Molecular characteristics of dissolved organic phosphorus in watershed runoff: Coupled influences of land use and precipitation.

Land use and precipitation are two major factors affecting phosphorus (P) pollution of watershed runoff. However, molecular characterization of dissolved organic phosphorus (DOP) in runoff under the joint influences of land use and precipitation remains limited. This study used Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) to study the molecular characteristics of DOP in a typical P-polluted watershed with spatially variable land use and precipitation. The results showed that low precipitation and intense human activity, including phosphate mining and associated industries, resulted in the accumulation of aliphatic DOP compounds in the upper reaches, characterized by low aromaticity and low biological stability. Higher precipitation and widespread agriculture in the middle and lower reaches resulted in highly unsaturated DOP compounds with high biological stability constituting a higher proportion, compared to in the upper reaches. While, under similar precipitation, more aliphatic DOP compounds characterized by lower aromaticity and higher saturation were enriched in the lower reaches due to more influence from urban runoff relative to the middle reaches. Photochemical and/or microbial processes did result in changes in the characteristics of DOP compounds during runoff processes due to the prevalence of low molecular weight and low O/C bioavailable aliphatic DOP molecules in the upper reaches, which were increasingly transformed into refractory compounds from the upper to middle reaches. The results of this study can increase the understanding of the joint impacts of land use and precipitation on DOP compounds in watershed runoff.

Unraveling the role of anthropogenic and hydrologic drivers with respect to the optical and molecular properties of dissolved organic matter and organic phosphorus in a P-contaminated river.

Anthropogenic and hydrological drivers are key factors influencing the fate of dissolved organic matter (DOM) and dissolved organic phosphorus (DOP) in river runoff. However, how anthropogenic disturbances and hydrological conditions jointly affect the composition and characteristics of DOM and DOP in river runoff remains unclear. This study used fluorescence spectroscopy, Fourier transform ion cyclotron resonance mass spectrometry, and the stable water isotopes to interpret the chemical composition and properties of DOM and DOP as well as their linkages to anthropogenic disturbances and hydrological conditions in a typical P-contaminated tributary to the central Yangtze River. The results show in the wet season, the average abundance of humic-like components in DOM exceeded 60 %, while the average abundance of tryptophan-like components in DOM exceeded 50 % in the dry season. During the dry season, hydrological conditions had a greater impact on highly unsaturated DOM compounds compared to anthropogenic disturbances because a decrease in precipitation reduced the transport of terrestrial DOM into aquatic systems and increased water retention time in the river, promoting the production of unsaturated compounds from photochemistry. The effects of the two factors were similar in the wet season because active agricultural activities and intense precipitation jointly facilitated the entry of exogenous humics into the runoff, leading to the similar relative abundance of highly unsaturated DOM compounds associated with both factors. Anthropogenic disturbances had a greater impact on aliphatic DOM and DOP than hydrological conditions, which was associated with intense human activities in the watershed, such as phosphate mining, agricultural cultivation, and domestic sewage discharge. This study provides new knowledge about the composition, properties and underlying mechanisms of DOM and DOP in the P-contaminated watershed runoff.

Impdh2 deficiency suppresses osteoclastogenesis through mitochondrial oxidative phosphorylation and alleviates ovariectomy-induced osteoporosis.

Abnormalities in osteoclastic generation or activity disrupt bone homeostasis and are highly involved in many pathologic bone-related diseases, including rheumatoid arthritis, osteopetrosis, and osteoporosis. Control of osteoclast-mediated bone resorption is crucial for treating these bone diseases. However, the mechanisms of control of osteoclastogenesis are incompletely understood. In this study, we identified that inosine 5'-monophosphate dehydrogenase type II (Impdh2) positively regulates bone resorption. By histomorphometric analysis, Impdh2 deletion in mouse myeloid lineage cells (Impdh2LysM-/- mice) showed a high bone mass due to the reduced osteoclast number. qPCR and western blotting results demonstrated that the expression of osteoclast marker genes, including Nfatc1, Ctsk, Calcr, Acp5, Dcstamp, and Atp6v0d2, was significantly decreased in the Impdh2LysM-/- mice. Furthermore, the Impdh inhibitor MPA treatment inhibited osteoclast differentiation and induced Impdh2-cytoophidia formation. The ability of osteoclast differentiation was recovered after MPA deprivation. Interestingly, genome-wide analysis revealed that the osteoclastic mitochondrial biogenesis and functions, such as oxidative phosphorylation, were impaired in the Impdh2LysM-/- mice. Moreover, the deletion of Impdh2 alleviated ovariectomy-induced bone loss. In conclusion, our findings revealed a previously unrecognized function of Impdh2, suggesting that Impdh2-mediated mechanisms represent therapeutic targets for osteolytic diseases.

Carboxyl graphene modified PEDOT:PSS organic electrochemical transistor for in situ detection of cancer cell morphology.

Circulating tumor cells in human peripheral blood play an important role in cancer metastasis. In addition to the size-based and antibody-based capture and separation of cancer cells, their electrical characterization is important for rare cell detection, which can prove fatal in point-of-care testing. Herein, an organic electrochemical transistor (OECT) biosensor made of solution-gated carboxyl graphene mixed with PEDOT:PSS for the detection of cancer cells in situ is reported. Carboxyl graphene was used in this work to modulate cancer cell morphology, which differs significantly from normal blood cells, to achieve rare cancer cell detection. When the concentration of carboxyl graphene mixed in PEDOT:PSS was increased from 0 to 5 mg mL-1, the cancer cell surface area increased from 218 µm2 to 530 µm2, respectively. A change in cell morphology was also detected by the OECT. Negative charges in the cancer cells induced a positive shift in gate voltage, which was approximately 40 mV for spherical-shaped cells. When the cell surface area increased, transfer curves of transistor revealed a negative shift in gate voltage. Therefore, the sensor can be used for in situ detection of cancer cell morphology during the cell capture process, which can be used to identify whether the captured cells are deformable.

Effects of reservoir construction on optical and molecular characteristics of dissolved organic matter in a typical P-contaminated river.

The source and composition characteristics of dissolved organic matter (DOM) are crucial to identify and evaluate the sources of pollution in the watershed. The construction of reservoirs changes the hydrological condition and pollutant fate of the river. However, the effects of reservoirs' construction on DOM in the watershed and the underlying mechanisms are still unclear. This study aims to examine and compare the characteristics of DOM in reservoirs and streams in the Huangbai River, a typical reservoir-affected and P-contaminated river within the Yangtze River catchment. The results showed that DOM in reservoirs was characterized by more contribution from autochthonous source, under the influence of reservoirs' construction; while, DOM in rivers was mainly originated from terrestrial input. Reservoirs had more lipid-like and protein-like compounds, while rivers contained more oxy-aromatic-like compounds. The percentage of CHOP molecules in reservoirs was significantly higher than that in rivers. The underlying mechanism is that more suitable conditions were created for plankton to grow after constructing reservoirs, which converted inorganic orthophosphate into organic phosphorus, and over time, organic phosphorus was gradually enriched in reservoirs, which exacerbated the risk of eutrophication in the reservoir water body. This study can provide theoretical support for monitoring and evaluation of water quality in reservoir-affected rivers.

Correction: Metal salt assisted electrospray ionization mass spectrometry for the soft ionization of GAP polymers in negative ion mode.

Correction for 'Metal salt assisted electrospray ionization mass spectrometry for the soft ionization of GAP polymers in negative ion mode' by Theoneste Muyizere et al., Analyst, 2020, 145, 34-45.

Metal salt assisted electrospray ionization mass spectrometry for the soft ionization of GAP polymers in negative ion mode.

Glycidyl azide polymers (GAP) are one of the most important energetic polymers, but it is still a challenge to elucidate their structures using mass spectrometry due to their fragility upon ionization. Herein we developed a soft metal salt assisted electrospray ionization (MSAESI) to characterize directly GAP polymers using mass spectrometry. This technique combines paper spray ionization and the complexing effect of anions from metal salts with GAP in the negative ion mode to softly ionize GAP polymers prior to mass spectrometry analysis. The effects of experimental parameters (e.g., ion mode, applied voltage, and type and concentration of metal salts) have been investigated in detail. In contrast to the positive ion mode, a softer ionization was observed for GAP polymers when the negative ion mode was applied. The radius and average charge of cations and anions in metal salts were found to play crucial roles in determining the performance of the MSAESI analysis of GAP. For a given charge number, a smaller radius of cations favored the soft ionization of GAP polymers (e.g., Na+ > K+ > Rb+), whereas a larger radius of anions led to a preferred performance (e.g., F- < Cl- < Br- < I-) due to variation in dissolution ability. For anions with multiple charges, the ones with fewer charges gave a more favorable ionization to the GAP sample because of their better complexing to GAP molecules than those with more charges in the structure of anions (e.g., NO3- > SO42- > PO43-). According to the experimental observation and evidence from mass spectrometry, we proposed the plausible electrospray mechanisms of MSAESI for GAP analysis with the involvement of metal salts. Moreover, the developed protocol has been applied successfully to the analysis of various GAP samples, and works for other types of sources such as nanoelectrospray ionization.

TiO2 Nanorod Arrays with Mesoscopic Micro-Nano Interfaces for in Situ Regulation of Cell Morphology and Nucleus Deformation.

Cell morphology and nucleus deformation are important when circulating tumor cells break away from the primary tumor and migrate to a distant organ. Cells are sensitive to the microenvironment and respond to the cell-material interfaces. We fabricated TiO2 nanorod arrays with mesoscopic micro-nano interfaces through a two-step hydrothermal reaction method to induce severe changes in cell morphology and nucleus deformation. The average size of the microscale voids was increased from 5.1 to 10.5 µm when the hydrothermal etching time was increased from 3 to 10 h, whereas the average distances between voids were decreased from 0.88 to 0.40 µm. The nucleus of the MCF-7 cells on the TiO2 nanorod substrate that was etched for 10 h exhibited a significant deformation, because of the large size of the voids and the small distance between voids. Nucleus defromation was reversible during the cells proliferate process when the cells were cultured on the mesoscopic micro-nano interface.This reversible process was regulated by combining of the uniform pressure applied by the actin cap and the localized pressure applied by the actin underneath the nucleus. Cell morphology and nucleus shape interacted with each other to adapt to the microenvironment. This mesoscopic micro-nano interface provided a new insight into the cell-biomaterial interface to investigate cell behaviors.

4,4'-Bis(2,2-diphenyl-vin-yl)-1,1'-biphen-yl.

The title mol-ecule, C(40)H(30), lies on an inversion center. The two unique phenyl rings form dihedral angles of 51.98 (8) and 67.58 (8)° with the essentially planar biphenyl unit [maximum deviation = 0.0360 (14) Å].