TRIP6 promotes neural stem cell maintenance through YAP-mediated Sonic Hedgehog activation.

In the adult mammalian brain, new neurons are continuously generated from neural stem cells (NSCs) in the subventricular zone (SVZ)-olfactory bulb (OB) pathway. YAP, a transcriptional co-activator of the Hippo pathway, promotes cell proliferation and inhibits differentiation in embryonic neural progenitors. However, the role of YAP in postnatal NSCs remains unclear. Here, we showed that YAP was present in NSCs of the postnatal mouse SVZ. Forced expression of Yap promoted NSC maintenance and inhibited differentiation, whereas depletion of Yap by RNA interference or conditional knockout led to the decline of NSC maintenance, premature neuronal differentiation, and collapse of neurogenesis. For the molecular mechanism, thyroid hormone receptor-interacting protein 6 (TRIP6) recruited protein phosphatase PP1A to dephosphorylate LATS1/2, therefore inducing YAP nuclear localization and activation. Moreover, TRIP6 promoted NSC maintenance, cell proliferation, and inhibited differentiation through YAP. In addition, YAP regulated the expression of the Sonic Hedgehog (SHH) pathway effector Gli2 and Gli1/2 mediated the effect of YAP on NSC maintenance. Together, our findings demonstrate a novel TRIP6-YAP-SHH axis, which is critical for regulating postnatal neurogenesis in the SVZ-OB pathway.

Monoclonal enolase-1 blocking antibody ameliorates pulmonary inflammation and fibrosis.

BACKGROUND: Idiopathic pulmonary fibrosis (IPF) is a chronic fatal disease with limited therapeutic options. The infiltration of monocytes and fibroblasts into the injured lungs is implicated in IPF. Enolase-1 (ENO1) is a cytosolic glycolytic enzyme which could translocate onto the cell surface and act as a plasminogen receptor to facilitate cell migration via plasmin activation. Our proprietary ENO1 antibody, HL217, was screened for its specific binding to ENO1 and significant inhibition of cell migration and plasmin activation (patent: US9382331B2). METHODS: In this study, effects of HL217 were evaluated in vivo and in vitro for treating lung fibrosis. RESULTS: Elevated ENO1 expression was found in fibrotic lungs in human and in bleomycin-treated mice. In the mouse model, HL217 reduced bleomycin-induced lung fibrosis, inflammation, body weight loss, lung weight gain, TGF-ß upregulation in bronchial alveolar lavage fluid (BALF), and collagen deposition in lung. Moreover, HL217 reduced the migration of peripheral blood mononuclear cells (PBMC) and the recruitment of myeloid cells into the lungs. In vitro, HL217 significantly reduced cell-associated plasmin activation and cytokines secretion from primary human PBMC and endothelial cells. In primary human lung fibroblasts, HL217 also reduced cell migration and collagen secretion. CONCLUSIONS: These findings suggest multi-faceted roles of cell surface ENO1 and a potential therapeutic approach for pulmonary fibrosis.

Postmodified Dual Functional UiO Sensor for Selective Detection of Ozone and Tandemly Derived Sensing of Al3.

Development of highly sensitive and selective fluorescent sensors toward hazardous analytes represents great progress in fabricating sensing devices for practical applications. In this work, a highly selective sensor with dual functions has been fabricated via facile postmodification of the UiO-MOF. Butene modified salicylaldehyde is covalently linked to the UiO-66 scaffold via an efficient Schiff-base reaction, resulting in a highly fluorescent ozone sensor of UiO-66-butene. Ozonolysis of the terminal olefin followed by ß-elimination could significantly quench the bright blue fluorescence of UiO-66-butene, and linear turn-off detection of ozone in the range of 0-100 µM is well established. The detection is highly sensitive and selective, and a detection limit of 73 nM was calculated. Remarkably, the ozonolysis afforded product could further act as a selective sensor for Al3+ via turn-on fluorescence with a detection limit of 142 nM, representing a second potential sensing function. The chemically selective sequential ozonolysis/ß-elimination and remarkable dual functions offer the exclusive detection of ozone over other oxidative species as well as Al3+ over other cations following a tandem process, representing the first example of a direct MOF sensor for dual sensing of ozone and Al3+. This work demonstrates the potential of employing combinatorial principles for fabricating highly selective sensors, and postmodification of MOFs represents a promising facile strategy for developing various functional sensors.

Efficacy of low-molecular-weight heparin on the outcomes of in vitro fertilization/intracytoplasmic sperm injection pregnancy in non-thrombophilic women: a meta-analysis.

INTRODUCTION: The aim of our study was to evaluate the effect of low-molecular-weight heparin on pregnancy outcomes in women without thrombophilia during in vitro fertilization/intracytoplasmic sperm injection treatment. MATERIAL AND METHODS: We searched Pubmed, Web of Science, Embase, Cochrane and CNKI (from inception to 2 February 2018). Our study identified randomized controlled trials or quasi-randomized controlled trials comparing low-molecular-weight heparin subcutaneous treatment with no treatment or only luteal support control. The outcomes included live birth rate, clinical pregnancy rate and miscarriage rate. RESULTS: Five trials, including 935 women receiving in vitro fertilization/intracytoplasmic sperm injection treatment, were included in meta-analyses. There were 458 women receiving low-molecular-weight heparin and 477 in the control group. No significant differences for live birth rate, clinical pregnancy rate and miscarriage rate were found between the low-molecular-weight heparin and control groups. Of them, four trials reported live birth rate as an outcome and the risk ratio was 1.13 (95% confidence interval 0.88-1.43, p = 0.34). All five trials reported clinical pregnancy rate as an outcome, the risk ratio was 1.08 (95% confidence interval 0.87-1.32, p = 0.47). Three trials reported miscarriage rate and the risk ratio was 0.58 (95% confidence interval 0.30-1.10, p = 0.09). In women with two or more failed in vitro fertilization/intracytoplasmic sperm injection cycles, the risk ratio of live birth rate was 1.15 and the risk ratio of clinical pregnancy rate was 1.17. In women with three or more failed in vitro fertilization/intracytoplasmic sperm injection cycles, the risk ratios of live birth rate and clinical pregnancy rate were 1.36 and 1.35, respectively. CONCLUSIONS: Our results suggested that low-molecular-weight heparin had no effect on pregnancy success rate in non-thrombophilic women undergoing in vitro fertilization/intracytoplasmic sperm injection treatment. However, to justify the use of low-molecular-weight heparin in clinical practice, multicenter trials are still necessary.

Metal-Organic Framework Photosensitized TiO2 Co-catalyst: A Facile Strategy to Achieve a High Efficiency Photocatalytic System.

A 3D metal-organic framework (ADA-Cd=[Cd2 L2 (DMF)2 ]⋅3 H2 O where H2 L is (2E,2'E)-3,3'-(anthracene-9,10-diyl)diacrylic acid) constructed from diacrylate substituted anthracene, sharing structural characteristics with some frequently employed anthraquinone-type dye sensitizers, was introduced as an effective sensitizer for anatase TiO2 to achieve enhanced visible light photocatalytic performance. A facile mechanical mixing procedure was adopted to prepare the co-catalyst denoted as ADA-Cd/TiO2 , which showed enhanced photodegradation ability, as well as sustainability, towards several dyes under visible light irradiation. Mechanistic studies revealed that ADA-Cd acted as the antenna to harvest visible light energy, generating excited electrons, which were injected to the conduction band (CB) of TiO2 , facilitating the separation efficiency of charge carriers. As suggested by the results of control experiments, combined with the corresponding redox potential of possible oxidative species, . O2- , generated from the oxygen of ambient air at the CB of TiO2 was believed to play a dominant role over . OH and h+ . UV/Vis and photoluminescence technologies were adopted to monitor the generation of . O2- and . OH, respectively. This work presents a facile strategy to achieve a visible light photocatalyst with enhanced catalytic activity and sustainability; the simplicity, efficiency, and stability of this strategy may provide a promising way to achieve environmental remediation.

Anti-inflammatory effects of fimasartan via Akt, ERK, and NFκB pathways on astrocytes stimulated by hemolysate.

OBJECTIVE: The aim of this study was to investigate whether fimasartan, a novel angiotensin II receptor blocker, modulates hemolysate-induced inflammation in astrocytes. METHODS: We stimulated astrocytes with hemolysate to induce hemorrhagic inflammation in vitro. Astrocytes were pretreated with fimasartan and then incubated with hemolysate at different durations. Anti-inflammatory cell signaling molecules including Akt, extracellular signal regulated kinase (ERK), NFκB and cyclooxygenase-2 (COX-2) were assessed by western blotting. Pro-inflammatory mediators were evaluated by real-time RT-PCR and ELISA. RESULTS: The stimulation by hemolysate generated a robust activation of inflammatory signaling pathways in astrocytes. Hemolysate increased the phosphorylation of Akt at 1 h, and ERK1/2 at 20 min compared with the control group and promoted the degradation of IκBα. Pretreated fimasartan significantly decreased hemolysate-induced phosphorylation of Akt and ERK1/2. In addition, fimasartan also suppressed NFκB-related inflammatory pathways induced by hemolysate, including reduction of the gene expression of NFκB, and decreased nuclear translocation of NFκB and degradation of IκB. This reduction of inflammatory upstream pathways decreased the expression of inflammatory end-products: COX-2 and interleukin-1 (IL-1ß). Furthermore, the expression of COX-2 was attenuated by both Akt inhibitor (LY294002) and ERK inhibitor (U0126), and IκBα degradation was suppressed by LY294002. CONCLUSIONS: These results demonstrate that pretreatment with fimasartan to astrocytes suppresses the inflammatory responses induced by hemolysate. Akt, ERK and NFκB were associated with hemolysate-induced COX-2 and IL-1ß expression. Based on these mechanisms, fimasartan could be a candidate anti-inflammatory regulator for the treatment of intracerebral hemorrhage.

miR-10b is overexpressed in hepatocellular carcinoma and promotes cell proliferation, migration and invasion through RhoC, uPAR and MMPs.

BACKGROUND: Recently, miR-10b is identified as a miRNA highly expressed in many human cancers, promoting cell migration and invasion. However, the specific function of miR-10b in hepatocellular carcinoma (HCC) is unclear at this point. METHODS: The miR-10b expression levels in 60 paired different TNM Stage HCC tumor tissues compared with adjacent non-tumor (ANT) tissues, normal tissue control (8 benign tumor and 7 normal liver tissues), 3 normal liver and 7 HCC cell lines were measured by real-time quantitative RT-PCR and to evaluate their association with HCC clinicopathologic features. Invasion assay, MTT proliferation assay and wound-healing assay were performed to test the invasion and proliferation of HCC cell after transfection. The effect of miR-10b on HCC in vivo was validated by murine xenograft model. RESULTS: We found that miR-10b expression was increased in human HCC tissues and cell lines compared with normal control, respectively. The expression of miR-10b was correlated with HCC metastatic ability. Overexpression of miR-10b in MHCC-97L cells increased cell motility and invasiveness, whereas inhibition of miR-10b in MHCC-97H cells reduced cell motility and invasiveness in vitro and in vivo. We also showed that HOXD10 was negatively regulated by miR-10b at the posttranscriptional level, via a specific target site within the 3'UTR by luciferase reporter assay. Furthermore, we found that miR-10b induced HCC cell invasion and migration by modulating the HOXD10 target gene RhoC, uPAR, MMP-2 and MMP-9 expression. CONCLUSIONS: Our results suggested that miR-10b was overexpressed in HCC and promoted HCC cell migration and invasion through the HOXD10/ RhoC/ uPAR/ MMPs pathway which may provide a novel bio-target for HCC therapy.

A stable microporous mixed-metal metal-organic framework with highly active Cu2+ sites for efficient cross-dehydrogenative coupling reactions.

Two metalloporphyrin octacarboxylates were used to link copper(II) nodes for the formation of two novel porous mixed-metal metal-organic frameworks (M'MOFs) containing nanopore cages (2.1 nm in diameter) or nanotubular channels (1.5 nm in diameter). The highly active Cu(2+) sites on the nanotubular surfaces of the stable porous M'MOF ZJU-22, stabilized by three-connected nets, lead to the superior catalytic activity for the cross-dehydrogenative coupling (CDC) reaction.

Metalloporphyrinic framework containing multiple pores for highly efficient and selective epoxidation.

Metalloporphyrin Mn(III)Cl-5,10,15,20-tetrakis(3,5-biscarboxylphenyl)porphyrin, having eight carboxylate groups in multiple coordination modes, connects with paddle-wheel Zn2(COO)4 units for the construction of an interesting porous porphyrinic framework that demonstrates high efficiency and stability upon epoxidation of olefins with excellent substrate size selectivity.

Towards an E-nose: Metal-organic frameworks based quartz crystal microbalance array for fruit ripeness indexing.

Ethylene is a hormone for fruit ripening control, and for the purpose of maintaining plant quality, ethylene monitoring is crucial. Due to the simple structure and limited functionality, the technical realization of ethylene detection by an artificial sensor remains a challenge. In this paper, we present a metal-organic frameworks (MOFs) array based electronic nose (e-nose) for rapid and accurate determination of ethylene. Six zirconium-based MOFs with systematically modified pore sizes and π-π binding sites have been prepared and fabricated into a sensor array using quartz crystal microbalance (QCM) technology. By virtue of the synergistic features of six MOF sensors, selectivity detection of ethylene has been achieved. The detection limit reaches to 0.27 ± 0.02 ppm, and high selectivity and stability (98.29 % ± 0.88 %) could also be confirmed. By submitting data to machine learning algorithm, an e-nose system could be established for discriminating ethylene from mixtures with a qualitative accuracy of 90.30 % and quantitative accuracy of 98.89 %. Practical evaluation suggests that the e-nose could index the fruit quality based on the accurate detection of ethylene released during fruit ripeness. This work demonstrates the promising potential of fabricating MOFs based e-nose systems for practical monitoring applications by selectively detecting challengeable target molecules.

Zinc hexacyanoferrate/g-C3N4 nanocomposites with enhanced photothermal and photodynamic properties for rapid sterilization and wound healing.

Photoactivated therapy has gradually emerged as a promising and rapid method for combating bacteria, aimed at overcoming the emergence of drug-resistant strains resulting from the inappropriate use of antibiotics and the subsequent health risks. In this work, we report the facile fabrication of Zn3[Fe(CN)6]/g-C3N4 nanocomposites (denoted as ZHF/g-C3N4) through the in-situ loading of zinc hexacyanoferrate nanospheres onto two-dimensional g-C3N4 sheets using a simple metal-organic frameworks construction method. The ZHF/g-C3N4 nanocomposite exhibits enhanced antibacterial activity through the synergistic combination of the excellent photothermal properties of ZHF and the photodynamic capabilities of g-C3N4. Under dual-light irradiation (420 nm + 808 nm NIR), the nanocomposites achieve remarkable bactericidal efficacy, eliminating 99.98% of Escherichia coli and 99.87% of Staphylococcus aureus within 10 minutes. Furthermore, in vivo animal experiments have demonstrated the outstanding capacity of the composite in promoting infected wound healing, achieving a remarkable wound closure rate of 99.22% after a 10-day treatment period. This study emphasizes the potential of the ZHF/g-C3N4 nanocomposite in effective antimicrobial applications, expanding the scope of synergistic photothermal/photodynamic therapy strategies.

Highly efficient C-H oxidative activation by a porous Mn(III) -porphyrin metal-organic framework under mild conditions.

A simple strategy to rationally immobilize metalloporphyrin sites into porous mixed-metal-organic framework (M'MOF) materials by a metalloligand approach has been developed to mimic cytochrome P450 monooxygenases in a biological system. The synthesized porous M'MOF of [Zn2 (MnOH-TCPP)(DPNI)]⋅0.5 DMF⋅EtOH⋅5.5 H2 O (CZJ-1; CZJ=Chemistry Department of Zhejiang University; TCPP=tetrakis(4-carboxyphenyl)porphyrin); DPNI=N,N'-di(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide) has the type of doubly interpenetrated cubic α-Po topology in which the basic Zn2 (COO)4 paddle-wheel clusters are bridged by metalloporphyrin to form two-dimensional sheets that are further bridged by the organic pillar linker DPNI to form a three-dimensional porous structure. The porosity of CZJ-1 has been established by both crystallographic studies and gas-sorption isotherms. CZJ-1 exhibits significantly high catalytic oxidation of cyclohexane with conversion of 94 % to the mixture of cyclohexanone (K) and cyclohexanol (A) (so-called K-A oil) at room temperature. We also provided solid experimental evidence to verify the catalytic reaction that occurred in the pores of the M'MOF catalyst.

Four metalloporphyrinic frameworks as heterogeneous catalysts for selective oxidation and aldol reaction.

Four porous metalloporphyrinic framework materials, [(CH3)2NH2][Zn2(HCOO)2(Mn(III)-TCPP)]·5DMF·2H2O (1; H6TCPP = tetrakis(4-carboxyphenyl)porphyrin), [(CH3)2NH2][Cd2(HCOO)2(Mn(III)-TCPP)]·5DMF·3H2O (2), [Zn2(HCOO)(Fe(III)(H2O)-TCPP)]·3DMF·H2O (3), and [Cd3(H2O)6(µ2-O)(Fe(III)-HTCPP)2]·5DMF (4) were synthesized by heating a mixture of M(III)Cl-H4TCPP (M = Mn and Fe) and M' (M' = Zn or Cd) nitrate in a mixed solvent of DMF and acetic acid. Compounds 1-3 are built up from M'2(COO)4 paddle-wheel subunits bridged by M(III)-TCPP and formate ligands to form their 3D connections. The formate pillar heterogeneously connects with M and M' cations in 1 and 2 and homogeneously joins M' cations in 3. The µ2-O bridged Fe(III)-HTCPP dimer performs as a decadentate ligand to link 10 cadmium cations for the formation of an interesting 3D coordination network of 4. The four porphyrinic frameworks present interesting catalytic properties in the selective epoxidation of olefins, oxidation of cyclohexane, and intermolecular aldol reaction of aldehydes and ketones.

[Analysis of obstetric outcomes for different types of placenta previa].

OBJECTIVE: To explore the maternal and perinatal outcomes for different types of placenta previa (PP). METHODS: A total of 343 pregnancies with PP from January 2003 to December 2012 at our hospital were retrospectively reviewed. The general profiles, maternal and perinatal outcomes of different types of 325 singleton PP were evaluated. RESULTS: Among them, 221 pregnancies were of complete PP. There were partial (n = 22) and marginal (n = 82) PP. Proportions of previous vaginal and cesarean deliveries in women with complete and partial PP were higher than those with marginal PP (P < 0.05). Compared with marginal PP group, ratio of placenta in the uterus posterior wall prepartum hemorrhage and probability of blood transfusion and neonatal asphyxia were much higher in complete and partial PP. The gestational age at delivery and neonatal body weight with complete PP and partial PP marginal PP were higher than those of the other two groups (P < 0.05). As for the placenta adhesion, placenta accrete or postpartum hemorrhage, no difference existed among three groups placenta location. CONCLUSION: The gestational age at delivery, prepartum hemorrhage, probability of blood transfusion and perinatal outcome in women with PP are related with the type of PP. Both complete and partial PP have relatively worse outcomes. The type of PP has no effect on placenta adhesion, placenta accrete or postpartum hemorrhage.

[Study on high-temperature phase change of tobermorite].

In the present paper, the high-temperature phase change of pure tobermorite was investigated by TGA/DSC, X-ray diffraction and infrared spectroscopy (IR) respectively. The DSC results showed that four interlayer water molecules were lost when they were heated at 300 degrees C. As the temperature increased to 724 degrees C, Si-O-H bonds were cleaved and dehydroxylation occurred. The XRD results showed that many diffraction peaks o f tobermorite disappeared and the crystal structure was broken and collapsed. Then tobermorite tends to be disordered and amorphous. When the calcination temperature increased to 861 degrees C, the disordered structure recombined to wollastonite, and the crystal structure became ordered and stable. Finally, the structure completely transformed to 2M-wollastonite at 1 000 degrees C. It should include the process of high-temperature phase change of tobermorite: tobermorite --> dehydration tobermorite --> dehydroxylation tobermorite --> wollastonite.

Tear inflammation related indexes after cataract surgery in elderly patients with type 2 diabetes mellitus.

BACKGROUND: Quantitative studies on the changes in inflammation-related content in tears, especially the effect of diabetes, are lacking. In this study, we measured the preoperative and postoperative tear inflammatory mediator levels in cataract patients, focusing on the expression of inflammatory factors in postoperative cataracts in the diabetic, and investigated the effect of drugs on the control of postoperative inflammation. AIM: To study the expression of inflammatory factors in elderly people with type 2 diabetes after cataract surgery. METHODS: Patients with a mean age of 70.3 ± 6.3 years were divided into group A (composed of elderly patients with cataracts and type 2 diabetes, n = 20 eyes) and group B (patients with age-related cataract, n = 20 eyes). Their tears were collected before each operation and on days 1 and 3, and weeks 1, 2, 3, and 4 post-surgery. Saline (150 µL) was dropped into the conjunctival sac of the surgical eye, followed by oculogyration in four directions. The fluid in the conjunctival sac was extracted using a sterile syringe and stored in Eppendorf tubes at -80 °C until measurement. The expression levels of matrix metalloproteinase-2 (MMP-2), MMP-9, tissue inhibitor of metalloproteinase-1 (TIMP-1), TIMP-2, interleukin-6 (IL-6), and IL-20 in tear fluid were measured using enzyme-linked immunosorbent assays. RESULTS: The postoperative expression levels of MMP-2, MMP-9, TIMP-2, IL-6, and IL-20 in group A were significantly higher than those in group B, whereas the concentration of TIMP-1 in group A remained lower than that in group B. The levels of MMP-2 and IL-6 in both groups continuously increased until the peak in the first postoperative week, and then gradually decreased over the next three weeks. Ultimately, MMP-2 declined to a lower level than that preoperatively at week 4, but IL-6 decreased to the same level as that preoperatively. The level of MMP-9 peaked in the first two weeks postoperative and then returned to the same level as 1-day post-operation. The concentration of TIMP-1 post-operation remained constant at a lower level than before surgery, and TIMP-2 Levels remained stable in both groups. IL-20 content started to increase in the third week after surgery. CONCLUSION: Inflammatory factor levels in tears fluctuated before and post-operation, which indicated more severe postoperative inflammation in the first two weeks.

Human pathogens in ticks removed from humans in Hebei, China.

Ticks are the hosts or vectors of many human pathogens, including viruses, bacteria and protozoa, and can transmit these causative agents to humans when feeding on human bodies. In this study, 26 ticks removed from humans in Hebei, China were tested for the presence of human-pathogenic microorganisms by Polymerase Chain Reaction (PCR) or Reversed Transcript PCR (RT-PCR). As a result, 11 ticks tested positive for at least one human pathogen. Specifically, four validated human pathogens, including Rickettsia raoultii, Candidatus Rickettsia tarasevichiae, Babesia venatorum, and Borrelia garinii, as well as Anaplasma ovis with zoonotic potential, were identified in Ixodes persulcatus, Dermacentor silvarum and Haemaphysalis concinna. Importantly, this is the first report of Anaplasma and Babesia species pathogenic to humans in Hebei province. Moreover, the co-infections, including double infection and quadruple infection were observed. In addition, Candidatus R. principis with unknown pathogenicity was identified in one tick, which may be the same species as Candidatus R. hongyuanensis based on the nucleotide identity and phylogenetic analysis. Concluding, four validated tick-borne pathogens and one with zoonotic potential were identified in ticks parasitizing humans, suggesting the potential high public health risk in the local human population.

Chiral MOF Derived Wearable Logic Sensor for Intuitive Discrimination of Physiologically Active Enantiomer.

Chiral sensors have attracted growing interest due to their application in health monitoring. However, rational design of wearable logic chiral sensors remains a great challenge. In this work, a dual responsive chiral sensor RT@CDMOF is prepared through in situ self-assembly of chiral γ-cyclodextrin metal-organic framework (CDMOF), rhodamine 6G hydrazide (RGH), and tetracyanovinylindane (TCN). The embedded RGH and TCN inherit the chirality of host CDMOF, producing dual changes both in fluorescence and reflectance. RT@CDMOF is explored as a dual channel sensor for chiral discrimination of lactate enantiomers. Comprehensive mechanistic studies reveal the chiral binding process, and carboxylate dissociation is confirmed by impedance and solid-state 1 H nuclear magnetic resonance (NMR). A flexible membrane sensor is successfully fabricated based on RT@CDMOF for wearable health monitoring. Practical evaluation confirms the potential of fabricated membrane sensor in point-of-care health monitoring by indexing the exercise intensity. Based on above, a chiral IMPLICATION logic unit can be successfully achieved, demonstrating the promising potential of RT@CDMOF in design and assembly of novel smart devices. This work may open a new avenue to the rational design of logic chiral sensors for wearable health monitoring applications.

Porous metalloporphyrinic frameworks constructed from metal 5,10,15,20-tetrakis(3,5-biscarboxylphenyl)porphyrin for highly efficient and selective catalytic oxidation of alkylbenzenes.

We incorporate metal 5,10,15,20-tetrakis(3,5-biscarboxylphenyl)porphyrin (M-H(8)OCPP), for the first time, into porous metal-organic frameworks. The self-assembled porous metalloporphyrinic frameworks [Mn(5)Cl(2)(MnCl-OCPP)(DMF)(4)(H(2)O)(4)]·2DMF·8CH(3)COOH·14H(2)O (ZJU-18; ZJU = Zhejiang University), [Mn(5)Cl(2)(Ni-OCPP)(H(2)O)(8)]·7DMF·6CH(3)COOH·11H(2)O (ZJU-19), and [Cd(5)Cl(2)(MnCl-OCPP)(H(2)O)(6)]·13DMF·2CH(3)COOH·9H(2)O (ZJU-20) are isostructural as revealed by their single X-ray crystal structures. The metalloporphyrin octacarboxylates (M-OCPP) (M = Mn(III)Cl for ZJU-18 and ZJU-20, M = Ni(II) for ZJU-19) are bridged by binuclear and trinuclear metal carboxylate secondary building units to form a 3-periodic, binodal, edge-transitive net with Reticular Chemistry Structure Resource symbol tbo with pore windows of about 11.5 Å and pore cages about 21.3 Å in diameter. The porous nature of these metalloporphyrinic frameworks is further established by sorption studies in which different substrates such as ethanol, acetonitrile, acetone, cyclohexane, benzene, toluene, ethylbenzene, and acetophenone can readily have access to the pores. Their catalytic activities for the oxidation of alkylbenzenes were examined at 65 °C using tert-butyl hydroperoxide as the oxidant. The results indicate that ZJU-18 is much superior to ZJU-19, ZJU-20, and homogeneous molecular MnCl-Me(8)OCPP, exhibiting highly efficient and selective oxidation of ethylbenzene to acetophenone in quantitative >99% yield and a turnover number of 8076 after 48 h.