The interaction of size-selected Ru3 clusters with TiO2: depth-profiling of encapsulated clusters.

Ru is a metal of interest in catalysis. Monodisperse Ru3 clusters as catalytic sites are relevant for the development of catalysts because clusters use significantly lower amounts of precious materials for forming active sites due to the small size of the cluster. However, retaining the mono-dispersity of the cluster size after deposition is a challenge because surface energy could drive both agglomeration and encapsulation of the clusters. In the present work Ru3 clusters are deposited by chemical vapor deposition (CVD) of Ru3(CO)12 and cluster source depositions of bare Ru3 onto radio frequency sputter-deposited TiO2 (RF-TiO2) substrates, TiO2(100), and SiO2. When supported on RF-TiO2, bare Ru3 is encapsulated by a layer of titania substrate material during deposition with a cluster source. Ligated Ru3(CO)12 is also encapsulated by a layer of titania when deposited onto sputter-treated RF-TiO2, but only through heat treatment which is required to remove most of the ligands. The titania overlayer thickness was determined to be 1-2 monolayers for Ru3(CO)12 clusters on RF-TiO2, which is thin enough for catalytic or photocatalytic reactions to potentially occur even without clusters being part of the very outermost layer. The implication for catalysis of the encapsulation of Ru3 into the RF-TiO2 is discussed. Temperature-dependent X-ray photoelectron spectroscopy (XPS), angle-resolved XPS, and temperature-dependent low energy ion scattering (TD-LEIS) are used to probe how the cluster-surface interaction changes due to heat treatment and scanning transmission electron microscopy (STEM) was used to image the depth of the surface from side-on.

Genetic association study of intron variants in the forkhead box protein P3 gene in Chinese patients diagnosed with cervical cancer.

The aim of this study was to investigate the effects of forkhead box protein P3 (FOXP3) intron single nucleotide variants (SNVs) in high-risk human papilloma virus (HR-HPV) infection and cervical cancer (CC) malignant lesions. We performed FOXP3 genotyping in 350 patients with CC and 350 healthy controls using the ImLDR multiple single nucleotide polymorphism genotyping technology. The heterozygous mutation TC in rs2294021 decreased the risk of HR-HPV infection and CC malignant lesions (TC vs. TT: OR = 0.71, 95% CI = 0.51-0.99); the dominant model TC+CC and allele C in rs2294021 decreased the risk of CC malignant lesions (TC+CC vs. TT: OR = 0.69, 95% CI = 0.50-0.95; C vs. T: OR = 0.78, 95% CI = 0.63-0.97). The heterozygous mutation GA, dominant model GA+AA and allele A in rs3761549 also decreased the risk of HR-HPV infection and CC malignant lesions (GA vs. GG: OR = 0.70, 95% CI = 0.51-0.96; GA+AA vs. GG: OR = 0.69, 95% CI = 0.51-0.94; A vs. G: OR = 0.75, 95% CI = 0.58-0.96). Patients with CC and HR-HPV infection carrying rs2294021 TC and rs3761549 GA had lower expression of FOXP3 protein. Haplotype analysis revealed that T-C-A decreased the risk of HR-HPV infection. Furthermore, we found a significant association between immune cells infiltration and prognosis in patients with CC. Our findings demonstrated that rs2294021 and rs3761549 variants may protect against HR-HPV and CC malignant lesions by downregulating FOXP3 and that FOXP3 was associated with immune cells infiltration, which affected the prognosis of CC.

Cerium oxide nanoparticles improve cotton salt tolerance by enabling better ability to maintain cytosolic K+/Na+ ratio.

BACKGROUND: Salinity is a worldwide factor limiting the agricultural production. Cotton is an important cash crop; however, its yield and product quality are negatively affected by soil salinity. Use of nanomaterials such as cerium oxide nanoparticles (nanoceria) to improve plant tolerance to stress conditions, e.g. salinity, is an emerged approach in agricultural production. Nevertheless, to date, our knowledge about the role of nanoceria in cotton salt response and the behind mechanisms is still rare. RESULTS: We found that PNC (poly acrylic acid coated nanoceria) helped to improve cotton tolerance to salinity, showing better phenotypic performance, higher chlorophyll content (up to 68% increase) and biomass (up to 38% increase), and better photosynthetic performance such as carbon assimilation rate (up to 144% increase) in PNC treated cotton plants than the NNP (non-nanoparticle control) group. Under salinity stress, in consistent to the results of the enhanced activities of antioxidant enzymes, PNC treated cotton plants showed significant lower MDA (malondialdehyde, up to 44% decrease) content and reactive oxygen species (ROS) level such as hydrogen peroxide (H2O2, up to 79% decrease) than the NNP control group, both in the first and second true leaves. Further experiments showed that under salinity stress, PNC treated cotton plants had significant higher cytosolic K+ (up to 84% increase) and lower cytosolic Na+ (up to 77% decrease) fluorescent intensity in both the first and second true leaves than the NNP control group. This is further confirmed by the leaf ion content analysis, showed that PNC treated cotton plants maintained significant higher leaf K+ (up to 84% increase) and lower leaf Na+ content (up to 63% decrease), and thus the higher K+/Na+ ratio than the NNP control plants under salinity stress. Whereas no significant increase of mesophyll cell vacuolar Na+ intensity was observed in PNC treated plants than the NNP control under salinity stress, suggesting that the enhanced leaf K+ retention and leaf Na+ exclusion, but not leaf vacuolar Na+ sequestration are the main mechanisms behind PNC improved cotton salt tolerance. qPCR results showed that under salinity stress, the modulation of HKT1 but not SOS1 refers more to the PNC improved cotton leaf Na+ exclusion than the NNP control. CONCLUSIONS: PNC enhanced leaf K+ retention and Na+ exclusion, but not vacuolar Na+ sequestration to enable better maintained cytosolic K+/Na+ homeostasis and thus to improve cotton salt tolerance. Our results add more knowledge for better understanding the complexity of plant-nanoceria interaction in terms of nano-enabled plant stress tolerance.

Sn-modification of Pt7/alumina model catalysts: Suppression of carbon deposition and enhanced thermal stability.

An atomic layer deposition process is used to modify size-selected Pt7/alumina model catalysts by Sn addition, both before and after Pt7 cluster deposition. Surface science methods are used to probe the effects of Sn-modification on the electronic properties, reactivity, and morphology of the clusters. Sn addition, either before or after cluster deposition, is found to strongly affect the binding properties of a model alkene, ethylene, changing the number and type of binding sites, and suppressing decomposition leading to carbon deposition and poisoning of the catalyst. Density functional theory on a model system, Pt4Sn3/alumina, shows that the Sn and Pt atoms are mixed, forming alloy clusters with substantial electron transfer from Sn to Pt. The presence of Sn also makes all the thermally accessible structures closed shell, such that ethylene binds only by π-bonding to a single Pt atom. The Sn-modified catalysts are quite stable in repeated ethylene temperature programmed reaction experiments, suggesting that the presence of Sn also reduces the tendency of the sub-nano-clusters to undergo thermal sintering.

Mn3 O4 Nanoparticles Alleviate ROS-Inhibited Root Apex Mitosis Activities to Improve Maize Drought Tolerance.

Poly (acrylic) acid coated Mn3O4 nanoparticles (PAA@Mn3 O4 nanoparticles (PMO, 11.02 nm, -28.93 mV)) are synthesized to investigate whether they can help to improve maize drought tolerance and the relevant mechanisms behind this. In planta experimental results show that under drought (15% PEG 6000, polyethylene glycol, mimicking drought stress, 96 h), compared with the control plants, 500 mg L-1 PMO (root application, 96 h) improves maize drought tolerance, showing an increase of root length (21.6%), shoot length (21.2%), fresh weight (7.8%) and total protein (67.2%) content. In addition, PMO significantly decreases the malondialdehyde (MDA) content by 74.7% in maize under drought, compared with the control group. Further, PMO treated maize root apex shows significantly increased mitotic index (MI, 35.5%), and decreased hydrogen peroxide (40.9%). Compared with the control under drought (15% PEG, 96 h), thr root apex of maize plants treated with PMO (500 mg L-1 , root application, 96 h) have significantly lower level of H2 O2 . Overall, the results show that PMO can alleviate drought-inhibited cell mitosis activities via maintaining ROS (reactive oxygen species) homeostasis. In this study, it is not only shown that PMO can be a good nano-regulator candidate to improve maize drought tolerance, but also that PMO has potential to modulate plant cell mitosis activities.

Cell Wall Pectin Content Refers to Favored Delivery of Negatively Charged Carbon Dots in Leaf Cells.

In this work, we systematically investigated how cell wall and cell wall components affect the delivery of charged carbon quantum dots (CDs, from -34 to +41 mV) to leaf cells of cucumber and Arabidopsis plants. Four different types of leaf cells in cucumber and Arabidopsis were used, i.e., protoplasts (without cell wall), isolated individual cells (cell wall hydrolyzed with pectinase), regenerated individual cells (cell wall regenerated from protoplast), and intact leaf cells (intact cell wall, in planta). Leaf cells were incubated with charged CDs (0.5 mg/mL) for 2 h. Confocal imaging results showed that protoplasts, regenerated individual cells, and leaf cells showed favored uptake of the negatively charged CDs (-34 mV) compared to the PEI (polyethylenimine) coated and positively charged carbon dots [PEI600-CDs (17 mV) and PEI10K-CDs (41 mV)], while in isolated individual cells, the trend is opposite. The results of the content of the cell wall components showed that no significant changes in the total cell wall content were found between isolated individual cells and regenerated individual cells (1.28 vs 1.11 mg/106 cells), while regenerated individual cells showed significant higher pectin content [water-soluble pectin (0.13 vs 0.06 mg/106 cells, P < 0.01), chelator-soluble pectin (0.04 vs 0.01 mg/106 cells, P < 0.01), and alkaline pectin (0.02 vs 0.01 mg/106 cells, P < 0.01)] and significant lower cellulose content (0.13 vs 0.32 mg/106 cells, P < 0.01) than the isolated individual cells. No difference of the hemicellulose content was found between isolated individual cells and regenerated individual cells (0.20 vs 0.21 mg/106 cells). Our results suggest that compared with cellulose and hemicellulose in the cell wall, the pectin is a more important factor referring to the favored uptake of negatively charged carbon dots in leaf cells. Overall, this work provides a method to study the role of cell wall components in the uptake of nanoparticles in plant cells and also points out the importance of understanding the interactions between cell barriers and nanoparticles to design nanoparticles for agricultural use.

"Magic" Sinter-Resistant Cluster Sizes of Ptn Supported on Alumina.

Subnano cluster catalysts, while highly promising due to unique activity, selectivity, and atom-efficiency, are limited in wider applications, as they are prone to deactivation via sintering. Even size-selection, which was previously shown to reduce sintering of nanoparticles, cannot reduce the sintering of highly fluxional subnano clusters due to their inherent isomeric diversity. Here, we use a combination of theory and experiment to show that Pt clusters on Al2O3 exhibit size-dependent sintering resistance. We furthermore show that Pt4/Al2O3 and Pt7/Al2O3 are "magic" sinter-resistant cluster sizes. Their stability is attributed to the greater degree of bulk-like crystallinity of the dominant isomers. In addition, we identify different spatial signatures characteristic of the sintering of clusters with differing sintering stabilities.

The interaction of size-selected Ru3 clusters with RF-deposited TiO2: probing Ru-CO binding sites with CO-temperature programmed desorption.

Small Ru clusters are efficient catalysts for chemical reactions such as CO hydrogenation. In this study 3-atom Ru3 clusters were deposited onto radio frequency (RF)-deposited TiO2 which is an inexpensive, nanoparticulate form of TiO2. TiO2 substrates are notable in that they form strong metal-substrate interactions with clusters. Using temperature programmed desorption to probe Ru-CO binding sites, and X-ray photoelectron spectroscopy to provide chemical information on clusters, differences in cluster-support interactions were studied for Ru3 deposited using both an ultra-high vacuum cluster source and chemical vapour deposition of Ru3(CO)12. The TiO2 was treated with different Ar+ sputter doses prior to cluster depositions, and SiO2 was also used as a comparison substrate. For cluster source-deposited Ru3, heating to 800 K caused cluster agglomeration on SiO2 and oxidation on non-sputtered TiO2. For cluster source-deposited Ru3 on sputtered TiO2 substrates, all Ru-CO binding sites were blocked as-deposited and it was concluded that for the binding sites to be preserved for potential catalytic benefit, sputtering of TiO2 before cluster deposition cannot be applied. Conversely, for Ru3(CO)12 on sputtered TiO2 the clusters were protected by their ligands and Ru-CO binding sites were only blocked once the sample was heated to 723 K. The mechanism for complete blocking of CO sites on sputtered TiO2 could not be directly determined; however, comparisons to the literature indicate that the likely reasons for blocking of the CO adsorption sites are encapsulation into the TiO x layer reduced through sputtering and also partial oxidation of the Ru clusters.

Assessment of metal contamination in estuarine surface sediments from Dongying City, China: Use of a modified ecological risk index.

Surface sediments and clam Meretrix meretrix were collected from a northern estuarine region in Dongying City, China. Sediments were analysed for heavy metals (Hg, As, Cd, Cr, Cu, Pb, and Zn) and the clams were tested for metallothioneins (MTs) and lysosomal membrane stability (LMS). The heavy metal total concentrations decreased in the order of Cr>Zn>Cu>Pb>As>Cd>Hg. The results of Bureau Communautaire de Référence (BCR) sequential extraction of heavy metals showed that the geochemical speciation of all heavy metals was dominated by residual fraction. According to the responses of biomarkers in M. meretrix, the modified potential ecological risk index (PERI-B) can more accurately reflect heavy metals pollution. PERI-B showed all sediment samples have low or moderate risk, except at site S10 (considerable risk), and the main contribution of ecological risk heavy metals were Cd and Hg.

MicroRNA-206: Effective Inhibition of Gastric Cancer Progression through the c-Met Pathway.

MicroRNAs are endogenous short chain nucleotide RNAs that regulate gene function by direct binding of target mRNAs. In this study, we investigated the effects of microRNA-206 (miR-206) on the development of gastric cancer. miR-206 was first confirmed to be downregulated in gastric cancer specimens. Conversely, upregulation of c-Met was confirmed in tissue samples of human gastric cancer, with its level inversely correlated with miR-206 expression. Introduction of miR-206 inhibited cellular proliferation by inducing G1 cell cycle arrest, as well as migration and invasion. Moreover, important proliferation and/or migration related molecules such as c-Met, CDK4, p-Rb, p-Akt and p-ERK were confirmed to be downregulated by Western blot analysis. Targeting of c-Met also directly affected AGS cell proliferation, migration and invasion. In vivo, miR-206 expressing tumor cells also displayed growth delay in comparison to unaffected tumor cells. Our results demonstrated that miR-206 suppressed c-Met expression in gastric cancer and could function as a potent tumor suppressor in c-Met overexpressing tumors. Inhibition of miR-206 function could contribute to aberrant cell proliferation and migration, leading to gastric cancer development.

Development and comparison of intramuscularly long-acting paliperidone palmitate nanosuspensions with different particle size.

The main purpose of this study was to develop and compare the pharmacokinetic behavior of two paliperidone palmitate (PP) nanosuspensions with different particle size after intramuscular (i.m.) administration. PP nanosuspensions were prepared by wet media milling method and the mean particle size of nanosuspension was controlled as 1,041 ± 6 nm (A) and 505 ± 9 nm (B), respectively. The morphology of nanosuspensions was observed by scanning electron microscope (SEM). Differential scanning calorimeter (DSC) and powder X-ray diffraction (PXRD) confirmed the crystallinity of PP in nanosuspensions. The physical and chemical stabilities of nanosuspensions A and B were investigated by particle analyzer and HPLC after storage for 2 months at 25°C, 4°C and mechanical shaking condition. No obvious change in particle size and chemical degradation of drug were observed. Following single-dose i.m. administration to beagle dogs, the release of paliperidone lasted for nearly 1 month. The Tmax of nanosuspensions A and B was 6 (d) and 10 (d). The AUC0-t and Cmax of nanosuspensions A was 2.0-fold and 1.8-fold higher than nanosuspensions B (p<0.05). The results demonstrated that PP nanosuspensions formulation had long-acting effect. Nanosuspension A with a larger particle size performed better than nanosuspension B. As a result, it is important to design appropriate particle size of nanosuspensions for i.m. administration in order to produce larger therapeutic effect.

Major dietary patterns and risk of asymptomatic hyperuricemia in Chinese adults.

In this study, we conducted a case-control study to evaluate the association of major dietary patterns and asymptomatic hyperuricemia taking account of blood lipids in Chinese adults. 187 cases with confirmed asymptomatic hyperuricemia and 187 controls were frequency matched on age, gender and area of residence. We conducted factor analysis using dietary information from a validated food frequency questionnaire to derive dietary patterns. The association between major dietary patterns and asymptomatic hyperuricemia was assessed by logistic regression analysis. Three major dietary patterns were found: 1) "animal products and fried food," 2) "western," 3) "soybean products and fruit." In multivariate analyses the "animal products and fried food" pattern score was associated with an odds ratio (OR) of 2.15 (95% CI, 1.22-3.76) compared with the lowest tertile. The OR for the top tertile of score for "soybean products and fruit" pattern was 0.32 (95% CI, 0.19-0.57) compared with the lowest tertile of "soybean products and fruit" pattern score. The significant association of these two patterns and asymptomatic hyperuricemia persisted after further adjusting for blood lipids. On the other hand, the "western" pattern was not associated with asymptomatic hyperuricemia. We observed a positive relationship between the "animal products and fried food" pattern and asymptomatic hyperuricemia, and a negative relationship between the "soybean products and fruit" pattern and asymptomatic hyperuricemia, independent of blood lipids.