Solvent-free selective hydrogenation of nitroaromatics to azoxy compounds over Co single atoms decorated on Nb2O5 nanomeshes.

The solvent-free selective hydrogenation of nitroaromatics to azoxy compounds is highly important, yet challenging. Herein, we report an efficient strategy to construct individually dispersed Co atoms decorated on niobium pentaoxide nanomeshes with unique geometric and electronic properties. The use of this supported Co single atom catalysts in the selective hydrogenation of nitrobenzene to azoxybenzene results in high catalytic activity and selectivity, with 99% selectivity and 99% conversion within 0.5 h. Remarkably, it delivers an exceptionally high turnover frequency of 40377 h-1, which is amongst similar state-of-the-art catalysts. In addition, it demonstrates remarkable recyclability, reaction scalability, and wide substrate scope. Density functional theory calculations reveal that the catalytic activity and selectivity are significantly promoted by the unique electronic properties and strong electronic metal-support interaction in Co1/Nb2O5. The absence of precious metals, toxic solvents, and reagents makes this catalyst more appealing for synthesizing azoxy compounds from nitroaromatics. Our findings suggest the great potential of this strategy to access single atom catalysts with boosted activity and selectivity, thus offering blueprints for the design of nanomaterials for organocatalysis.

Geometric and Electronic Engineering of Atomically Dispersed Copper-Cobalt Diatomic Sites for Synergistic Promotion of Bifunctional Oxygen Electrocatalysis in Zinc-Air Batteries.

The development of rechargeable zinc-air batteries is heavily dependent on bifunctional oxygen electrocatalysts to offer exceptional oxygen reduction/evolution reaction (ORR/OER) activities. However, the design of such electrocatalysts with high activity and durability is challenging. Herein, a strategy is proposed to create an electrocatalyst comprised of copper-cobalt diatomic sites on a highly porous nitrogen-doped carbon matrix (Cu-Co/NC) with abundantly accessible metal sites and optimal geometric and electronic structures. Experimental findings and theoretical calculations demonstrate that the synergistic effect of Cu-Co dual-metal sites with metal-N4 coordination induce asymmetric charge distributions with moderate adsorption/desorption behavior with oxygen intermediates. This electrocatalyst exhibits extraordinary bifunctional oxygen electrocatalytic activities in alkaline media, with a half-wave potential of 0.92 V for ORR and a low overpotential of 335 mV at 10 mA cm-2 for OER. In addition, it demonstrates exceptional ORR activity in acidic (0.85 V) and neutral (0.74 V) media. When applied to a zinc-air battery, it achieves extraordinary operational performance and outstanding durability (510 h), ranking it as one of the most efficient bifunctional electrocatalysts reported to date. This work demonstrates the importance of geometric and electronic engineering of isolated dual-metal sites for boosting bifunctional electrocatalytic activity in electrochemical energy devices.

Engineering the Electronic Structure of Single-Atom Iron Sites with Boosted Oxygen Bifunctional Activity for Zinc-Air Batteries.

Rechargeable zinc-air batteries typically require efficient, durable, and inexpensive bifunctional electrocatalysts to support oxygen reduction/evolution reactions (ORR/OER). However, sluggish kinetics and mass transportation challenges must be addressed if the performance of these catalysts is to be enhanced. Herein, a strategy to fabricate a catalyst comprising atomically dispersed iron atoms supported on a mesoporous nitrogen-doped carbon support (Fe SAs/NC) with accessible metal sites and optimized electronic metal-support interactions is developed. Both the experimental results and theoretical calculations reveal that the engineered electronic structures of the metal active sites can regulate the charge distribution of Fe centers to optimize the adsorption/desorption of oxygenated intermediates. The Fe SAs/NC containing Fe1 N4 O1 sites achieves remarkable ORR activity over the entire pH range, with half-wave potentials of 0.93, 0.83, and 0.75 V (vs reversible hydrogen electrode) in alkaline, acidic, and neutral electrolytes, respectively. In addition, it demonstrates a promising low overpotential of 320 mV at 10 mA cm-2 for OER in alkaline conditions. The zinc-air battery assembled with Fe SAs/NC exhibits superior performance than that of Pt/C+RuO2 counterpart in terms of peak power density, specific capacity, and cycling stability. These findings demonstrate the importance of the electronic structure engineering of metal sites in directing catalytic activity.

Knockdown of mediator complex subunit 27 suppresses gastric cancer cell metastasis and angiogenesis via Wnt/ß-catenin pathway.

Mediator complex (MED) contains 28 subunits, functions as a transcription machinery through interaction with RNA polymerase II and modulates gene expression involved in cell survival and growth. MED27, as an oncogene, stimulates malignant behavior of various tumors. Role of MED27 in gastric cancer was assessed in this study. Firstly, bioinformatics analysis predicted that MED27 was elevated in gastric cancer. Gastric cancer cells also showed higher expression of MED27 than normal gastric epithelial cells. Secondly, functional assays revealed that silencing of MED27 decreased cell viability, and reduced proliferation of gastric cancer. Cell invasion and migration of gastric cancer were also inhibited by loss of MED27. Moreover, knockdown of MED27 inhibited angiogenesis of gastric cancer. Thirdly, nuclear protein of ß-catenin in gastric cancer was reduced by silencing of MED27. Lastly, in vivo tumor growth of gastric cancer was suppressed by interference of MED27. In conclusion, MED27 functioned as an oncogene in gastric cancer through promoting cell metastasis and angiogenesis.

Overexpressed IncRNA GATA3-AS1 in Preeclampsia and Its Effects on Trophoblast Proliferation and Migration by the miR-488-3p/ROCK1 Axis.

Recently, dysregulation of long noncoding RNAs (lncRNAs) has been reported to be involved in the pathogenesis of preeclampsia (PE). Here, the role and molecular mechanisms of lncRNA GATA3 antisense RNA 1, GATA3-AS1 in PE were explored. The expression of GATA3-AS1, miR-488-3p and Rho-associated coiled-coil-containing protein kinase 1 (ROCK1) in placental tissues from patients with PE was measured by reverse transcription quantitative PCR (RT-qPCR). Proliferation, migration, invasion, and apoptosis of trophoblast cells were examined by 5-ethynyl-2'-deoxyuridine (EdU), wound healing, Transwell, and flow cytometry analyses. The subcellular localization of GATA3-AS1 in trophoblast cells was determined by fluorescent hybridization (FISH) assay. The interactions among GATA3-AS1, miR-488-3p and ROCK1 were identified by luciferase reporter and RNA pulldown assays. Our results showed that GATA3-AS1 and ROCK1 were overexpressed while miR-488-3p was downregulated in placental samples with PE. Functionally, GATA3-AS1 overexpression promoted trophoblast cell apoptosis and inhibited cell proliferation, migration, and invasion. Mechanically, GATA3-AS1 acted as a molecular sponge of miR-488-3p and miR-488-3p targeted ROCK1 in trophoblast cells. In rescue assays, ROCK1 overexpression or miR-488-3p downregulation reversed the effects of GATA3-AS1 silencing on trophoblast cell phenotypes. GATA3-AS1 is overexpressed in PE and promotes PE progression by the miR-488-3p/ROCK1 axis.

Deep Learning Algorithm-Based Magnetic Resonance Imaging Feature-Guided Serum Bile Acid Profile and Perinatal Outcomes in Intrahepatic Cholestasis of Pregnancy.

This study was aimed to explore magnetic resonance imaging (MRI) based on deep learning belief network model in evaluating serum bile acid profile and adverse perinatal outcomes of intrahepatic cholestasis of pregnancy (ICP) patients. Fifty ICP pregnant women diagnosed in hospital were selected as the experimental group, 50 healthy pregnant women as the blank group, and 50 patients with cholelithiasis as the gallstone group. Deep learning belief network (DLBN) was built by stacking multiple restricted Boltzmann machines, which was compared with the recognition rate of convolutional neural network (CNN) and support vector machine (SVM), to determine the error rate of different recognition methods on the test set. It was found that the error rate of deep learning belief network (7.68%) was substantially lower than that of CNN (21.34%) and SVM (22.41%) (P < 0.05). The levels of glycoursodeoxycholic acid (GUDCA), glycochenodeoxycholic acid (GCDCA), and glycocholic acid (GCA) in the experimental group were dramatically superior to those in the blank group (P < 0.05). Both the experimental group and the blank group had notable clustering of serum bile acid profile, and the experimental group and the gallstone group could be better distinguished. In addition, the incidence of amniotic fluid contamination, asphyxia, and premature perinatal infants in the experimental group was dramatically superior to that in the blank group (P < 0.05). The deep learning confidence model had a low error rate, which can effectively extract the features of liver MRI images. In summary, the serum characteristic bile acid profiles of ICP were glycoursodeoxycholic acid, glycochenodeoxycholic acid, and glycocholic acid, which had a positive effect on clinical diagnosis. The toxic effects of high concentrations of serum bile acids were the main cause of adverse perinatal outcomes and sudden death.

MiR-125b-5p ameliorates hypoxia/reoxygenation-induced endothelial cell dysfunction and attenuates reduced uterine perfusion pressure-induced hypertension in pregnant rats via targeting BMF.

BACKGROUND AND PURPOSE: MicroRNA-125b-5p (miR-125b-5p) is downregulated in patients with gestational hypertension signs. However, the role of miR-125b-5p in pregnancy-induced hypertension (PIH) remains unknown. METHODS: The human placental microvascular endothelial cells (HPMECs) have undergone hypoxia and reoxygenation (H/R) treatment to establish PIH cellular model. Rats were performed with reduced uterine perfusion pressure (RUPP) operation to establish PIH animal model. RESULTS: MiR-125b-5p promoted viability while inhibited the apoptosis of H/R-treated HPMECs by downregulating BMF. MiR-125b-5p alleviated hypertensive symptoms and improved pregnancy outcomes in RUPP rats. CONCLUSION: MiR-125b-5p ameliorates H/R-induced HPMEC dysfunction and attenuates RUPP-induced hypertension in pregnant rats by downregulating BMF.

MicroRNA-195-5p facilitates endothelial dysfunction by inhibiting vascular endothelial growth factor A in gestational diabetes mellitus.

Gestational diabetes mellitus (GDM) is a common disorder during pregnancy associated with endothelial dysfunction in the placental vasculature. MicroRNAs (miRNAs), which are short noncoding RNAs that modulate post-transcriptional gene expression, affect GDM progression. MiR-195-5p was reported to be a putative biomarker for GDM diagnosis, whose expression was markedly elevated in serum of GDM patients. Therefore, our study intended to explore whether miR-195-5p regulates endothelial cell dysfunction in GDM. Human placental microvascular endothelial cells (hPMECs) were treated with high concentration of glucose to establish an in vitro GDM model. The apoptosis, proliferation and angiogenesis of hPMECs were detected by flow cytometry analysis, CCK-8 assay and tube formation assay. The binding between vascular endothelial growth factor A (VEGFA) and miR-195-5p was verified by luciferase reporter assay. GDM mouse model was established by intraperitoneal injection of streptozocin. Cell apoptosis and the pathological changes in GDM mouse placenta tissues were evaluated by TUNEL staining and HE staining. Gene expression was detected by RT-qPCR. Protein levels were evaluated by western blotting. In this study, miR-195-5p knockdown promoted the proliferation and angiogenesis as well as inhibited the apoptosis of HG-treated hPMECs. MiR-195-5p targeted VEGFA, whose expression was downregulated in HG-treated hPMECs. VEGFA silencing antagonized the influence of miR-195-5p knockdown on the phenotypes of HG-treated hPMECs. Additionally, miR-195-5p inhibition decelerated cell apoptosis and improved pathological changes in GDM mouse placenta tissues. MiR-195-5p level was negatively correlated to VEGFA level in GDM mouse placenta tissues. Overall, miR-195-5p facilitates the endothelial cell dysfunction by inhibiting VEGFA in GDM.

Immunogenomic characterization in gastric cancer identifies microenvironmental and immunotherapeutically relevant gene signatures.

BACKGROUND: Multiple molecular subtypes with distinct clinical outcomes in gastric cancer have been identified. Nonetheless, the immunogenomic subtypes of gastric cancer and its mediated tumor microenvironment (TME) characterizations have not been fully understood. METHODS: Six gastric cancer cohorts with 1506 samples were obtained. Unsupervised methods were used to perform immunogenomic phenotype clustering. The least absolute shrinkage and selection operator regression method was used to construct immunogenomic characterization score (IGCS). RESULTS: Three distinct immunogenomic phenotypes were determined. We observed a prominent survival difference between three phenotypes. The TME cell-infiltrating characteristics under these three phenotypes were highly consistent with three immune subtypes of tumors. Cluster 1, was characterized by the "immune-desert" phenotype, with relatively lower cell infiltration level (type 1 "cold tumor"); Cluster 2, characterized by "immune-inflamed" phenotype, with abundant innate and adaptive immune cell infiltration ("hot tumor"); Cluster 3, characterized by "immune-excluded" phenotype, with significant stromal activation and inactivated immune cell infiltration (type 2 "cold tumor"). We demonstrated IGCS signature was significantly correlated with TME inflammation and stroma activity, molecular subtypes, genetic variation, microsatellite instability, immune checkpoint molecules, and patient prognosis. High IGCS subtype, with poorer survival and enhanced stromal activity, presented an immune-exclusion and non-inflamed TME characterization. Low IGCS, related to increased mutation/neoantigen load and microsatellite instability, showed enhanced responses to anti-checkpoint immunotherapy. Four immunotherapy cohorts confirmed patients with low IGCS exhibited prominently enhanced clinical responses and treatment advantages. CONCLUSIONS: This study demonstrated the immunogenomic characterizations could play a crucial role in shaping the complexity and diversity of tumor microenvironment. Targeting tumor immunogenomic characteristic in order for changing adverse phenotypes may contribute to exploiting the novel immunotherapy combination strategies or novel immunotherapeutic drugs, and promoting the advance of tumor personalized immunotherapy.

Circ_0007121 Facilitates Trophoblastic Cell Proliferation, Migration, and Invasion via the Regulation of the miR-421/ZEB1 Axis in Preeclampsia.

Noncoding circular RNAs (circRNAs) have participated in the progression of preeclampsia (PE) via inhibiting microRNAs (miRNAs) to regulate gene expression. This study was designed to explore the miRNA/mRNA mechanism of hsa_circ_0007121 (circ_0007121) in PE. The expression detection of circ_0007121, microRNA-421 (miR-421), and zinc finger E-box binding homeobox 1 (ZEB1) was performed by quantitative real-time polymerase chain reaction (qRT-PCR). Cell proliferation was analyzed by Cell Counting Kit-8 (CCK-8) assay. Transwell assay was used to determine cell migration and invasion. Cell apoptosis was evaluated using flow cytometry. The protein levels of epithelial-mesenchymal transition (EMT) markers and ZEB1 were measured via western blot. The interaction between miR-421 and circ_0007121 or ZEB1 was validated by dual-luciferase reporter assay. The expression detection indicated that circ_0007121 was downregulated in PE patients and the clinical data revealed that circ_0007121 was related to PE. The upregulation of circ_0007121 promoted cell proliferation, migration, invasion, and EMT in trophoblastic cells. Furthermore, circ_0007121 was identified as a sponge of miR-421 and the function of circ_0007121 was dependent on the sponge effect on miR-421. Moreover, ZEB1 was a target of miR-421 and circ_0007121/miR-421 axis could regulate the expression of ZEB1. In addition, miR-421 overexpression repressed trophoblastic cell behaviors through downregulating the ZEB1 level. Altogether, circ_0007121 contributed to the development of trophoblastic cells by regulating the miR-421/ZEB1 axis.

CT Image Features under Reconstruction Algorithm in Analysis of the Effect of Probiotics Combined with Ursodeoxycholic Acid in Treatment of Intrahepatic Cholestasis of Pregnancy.

This research was to explore the adoption value of computed tomography (CT) images based on adaptive statistical iterative reconstruction (ASIR) algorithm in the evaluation of probiotics combined with ursodeoxycholic acid in the treatment of intrahepatic cholestasis of pregnancy (ICP). A total of 82 patients with ICP were selected as the research subjects and they were randomly rolled into experimental group (380 mg probiotics enteric-soluble capsule twice a day, combined with 90 mg ursodeoxycholic acid soft capsule three times a day) and control group (90 mg ursodeoxycholic acid soft capsule three times a day), with 41 cases in each. The treatment course was four months. The ASIR algorithm was constructed and applied to the CT image analysis and diagnosis of ICP patients. The effects of filtering back projection (FBP) reconstruction and ASIR algorithm on CT image quality, denoising degree, and artifacts of ICP patients were compared. Moreover, blood indicator levels of ICP patients before and after treatment were assessed. The results showed that the SD values of liver and gallbladder (20.77 Hu and 27.58 Hu) in the reconstructed image of the ASIR algorithm were significantly lower than those of the FBP algorithm (40.58 Hu and 45.63 Hu) (P < 0.05). The SNR values of the liver and gallbladder (3.68 and 2.05) of the reconstructed image were significantly higher than those of the FBP algorithm (1.91 and 1.19) (P < 0.05). The overall image quality after ASIR reconstruction (3.92 points) was significantly better than that of the FBP algorithm (2.36 points), and the image noise score (3.21 points) reconstructed by the FBP algorithm was higher than that by the ASIR algorithm (1.83 points). The artifact score of FBP reconstructed image (4.47 points) was greatly higher than that of ASIR algorithm (2.26 points) (P < 0.05). Before treatment, there was no remarkable difference in the indexes between the two groups of patients (P > 0.05). After treatment, the γ-glutamyltransferase (γ-GT) and alkaline phosphatase (ALP) levels (327.55 U/L and 778.15 µmol/L) of the experimental group of ICP patients were higher than those of the control group (248.63 U/L and 668.43 µmol/L), with substantial difference between the two groups (P < 0.05). The blood ammonia (BA) level (151.09 µmol/L) of the experimental group was lower than that of the control group (178.46 µmol/L), and the difference between the two groups was remarkable (P < 0.05). To sum up, the CT image denoising degree based on ASIR algorithm was high, with few artifacts and good overall quality. Probiotics combined with ursodeoxycholic acid in the treatment of ICP can effectively improve the liver function and intestinal flora of patients, which was of great significance in the clinical diagnosis and treatment of the disease.

MiRNA-621 exerts tumor suppressor function in gastric adenocarcinoma by targeting AURKA/GSK-3ß pathway.

Gastric adenocarcinoma is a major challenge to human health worldwide. Abnormal expression of miR-621 was found in many types of cancer. This research aimed to investigate the effects and detailed molecular mechanisms of miR-621 on gastric adenocarcinoma progression. The present study first showed that miR-621 was downregulated in gastric cancer patients, and its expression level was correlated with tumor size. MiR-621 overexpression inhibited viability, colony formation and proliferation of gastric cancer cells. AURKA was identified as a direct target of miR-621. AURKA knockdown induced decrease of p-GSK-3ß/GSK-3ß ratio and increase of p-ß-catenin/ß-catenin ratio which confirmed that AURKA positively regulated GSK-3ß phosphorylation. AURKA knockdown also inhibited proliferation of gastric adenocarcinoma cells. AURKA expression was negatively correlated with miR-621 level. In addition, AURKA overexpression reversed the effect of miR-621 on the growth of cancer cells. Taken together, our results suggest that miR-621 is an important tumor suppressor in gastric cancer and could be a promising target for the cancer treatment.

Therapeutic effect of erythropoietin on brain injury in premature mice with intrauterine infection.

OBJECTIVE: The objective of this study is to explore the protective effect of erythropoietin (EPO) on brain injury induced by intrauterine infection in premature infants and its related mechanism, so as to provide reference for clinical medication. METHODS: Intrauterine infection model is established by injecting lipopolysaccharide into pregnant mice, and HE staining of mouse placenta is used to judge whether the model of intrauterine infection is successful or not. Fifteen female rats are successfully pregnant and divided into intrauterine infection group (10 rats) and control group (5 rats). The mice in the intrauterine infection group are intraperitoneally injected with lipopolysaccharide (LPS) at a dose of 0.3 mg/kg. After delivery, 16 newborn mice in the control group are randomly selected as blank control group. 32 newborn mice in the intrauterine infection group are selected as model group, and then divided into infection group and EPO treatment group, 16 mice in each group. After birth, mice in the blank control group are intraperitoneally injected with 0.2 mL saline daily. The infected mice are intraperitoneally injected with 0.2 mL saline daily. The mice in the EPO treatment group are intraperitoneally injected with recombinant human erythropoietin (rhEPO) 5000 IU/kg daily. HE staining results, EPOR protein and NMDAR1 mRNA expression in brain tissue of three groups of neonatal mice were compared. RESULTS: Firstly, the blood vessels of the mice in the intrauterine infection group are markedly hyperemic and edematous, and the infiltration of neutrophils is increased. The white matter structure of the neonatal mice in the intrauterine infection group is loose and stained lightly. The nerve fibers in the brain are different in thickness and disordered in arrangement. The nucleus is small and dark stained. The number of glial cells in brain tissue increases significantly. Secondly, the EPOR protein expression and physiological level of neonatal mice in intrauterine infection group increase significantly at 3, 7 and 14 days after birth. Compared with the blank control group, the difference is statistically significant (P < 0.05). On the 3rd day after birth, the expression level of EPOR protein in the EPO treated group is significantly higher than that in the intrauterine infection group (P < 0.05). Thirdly, the expression level of NMDA R1mRNA in brain tissue of neonatal mice at birth, on the 3rd and 7th day after EPO treatment is significantly lower than that of intrauterine infection group (P < 0.05). CONCLUSION: EPO can promote the proliferation and differentiation of brain endogenous neural stem cells, and has a certain therapeutic effect on brain injury of premature mice caused by intrauterine infection.

Long noncoding RNA CDKN2B-AS1 interacts with miR-411-3p to regulate ovarian cancer in vitro and in vivo through HIF-1a/VEGF/P38 pathway.

Ovarian cancer (OC) is one of the most prevalent cancers with high fatality rate. In the present study, RT-PCR showed that the mRNA level of CDKN2B-AS1 was significantly upregulated while the miR-411-3p was downregulated in OC cell lines. In addition, the Sh-CDKN2B-AS1 resulted in the suppression of cell growth, invasion, migration and promotion of apoptosis, and miR-411-3p showed reversed results. Further studies demonstrated that CDKN2B-AS1 could directly interact with miR-411-3p, and that there was an inverse correlation between miR-411-3p and CDKN2B-AS1. Moreover, the in vivo experiments further demonstrated that Sh-CDKN2B-AS1 could inhibit the tumor growth. In addition, we examined the effect of CDKN2B-AS1 and miR-411-3p on HIF1a/VEGF/P38 axis. Consequently, Sh-CDKN2B-AS1 could suppress this pathway. In summary, our study demonstrated that the CDKN2B-AS1 interacted with miR-411-3p contributing to carcinogenesis in OC. Meanwhile, Sh-CDKN2B-AS1 showed anti-cancer role by promoting apoptosis and inhibiting cell growth, invasion and migration. Collectively, CDKN2B-AS1 modulated these activities possibly though miR-411-3p/HIF1a/VEGF/P38 pathway.

Microwave-induced synthesis of pyrophosphate Zr1-xTixP2O7 and TiP2O7 with enhanced sorption capacity for uranium (VI).

A series of nanostructured pyrophosphates Zr1-xTixP2O7 (x=0, 0.2, 0.4, 0.5, 0.6, 0.8, and 1.0), have been prepared via a facile microwave induced route in which zirconium hydroxide, titanium hydroxide and phosphoric acid were used as Zr, Ti and P sources, respectively. It is demonstrated the isomorphous substitution of Zr(4+) by Ti(4+) results in a decrease of the size and an enhancement of the adsorption capacity of the obtained particles for U(VI) in aqueous solution. The maximum amount of TiP2O7 for U(VI) reached up to 309.8 mgg(-1) under the experimental conditions (pH=5, t=60min and T=303K). The as-obtained specific metal pyrophosphates exhibit a considerably higher adsorption capability for U(VI) in aqueous solution compared with Zr1-xTixP2O7 prepared by calcined method, showing a high potential for U(VI) sequestration applications. The adsorption kinetics and thermodynamic analysis of Zr1-xTixP2O7 on adsorption of U (VI) were performed, and a possible adsoprtion mechanism was also proposed.

Directed self-assembly of epitaxial CoFe2O(4)-BiFeO3 multiferroic nanocomposites.

CoFe(2)O(4) (CFO)-BiFeO(3) (BFO) nanocomposites are an intriguing option for future memory and logic technologies due to the magnetoelectric properties of the system. However, these nanocomposites form with CFO pillars randomly located within a BFO matrix, making implementation in devices difficult. To overcome this, we present a technique to produce patterned nanocomposites through self-assembly. CFO islands are patterned on Nb-doped SrTiO(3) to direct the self-assembly of epitaxial CFO-BFO nanocomposites, producing square arrays of CFO pillars.

Water-dispersible iron oxide magnetic nanoparticles with versatile surface functionalities.

We report a simple one-pot strategy to prepare surface-function-alized, water-dispersible iron oxide nanoparticles. Small organic molecules that have desired functional groups such as amines, carboxylics, and thiols are chosen as capping agents and are injected into the reaction medium at the end of the synthesis. A diversity of functionalities are effectively introduced onto the surface of the nanoparticles with a minimal consumption of solvents and chemical resources by simply switching the capping ligand to form the ligand shell. The resulting nanocrystals are quasi-spherical and narrowly size-distributed. Energy-dispersive X-ray analysis and Fourier transform infrared spectroscopy studies suggest a successful surface modification of iron oxide nanoparticles with selected functionalities. The colloidal stabilities are characterized by dynamic light scattering and zeta potential measurements. The results imply that functionalized nanoparticles are very stable and mostly present as individual units in buffer solutions. The pedant functional groups of the capping ligand molecules are very reactive, and their availabilities are investigated by covalently linking fluorescent dyes to the nanoparticles through the cross-linking of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride. The quenched quantum yield and shortened lifetime of the dyes strongly indicate a direct bonding between the functional group of the nanoparticles and the fluorescent molecules.

Construction of metal-organic oxides from molybdophosphonate clusters and copper-bipyrimidine building blocks.

A series of organic-inorganic hybrid materials of the copper(II)-molybdophosphonate family have been prepared using conventional hydrothermal conditions. The reactions of MoO(3), copper(II) acetate, bipyrimidine (bpyr), a phosphonic acid, and water at temperatures below 160 degrees C and in the presence of a mineralizer such as acetic acid or HF provided crystalline samples of materials of the general class {Cu(2)(bpyr)}(4+)/Mo(x)O(y)-phosphonate. The recurrent themes of the structures are the presence of the binuclear {Cu(2)(bpyr)}(4+) and pentanuclear {Mo(5)O(15)(O(3)PR)(2)}(4-) building blocks. For the alkylphosphonate-containing materials, [{Cu(2)(bpyr)(2)}Mo(5)O(15)(O(3)PCH(3))(2)].2.5H(2)O (1.2.5H(2)O) is two-dimensional and exhibits {Cu(bpyr)}(n)(2n+) chains, while [{Cu(2)(bpyr)(H(2)O)}Mo(5)O(15)(O(3)PCH(2)CH(3))(2)] (2) is three-dimensional. The diphosphonate series of materials {{Cu(2)(bpyr)}(4+)[Mo(5)O(15){O(3)P(CH(2))(n)PO(3)}](4-) with n = 2-6 (4, 5, 7-9) in all cases contain the characteristic [Mo(5)O(15){O(3)P(CH(2))(n)PO(3)}](n)(2n+) chains, linked through {Cu(2)(bpyr)}(4+) rods into three-dimensional frameworks. When n = 1, the three-dimensional phase [{Cu(2)(bpyr)}MoO(2)(HO(3)PCH(2)PO(3))(2)].2H(2)O (3.2H(2)O) is obtained, the exclusive example of a structure constructed from isolated {MoO(6)} polyhedra rather than pentamolybdate clusters. The Ni(II)-containing phase [{Ni(2)(bpyr)(H(2)O)(4)}Mo(5)O(15){O(3)P(CH(2))(3)PO(3)}].9H(2)O (6.9H(2)O) was also prepared and compared to the structure of the Cu(II) analogue, [{Cu(2)(bpyr)(H(2)O)(4)}Mo(5)O(15){O(3)P(CH(2))(3)PO(3)}].3H(2)O (5.3H(2)O). Magnetic susceptibility studies of the compounds revealed that the magnetic behavior was consistent in all cases with antiferromagnetically coupled dimers. However, the magnitude of the exchange coupling was clearly dependent on the orientation of the M(II) mean equatorial or basal planes relative to the bipyrimidine plane. Thus, when the metal and bipyrimidine planes are nearly coplanar, the J values are in the -77 to -87 cm(-1) range, while J values of -2 to -5 cm(-1) are observed for the compounds with out-of-plane orientations.

Solid-state coordination chemistry of copper(II) tetrazolates: anion control of frameworks constructed from trinuclear copper(II) building blocks.

The products of the reactions of copper(II) starting materials with 4-pyridyltetrazole (4-Hpt) in N,N-dimethylformamide (DMF)/methanol solutions are determined by the anion identity and concentration. In the absence of chloride, the 3-D open-framework material [Cu(3)(OH)(3)(4-pt)(3)(DMF)(4)].5DMF.3MeOH (1.5DMF.3MeOH) is isolated, while variations in the chloride concentration yield the 2-D and 3-D materials, 2 and 3, respectively. All three structures exhibit trinuclear copper(II) building blocks: the triangular {Cu(3)(mu(3)-OH)}(5+) core in 1 and {Cu(3)Cl(4)(4-pt)(4)(4-Hpt)(2)}(2-) and {Cu(3)Cl(2)(4-pt)(8)}(4-) chains in 2 and 3, respectively. All three materials display microporosity, which is highly dependent on the method of sample preparation.