Global variability in seawater Mg:Ca and Sr:Ca ratios in the modern ocean.

Seawater Mg:Ca and Sr:Ca ratios are biogeochemical parameters reflecting the Earth-ocean-atmosphere dynamic exchange of elements. The ratios' dependence on the environment and organisms' biology facilitates their application in marine sciences. Here, we present a measured single-laboratory dataset, combined with previous data, to test the assumption of limited seawater Mg:Ca and Sr:Ca variability across marine environments globally. High variability was found in open-ocean upwelling and polar regions, shelves/neritic and river-influenced areas, where seawater Mg:Ca and Sr:Ca ratios range from ∼4.40 to 6.40 mmol:mol and ∼6.95 to 9.80 mmol:mol, respectively. Open-ocean seawater Mg:Ca is semiconservative (∼4.90 to 5.30 mol:mol), while Sr:Ca is more variable and nonconservative (∼7.70 to 8.80 mmol:mol); both ratios are nonconservative in coastal seas. Further, the Ca, Mg, and Sr elemental fluxes are connected to large total alkalinity deviations from International Association for the Physical Sciences of the Oceans (IAPSO) standard values. Because there is significant modern seawater Mg:Ca and Sr:Ca ratios variability across marine environments we cannot absolutely assume that fossil archives using taxa-specific proxies reflect true global seawater chemistry but rather taxa- and process-specific ecosystem variations, reflecting regional conditions. This variability could reconcile secular seawater Mg:Ca and Sr:Ca ratio reconstructions using different taxa and techniques by assuming an error of 1 to 1.50 mol:mol, and 1 to 1.90 mmol:mol, respectively. The modern ratios' variability is similar to the reconstructed rise over 20 Ma (Neogene Period), nurturing the question of seminonconservative behavior of Ca, Mg, and Sr over modern Earth geological history with an overlooked environmental effect.

An All-Solid-State Silicate Ion-Selective Electrode Using PbSiO3 as a Sensitive Membrane.

Ion-Selective Electrode (ISE) is an emerging technology for in situ monitoring of the chemical concentrations of an aqueous environment. In this work, we reported a novel all-solid-state silicate ISE, using an Ag/Pb/PbSiO3 electrode. This electrode responded to aqueous SiO32- with a reasonable slope of -31.34 mV/decade and a good reproductivity. The linear range covered from 10-5 M to 10-1 M, for the Na2SiO3 solutions and the response time was generally less than 5 s. Its potentiometric response to pH and silicate indicated that the prepared electrode was sensitive to silicate, rather than pH. Compared to the traditional liquid ISE, our all-solid-state silicate electrode was resistant to high pressure and could be used in situ, in deep water. In addition, the miniaturized electrodes (diameter of 0.4 mm and a length of 2⁻3 cm) could be easily integrated into a multi-modal sensor, which could simultaneously determine multiple parameters. Our prepared silicate ISE could potentially be used to determine the presence of silicate in a low-chloride aqueous environment, where the ISE exhibited better selectivity for silicate, over interfering ions such as, SO4²-, NO3-, CH3COO-, CO3²-, and PO4³-.

Synthetic multispecies microbial communities reveals shifts in secondary metabolism and facilitates cryptic natural product discovery.

Chemically mediated interactions have been hypothesized to be essential for ecosystem functioning as co-occurring organisms can influence the performance of each other by metabolic means. Here, we present a co-culture device that allows co-culturing of microorganisms that are physically separated but can exchange chemical signals and metabolites. This setup was adopted to perform investigations on the secondary metabolisms of both a fungal-bacterial community and an actinomycetic-actinomycetic community. This study employed a metabolomics approach integrating LC-MS profiling, multivariate data analysis and molecular networking techniques. LC-MS measurements revealed a pronounced influence of such chemical communication on the metabolic profiles of synthetic co-culture communities with a group of molecules being induced or upregulated in co-cultures. A novel antibiotic exhibiting antibiotic properties against Klebsiella pneumoniae was unveiled in the fungal-bacterial community. Besides, a further survey of the fungal-bacterial cross-talk indicated that the production of co-culture-induced diphenyl ethers by fungi might result from the fungal response against the secretion of surfactins by bacteria in the cross-talk. This study demonstrated that the presented co-culture device and the metabolomic routine would facilitate the investigation on chemically mediated interactions in nature as well as cryptic natural products discovery.

New compounds from a hydrothermal vent crab-associated fungus Aspergillus versicolor XZ-4.

Three new quinazoline derivatives (1-3), one new oxepin-containing natural product (4) and four new cyclopenin derivatives (5-7 and 9) have been isolated from an EtOAc extract of the Taiwan Kueishantao hydrothermal vent crab-associated fungus Aspergillus versicolor XZ-4. Their planar structures were established by HRMS, 1D and 2D NMR spectroscopic data analyses. The absolute configurations for compounds 1 and 4 were determined by chiral phase HPLC analysis of their hydrolysis products. The absolute configurations of 2, 3 and 7 were defined mainly by comparison of the quantum chemical TDDFT calculated and the experimental ECD spectra, and the absolute configuration of 5 was deduced from comparison of the optical rotation values reported in the literature. The presence of two atropisomers of 5 was established by NOE analyses. The Ile & Val units in compounds 1-3 allowed the assignment of a new quinazoline skeleton and it's the first time the configuration of isoleucine in the quinazoline skeleton was defined. A series of 7-methoxy cyclopenin derivatives were reported for the first time in this study. The bioevaluation of compounds 5, 7, 8 and 9 revealed inhibitory activities against E. coli at MIC values around 32 µg mL-1.

Stress-driven discovery of a cryptic antibiotic produced by Streptomyces sp. WU20 from Kueishantao hydrothermal vent with an integrated metabolomics strategy.

Marine hydrothermal microorganisms respond rapidly to the changes in the concentrations and availability of metals within hydrothermal vent microbial habitats which are strongly influenced by elevated levels of heavy metals. Most hydrothermal vent actinomycetes possess a remarkable capability for the synthesis of a broad variety of biologically active secondary metabolites. Major challenges in the screening of these microorganisms are to activate the expression of cryptic biosynthetic gene clusters and the development of technologies for efficient dereplication of known compounds. Here, we report the identification of a novel antibiotic produced by Streptomyces sp. WU20 isolated from the metal-rich hydrothermal vents in Taiwan Kueishantao, following a strategy based on metal induction of silent genes combined with metabolomics analytical methods. HPLC-guided isolation by tracking the target peak resulted in the characterization of the novel compound 1 with antimicrobial activity against Bacillus subtilis. The stress metabolite 1 induced by nickel is structurally totally different compared with the normally produced compounds. This study underlines the applicability of metal induction combined with metabolic analytical techniques in accelerating the exploration of novel antibiotics and other medically relevant natural products.

An Unusual Conformational Isomer of Verrucosidin Backbone from a Hydrothermal Vent Fungus, Penicillium sp. Y-50-10.

A new verrucosidin derivative, methyl isoverrucosidinol (1), was isolated from the marine fungus Penicillium sp. Y-50-10, dwelling in sulfur rich sediment in the Kueishantao hydrothermal vents off Taiwan. The structure was established by spectroscopic means including HRMS and 2D-NMR spectroscopic analysis. The absolute configuration was defined mainly by comparison of quantum chemical TDDFT calculated and experimental ECD spectra. Among hitherto known compounds with a verrucosidine backbone isolated from natural resource, compound 1 represents the first example of a new conformational isomer of its skeleton, exhibiting antibiotic activity against Bacillus subtilis with MIC value 32 µg/mL.

Tourism image classification based on convolutional neural network SqueezeNet--Taking Slender West Lake as an example.

Tourism image classification plays an important role in the study of clarifying the real perception of tourism resources by tourists, which cannot be studied in depth by human vision alone. The development of convolutional neural networks in computer vision brings new opportunities for tourism image classification research. In this study, SqueezeNet, a lightweight convolutional neural network, was selected and improved on the basis of the original model for 3740 Slender West Lake tourism image datasets. It is found that the validation accuracy of the model is up to 85.75%, and the size is only 2.64 MB, which is a good classification effect. This reduces the parameters while ensuring high accuracy classification of tourism images, providing a more scientific reference for the study of tourism images and pointing out a new direction for the development and planning of tourism resources.

Synthesis and Characterization of Multiple Stimuli-Responsive Fluorescent Polymer Hydrogels Based on Terpyridine and N-Isopropylacrylamide.

A series of stimuli-responsive fluorescent hydrogels were successfully synthesized via micelle radical copolymerization of hydrophilic acrylamide (AM), hydrophobic chromophore terpyridine-based monomer (TPY), and N-isopropylacrylamide (NIPAM). These hydrogels presented blue emissions (423-440 nm) under room temperature, which is caused by the π-π* transition of the conjugated structures. Once the ambient temperature was increased to 55 °C, the fluorescence color changed from blue (430 nm) to pink (575 nm) within 10 min, subsequently to yellow (535 nm), and eventually back to pink. The thermal-responsive properties are attributed to the transition of the TPY units from unimer to dimer aggregation via the intermolecular charge transfer complex at high temperatures. The hydrogels showed pH-responsive properties. The emission peak of the hydrogel exhibited a blue shift of ~54 nm from neuter conditions to acidic conditions, while a 6 nm red shift to an alkaline environment was observed. The hydrogels demonstrated an obvious change in fluorescence intensity and wavelength upon adding different metal ions, which is caused by the coordination between the terpyridine units incorporated on the backbones and the metal ions. As a consequence, the hydrogels presented a sharp quenching fluorescence interaction with Fe2+, Fe3+, Cu2+, Hg2+, Ni2+, and Co2+, while it exhibited an enhanced fluorescence intensity interaction with Sn2+, Cd2+, and Zn2+. The microstructural, mechanical, and rheological properties of these luminescent hydrogels have been systematically investigated.

Robust room temperature perpendicular magnetic anisotropy and anomalous Hall effect of sputtered NiCo2O4film.

Inverse spinel ferrimagnetic NiCo2O4(NCO) exhibits volatile physical properties due to the complex ion/valence occupation, which complicates the study its intrinsic properties. In this work, robust room temperature perpendicular magnetic anisotropy (PMA) is distinctly observed in high-quality RF-sputtered NCO film down to 3 uc (2.4 nm), confirmed by the room temperature anomalous Hall effect. The NCO films show a good metallic conductivity with a dimensional driven metal-insulator transition. The scaling relation between anomalous Hall conductivity (σxy) and the longitudinal conductivity (σxx) reveals the dirty metal behavior in conjunction with the contribution of intrinsic Berry phase or disorder-enhanced electron correlation contribute to the anomalous Hall effect for thick films while the dirty scaling law dominates for the thin films. This work introduces an oxide candidate with robust room temperature PMA as well as massive production ability for the functional spintronic applications.

Record high room temperature resistance switching in ferroelectric-gated Mott transistors unlocked by interfacial charge engineering.

The superior size and power scaling potential of ferroelectric-gated Mott transistors makes them promising building blocks for developing energy-efficient memory and logic applications in the post-Moore's Law era. The close to metallic carrier density in the Mott channel, however, imposes the bottleneck for achieving substantial field effect modulation via a solid-state gate. Previous studies have focused on optimizing the thickness, charge mobility, and carrier density of single-layer correlated channels, which have only led to moderate resistance switching at room temperature. Here, we report a record high nonvolatile resistance switching ratio of 38,440% at 300 K in a prototype Mott transistor consisting of a ferroelectric PbZr0.2Ti0.8O3 gate and an RNiO3 (R: rare earth)/La0.67Sr0.33MnO3 composite channel. The ultrathin La0.67Sr0.33MnO3 buffer layer not only tailors the carrier density profile in RNiO3 through interfacial charge transfer, as corroborated by first-principles calculations, but also provides an extended screening layer that reduces the depolarization effect in the ferroelectric gate. Our study points to an effective material strategy for the functional design of complex oxide heterointerfaces that harnesses the competing roles of charge in field effect screening and ferroelectric depolarization effects.

A Supramolecular Hydrogel Based on Copolymers of Acrylic Acid and Maleic Anhydride Derivatives with Terpyridine Motifs.

A kind of terpyridine derivative (NH2-Tpy) in which the amino was incorporated by a short alkyl chain was synthesized. Through grafting of terpyridine units into the hydrophilic copolymers of maleic anhydride and acrylic acid PAAMa via the reaction of the amino groups in NH2-Tpy and the maleic anhydride units, a series of gelator polymers-P1, P2, and P3-containing different contents of terpyridine units was synthesized. Under coordination of Ni2+ and terpyridine ligands in linear polymers, the supramolecular hydrogels H1, H2, and H3 with different cross-linking degrees were prepared. The linear polymers P1-P3 had a strong absorption peak at about 290 nm in the UV-vis spectra which was attributed to π-π* transition, and there was a new peak at about 335 nm led by the metal-to-ligands charge transfer (MLCT) when coordinated with Ni2+ ions. According to the rheological behaviors, the storage modulus (G') was larger than the loss modulus (G''). These hydrogels showed typical gel-like characteristics when the terpyridine content of the hydrogels exceeded 10%, and the hydrogels showed liquid-like characteristics when the terpyridine content of the hydrogels was less than 7%. The results of the micromorphological investigation of the xerogels from SEM illustrated the metal-terpyridine coordination cross-linking could have an important influence on the microstructures of the resulting hydrogels. Furthermore, these hydrogels based on supramolecular cross-links exhibited reversible solution-gel transition at different environmental temperatures. At the same time, the equilibrium swelling of the supramolecular hydrogels was 8.0-12.3 g/g, which increased with the decrease in the content of the terpyridine units in the resulting hydrogels.

The Positive Temperature Coefficient of Resistivity in BiFeO3 Films.

The use of lead-free ceramic film materials with positive temperature coefficient of resistivity (PTCR) is widespread in temperature heaters and sensors in micro-electromechanical systems. In this research, the out of plane transport properties of the BiFeO3 (BFO) films have been studied. Surprisingly, PTCR was found in the BFO ceramic films due to the strongly correlated interaction between the multiferroic material BFO and the superconductor YBCO perovskite oxides. To our knowledge, this is the first report on the PTCR effect of BFO films. The BFO/YBCO interface and the bulk conductivity of BFO are important for the PTCR effect, as they make it possible to compare the transport properties of Au/BFO/YBCO- and YBCO/BFO/YBCO-type structures. PTCR was observed in Au/BFO/YBCO at a bias voltage of more than 2 V, but not in the YBCO/BFO/YBCO, even with a 40 V bias voltage. PTCR was found after BFO breakdown of a YBCO/BFO/YBCO capacitor. This indicated that the conductivity of BFO is critical for PTCR. The dependence of PTCR on the superconducting transition temperature illustrates that a cooper-pair can be injected into BFO. Our work presents a method by which to produce a lead-free ceramic film material with PTCR.

Synthesis and Characterization of Metallo-Supramolecular Polymers Based on Benzodipyrrolidone.

A simple route to the preparation of benzodipyrrolidone (BDP) based monomeric building blocks containing 2,2':6',2″-terpyridines is reported from a common precursor 4'-(4-pinacolatoboronphenyl)-2,2':6',2″-terpyridine via Suzuki coupling reaction. Self-assembly polymerization with ruthenium (II) ions under mild conditions yielded a series of novel metallo-supramolecular polymers with weak donor-acceptor (D-A) structures based on benzodipyrrolidone. The structure of the bridge connected BDP with terpyridine have a significant impact on the wavelength and intensity of the intramolecular charge transfer (ICT) absorption peak. The resulting metallo-polymers exhibited strong double absorption bands around 315 nm and 510 nm involved in π-π* transitions and ICT or metal to ligand charge transfer (MLCT) absorption bands. The forming of D-A structure and coordination with ruthenium (II) ions is favorable to narrow the energy gap and the energy gaps of the resulting metallo-supramolecular polymers are 2.01 and 1.62 eV, respectively.

Tunable 2D Group-III Metal Alloys.

Chemically stable quantum-confined 2D metals are of interest in next-generation nanoscale quantum devices. Bottom-up design and synthesis of such metals could enable the creation of materials with tailored, on-demand, electronic and optical properties for applications that utilize tunable plasmonic coupling, optical nonlinearity, epsilon-near-zero behavior, or wavelength-specific light trapping. In this work, it is demonstrated that the electronic, superconducting, and optical properties of air-stable 2D metals can be controllably tuned by the formation of alloys. Environmentally robust large-area 2D-Inx Ga1- x alloys are synthesized byConfinement Heteroepitaxy (CHet). Near-complete solid solubility is achieved with no evidence of phase segregation, and the composition is tunable over the full range of x by changing the relative elemental composition of the precursor. The optical and electronic properties directly correlate with alloy composition, wherein the dielectric function, band structure, superconductivity, and charge transfer from the metal to graphene are all controlled by the indium/gallium ratio in the 2D metal layer.

Terpyridine-Containing π-Conjugated Polymers for Light-Emitting and Photovoltaic Materials.

2,2':6',2″-Terpyridine (tpy) is a versatile moiety used in the construction of small novel molecules or polymers. Extending or coupling tpy with π-conjugation structures can result in interesting optoelectronic properties. This mini-review summarizes the significant progress made over the past decades in the study of tpy-containing π-conjugated polymers and their application in light-emitting and photovoltaic materials. When coordinated with metal ions, tpy exhibits immense potential for the synthesis of metallo-supramolecular or metallo-polymer materials. Therefore, tpy-based metallo-polymers are the primary focus of this study. Selected examples will be reviewed with a special emphasis on the properties of these functional systems, which can consequently help further their application in light-to-electricity or electricity-to-light conversion fields.

Comparative Study on the Elucidation of Sedimentary Phosphorus Species Using Two Methods, the SMT and SEDEX Methods.

Sedimentary phosphorus (P) forms are important representatives of P sources and their bioavailability as well as the potential of sediments to release P in water. In this study, surface sediments along a transect of the Changjiang Estuary and two transects along the Andong salt marsh in the southwest of Hangzhou Bay were subjected to the elucidation of sedimentary P species using the standards, measurements, and testing (SMT) and sequential extraction (SEDEX) methods. The results showed that the mean sedimentary P forms elucidated by the SMT method were as follows: organic P (OP; ∼11-14 mg/kg; ∼30-45% of total P; TP) > apatite P (∼5-15 mg/kg; ∼21-36% TP) > Fe/Al-P (∼8-14 mg/kg; ∼31-34% TP), with inorganic P (IP) composing 54-70% of TP. The mean sedimentary P forms elucidated by the SEDEX method were as follows: authigenic P (∼54-68 mg/kg; ∼41-46% TP) > extractable P (Ex-P; ∼36-53 mg/kg; ∼28-34%) > Fe-P (∼21-27 mg/kg; ∼13-19%) > OP (∼8.7-13 mg/kg; ∼5-8%) > detrital P (De-P; ∼2 mg/kg; ∼1-2% TP), with IP composed of ∼91-94% TP. These results showed that the SEDEX method elucidated higher concentrations of sedimentary P forms as well as the TP from these coastal sediments although the SMT method had the advantage of being more economic and faster. The results of both the SMT and SEDEX methods showed that the Andong salt marsh and Changjiang Estuary sediments had much bioavailable P. The mean percentages of bioavailable P from the SMT and SEDEX methods were ∼64-74% and 52-56% of TP, respectively, indicating that these sediments were prone to release P to the coastal areas.

Metallo-Supramolecular Hydrogels from the Copolymers of Acrylic Acid and 4-(2,2':6',2″-terpyridin-4'-yl)styrene.

Hydrophilic copolymers containing 2,2':6',2″-terpyridine moieties and acrylic acid (AA) units poly (acrylic acid-co-4-(2,2':6',2″-terpyridin-4'-yl)styrene) (P(AA-co-TPY)) were synthesized and characterized. Coordinated with different transition metal ions, the dilute aqueous solution of the copolymers exhibited red-shifted UV-vis absorption peaks of π-π* transition from 317 to 340 nm. Further, interacting with iron ions, the copolymer showed new absorption peaks at a longer wavelength region (570 nm) and the absorption intensity enhanced with increase of the ion concentration. When enough ions were added to coordinate with the 2,2':6',2″-terpyridine moieties, novel metallo-supramolecular hydrogels were obtained due to the formation of metal coordination bonds between polymer back bones and transition metal ions (Ni2+, Zn2+, Cd2+, Fe2+ and Cu2+), which acted as self-assembly crosslinking structures. The mechanical strength and morphology of the resulting metallo-supramolecular hydrogels have been investigated.

A polymeric ionic liquid as a cathode interlayer of organic photovoltaics with improved reproducibility.

A polymeric ionic liquid (PIL) was synthesized from a small-molecule one (MIL, the monomer), and they were used as cathode interlayers in organic solar cells. Compared with the MIL, the PIL can form a more uniform film for full coverage of an active layer and efficient cathode modification, resulting in higher device efficiency and reproducibility.

Magnetotransport Anomaly in Room-Temperature Ferrimagnetic NiCo2 O4 Thin Films.

The inverse spinel ferrimagnetic NiCo2 O4 presents a unique model system for studying the competing effects of crystalline fields, magnetic exchange, and various types of chemical and lattice disorder on the electronic and magnetic states. Here, magnetotransport anomalies in high-quality epitaxial NiCo2 O4 thin films resulting from the complex energy landscape are reported. A strong out-of-plane magnetic anisotropy, linear magnetoresistance, and robust anomalous Hall effect above 300 K are observed in 5-30 unit cell NiCo2 O4 films. The anomalous Hall resistance exhibits a nonmonotonic temperature dependence that peaks around room temperature, and reverses its sign at low temperature in films thinner than 20 unit cells. The scaling relation between the anomalous Hall conductivity and longitudinal conductivity reveals the intricate interplay between the spin-dependent impurity scattering, band intrinsic Berry phase effect, and electron correlation. This study provides important insights into the functional design of NiCo2 O4 for developing spinel-based spintronic applications.

Characteristics of Authigenic Minerals around the Sulfate-Methane Transition Zone in the Methane-Rich Sediments of the Northern South China Sea: Inorganic Geochemical Evidence.

Sediments at marine cold seep areas provide potential archives of past fluid flow, which allow insights into the evolution of past methane seepage activities. However, signals for anaerobic oxidation of methane (AOM) might be obscured in bulk sediments in cold-seep settings due to several factors, especially flood and turbidite deposition. Comprehensive inorganic data were gathered in this study to explore the availability of related records at cold seeps and to provide insights into the evolution of past methane seepage activities. Sediments collected from the site 973-4 in the Taixinan Basin on the northern slope of the South China Sea were characterized in terms of total carbon and sulfur, δ13C values of total organic carbon (δ13CTIC), δ34S values of chromium reducible sulfur (δ34SCRS), and foraminiferal oxygen and carbon isotopes. The results confirmed a strong correlation between formation of authigenic minerals and AOM. Moreover, the 34S enrichments and abundant chromium reducible sulfur (CRS) contents in the authigenic sulfides in the sulfate-methane transition zone (SMTZ) within 619-900 cm below seafloor (cmbsf) reflected past high methane fluxes supported by constant methane seepages. Lithological distribution and AMS (Accelerator Mass Spectra) 14C dating of planktonic foraminifera show that the turbidite (~35.14 ka) was related to a foraminifera-rich interval (Unit II: 440-619 cmbsf) and increased carbonate productivity during the last glacial maximum (LGM). Enrichment of Mo and U was observed accompanied by low contents of nutrient metals (Al, Ti, V, Ni, Fe, Mn, and Cu) in Unit II. The foraminifera-rich interval (Unit II) of cold seep sediments was probably linked to the phenomenon of inconsecutive sedimentary sequence due to the turbidites, which resulted in the lack of Fe, Mn, and Ba enrichment. There is no U enrichment but only Mo enrichment within Unit III, which might be related to H2S produced by AOM during the methane seepages. Based on the above results, it can be speculated that this area has experienced multiple-episodes of methane seep events. Further exploration of AOM should focus on the risks of rapid deposition, especially the impact of turbidity current on sediments.