubility, thermal characteristics, and photophysical properties are dramatically different from those of the all-carbon polystyrene analogues.

"Third-Generation"-Type Functional Tris(2-pyridyl)borate Ligands and Their Transition-Metal Complexes.

Phenyltris(2-pyridyl)borates (Tpyb) are a promising class of tripodal "scorpionate"-type ligands with potential utility in the development of transition-metal complexes with interesting optical, electronic, or magnetic properties and as building blocks to metallosupramolecular polymers. We report here a new class of "third-generation"-type Tpyb ligands that contain different functional groups attached to the boron-bound aryl moiety. The synthesis, characterization, and metal-ion complexation behavior of ligands with iodo and trimethylsilyl groups are discussed. The electrochemical and absorption characteristics of the corresponding low-spin iron(II) and ruthenium(II) complexes are compared. We demonstrate the further elaboration of iodo derivatives with alkynes via Sonogashira-Hagihara coupling, a process that proceeds with high yield for the iron(II) and ruthenium(II) complexes but not for the free ligand. Borylation of the silyl-substituted ruthenium(II) complex with BBr3 was also investigated. In addition to the expected borylation product Ru(Tpyb-Bpin)2, the replacement of one (major product) or two phenyl groups is observed, suggesting that electrophilic borylation occurs at both the C(Ph)-Si and the C(Ph)-B aromatic carbon atoms. The successful attachment of a range of different functional groups at the periphery of the Tpyb metal complexes is expected to provide opportunities to access new polymeric materials via C-C coupling or click-type reactions.

Methylmercury and sulfate-reducing bacteria in mangrove sediments from Jiulong River Estuary, China.

Estuaries are important sites for mercury (Hg) methylation, with sulfate-reducing bacteria (SRB) thought to be the main Hg methylators. Distributions of total mercury (THg) and methylmercury (MeHg) in mangrove sediment and sediment core from Jiulong River Estuary Provincial Mangrove Reserve, China were determined and the possible mechanisms of Hg methylation and their controlling factors in mangrove sediments were investigated. Microbiological and geochemical parameters were also determined. Results showed that SRB constitute a small fraction of total bacteria (TB) in both surface sediments and the profile of sediments. The content of THg, MeHg, TB, and SRB were (350 +/- 150) ng/g, (0.47 +/- 0.11) ng/g, (1.4 x10(11) +/- 4.1 x 10(9)) cfu/g dry weight (dw), and (5.0 x 10(6) +/- 2.7 x 10(6)) cfu/g dw in surficial sediments, respectively, and (240 +/- 24) ng/g, (0.30 +/- 0.15) ng/g, (1.9 x 10(11) +/- 4.2 x 10(10)) cfu/g dw, and (1.3 x 10(6) +/- 2.0 x 10(6)) cfu/g dw in sediment core, respectively. Results showed that THg, MeHg, TB, MeHg/THg, salinity and total sulfur (TS) increased with depth, but total organic matter (TOM), SRB, and pH decreased with depth. Concentrations of MeHg in sediments showed significant positive correlation with THg, salinity, TS, and MeHg/THg, and significant negative correlation with SRB, TOM, and pH. It was concluded that other microbes, rather than SRB, may also act as main Hg methylators in mangrove sediments.

Glu659Leu substitution of recombinant HIV fusion inhibitor C52L induces soluble expression in Escherichia coli with equivalent anti-HIV potency.

The C-peptides used to prevent HIV infection, such as T20 and C34, are chemically synthesized, making them costly drugs. The sensitivity of peptides to protease also restricts their clinical application. We showed previously that C52L, a recombinant peptide produced in bacteria, is a potent anti-HIV C-peptide, although most of the peptide accumulates in inclusion bodies. Here we applied leucine and glutamine scanning mutagenesis to the heptad-repeat of C52L to produce an optimized variant of C52L that is potent and soluble when expressed in bacteria. We present that the substitution of Asn656 and Glu659 with leucine (peptide L14 and L15, respectively) can increase the helical content of this peptide. These substitutions also result in soluble expression. We measured the inhibitory activities of these mutant peptides against laboratory-adapted HIV-1 strains and found that L15 and its parental peptide C52L have equivalent anti-HIV activities. Moreover, L15 was found to be more stable to proteinase K digestion than C52L. Thus, we show that the L15 peptide can be expressed in a soluble state and exhibits potent anti-HIV activity. This peptide may be further developed as an anti-HIV therapeutic and/or microbicide for the prevention of HIV sexual transmission.

[Distribution of Hg in mangrove plants and correlation with Hg speciation in sediments].

Plant is an important role in biogeochemical cycle of Hg. The aim of this study is to ascertain Hg accumulation in several kinds of mangrove plants, and to discuss relationship among Hg concentrations in mangrove plants and different Hg speciation in sediments. Contents of total mercury (THg) in mangrove plants and sediments were determined. Hg speciation was determined with a modified Tessier's method. Contents of THg of the mangrove plants were in the range of 817.5-3 197.6 ng/g. In detail, Hg concentration was (1 579.4 +/- 1 326.8) ng/g in Kandelia candel, (2 115.1 +/- 1 892.3) ng/g in Aegiceras corniculatum, (2 159.3 +/- 1 678.7) ng/g in Avicennia marina, (2 566.5 +/- 821.6) ng/g in Bruguiera gymnorrhiza, (2 104.3 +/- 1 661.8) ng/g in Excoecaria agallocha, (3 197.6 +/- 2 782.8) ng/g in Sonneratia apetala, (817.5 +/- 632.3) ng/g in Acanthus ilicifolius, (1 801.8 +/- 1 255.4) ng/g in Rhizophora. stylosa, respectively. There are obvious interspecific variation, and organic variation in THg contents of mangrove plants, which is closely related to environment and physiological characteristics of mangrove plants. Enrichment of THg in mangrove plants was inhomogeneous, following the order of Sonneratia apetala > Bruguiera gymnorrhiza > Avicennia marina > Aegiceras corniculatum > Excoecaria agallocha > Rhizophora stylosa > Kandelia candel > Acanthus ilicifolius. Mercury exists mainly in volatile form in most mangrove wetlands, but mainly in the form of residue in sediments from Shenzhen mangrove wetlands. Significantly positive correlations were found among Hg concentrations in leaves and stems of Sonneratia apetala and volatile Hg, exchangeable Hg of sediments. Significantly positive correlations were also found among Hg concentrations in leaves of Excoecaria agallocha and volatile Hg, exchangeable Hg of sediments. But, there is no significant correlation between Hg concentrations of most mangrove plants and different Hg speciation in sediments. It showed that plants assimilate Hg from different sources, such as water, sediment and air, and that Hg assimilated by plants could transfer among different plant organics.

[Distribution of mercury in surficial sediments from main mangrove wetlands of China].

Surficial sediment samples were collected from main mangrove wetlands of China, mercury, pH, salinity, organic matters, grain size, Fe/Hg, Mn/Hg were analyzed. Mercury content ranges from 2.3 to 903.6 ng x g(-1), with a average of (197 +/- 137.6) ng x g(-1). Compared with local background level, serious Hg pollution with high Hg content was found in 7 areas, including Luoyangqiao [(467.5 +/- 68.8) ng x g(-1)], Fugong [(438.2 +/- 147.0) ng x g(-1)], Ewan [(264.3 +/- 89.2) ng x g(-1)], Yaojiayu [(125.4 +/- 27.1) ng x g(-1)], Fujian Province; Sanya [(164.8 +/- 143.9) ng x g(-1)], Dongzhaigang [(314.1 +/- 335.7) ng x g(-1)], Hainan Province, Shenzhen [(179.9 +/- 7.7) ng x g(-1)], Guangdong Province. Hg content was similar with background value in the other 6 areas, including Yunxiao [(63.3 +/- 43.9)ng x g(-1)], Fujian Province; Gaoqiao [(178.6 +/- 127.0) ng x g(-1)], Guangdong Province; Daguansha [(26.1 +/- 18.8) ng x g(-1)], Shankou [(73.8 +/- 21.1) ng x g(-1)], Beilun estuary [(117.8 +/- 51.4) ng x g(-1)], Qinzhou Bay [(147.5 +/- 107.6) ng x g(-1)], Guangxi Autonomous Region. Discrepancy of total Hg concentrations in mangrove wetlands is due to many environmental factors and human activities. Parameters such as grain size, pH, organic matter, Fe/Hg, Mn/Hg are significantly correlated with total Hg respectively. Clay and Fe/Hg are obvious factors influencing total Hg concentration. Impact of environmental factors on mercury can be showed by regression equation.