Precise Post-Synthetic Modification of Heterometal-Organic Capsules for Selectively Encapsulating Tetrahedral Anions.

Post-synthetic modification plays a crucial role in precisely adjusting the structure and functions of advanced materials. Herein, we report the self-assembly of a tubular heterometallic Pd3Cu6L16 capsule that incorporates Pd(II) and CuL1 metalloligands. This capsule undergoes further modification with two tridentate anionic ligands (L2) to afford a bicapped Pd3Cu6L16L22 capsule with an Edshammer polyhedral structure. By employing transition metal ions, acid, and oxidation agents, the bicapped capsule can be converted into an uncapped one. This uncapped form can then revert back to the bicapped structure on the addition of Br- ions and a base. Interestingly, introducing Ag+ ions leads to the removal of one L2 ligand from the bicapped capsule, yielding a mono-capped Pd3Cu6L16L2 structure. Furthermore, the size of the anions critically influences the precise control over the post-synthetic modifications of the capsules. It was demonstrated that these capsules selectively encapsulate tetrahedral anions, offering a novel approach for the design of intelligent molecular delivery systems.

A Self-Assembled Capsule for Propylene/Propane Separation.

The development of energy-saving technology for the efficient separation of olefin and paraffin is highly important for the chemical industry. Herein, we report a self-assembled Fe4 L6 capsule containing a hydrophobic cavity, which can be used to encapsulate and separate propylene/propane. The successful encapsulation of propylene and propane by the Fe4 L6 cage in a water solution was documented by NMR spectroscopy. The binding constants K for the Fe4 L6 cage toward propylene and propane were determined to be (5.0±0.1)×103  M-1 and (2.1±0.7)×104  M-1 in D2 O at 25 °C, respectively. Experiments and theoretical studies revealed that the cage exhibited multiple weak interactions with propylene and propane. The polymer-grade propylene (>99.5 %) can be obtained from a mixture of propylene and propane by using the Fe4 L6 cage as a separation material in a U-shaped glass tube. This work provides a new strategy for the separation of olefin/paraffin.

Highly Boosting Circularly Polarized Luminescence of Chiral Metal-Imidazolate Frameworks.

To develop a simple and general method for improving the circularly polarized luminescence (CPL) performances of materials is of great significance. In this work, two pairs of CPL-active homochiral metal-organic frameworks (MOFs) P/M-Et and P/M-Et(Cd) with eta topology are reported. In comparison to the reported isomorphic Zn-imidazolate MOFs P-Me and M-Me, both luminescence dissymmetry factor (glum ) and photoluminescence quantum yields (ΦPL ) of P-Et and M-Et are largely improved by simply changing the methyl group to an ethyl group of ligands in P-Et and M-Et. Furthermore, the |glum | values are significantly amplified up to 0.015 from 0.0057 by introducing the non-luminescent halogenated aromatics, while an enhanced fluorescence efficiency is observed simultaneously (from 27.2% to 47.3%). The figure of merit value is about 40 times larger than that of P-Me and M-Me. Similarly, the CPL performances of P/M-Et(Cd) are improved by about five times after encapsulating fluorobenzene molecules. This work represents a new and simple method for developing CPL-active MOF materials.

Self-Assembly of a Pd4Cu8L8 Cage for Epoxidation of Styrene and Its Derivatives.

Herein we report a discrete heterometallic Pd4Cu8L8 cage with a tubular structure, which was synthesized by the assembly of copper metalloligands and PdII ions in a stepwise manner. The Pd4Cu8L8 cage has been unequivocally characterized by single-crystal X-ray diffraction, electrospray ionization-mass spectroscopy, and energy dispersive spectroscopy. The cage showed excellent catalytic activity in the epoxidation of styrene and its derivatives under conditions without using additional solvent, providing potential material for catalyzing the oxidation reactions.

Activation of Subcutaneous Mast Cells in Acupuncture Points Triggers Analgesia.

This review summarizes experimental evidence indicating that subcutaneous mast cells are involved in the trigger mechanism of analgesia induced by acupuncture, a traditional oriental therapy, which has gradually become accepted worldwide. The results are essentially based on work from our laboratories. Skin mast cells are present at a high density in acupuncture points where fine needles are inserted and manipulated during acupuncture intervention. Mast cells are sensitive to mechanical stimulation because they express multiple types of mechanosensitive channels, including TRPV1, TRPV2, TRPV4, receptors and chloride channels. Acupuncture manipulation generates force and torque that indirectly activate the mast cells via the collagen network. Subsequently, various mediators, for example, histamine, serotonin, adenosine triphosphate and adenosine, are released from activated mast cells to the interstitial space; they or their downstream products activate the corresponding receptors situated at local nerve terminals of sensory neurons in peripheral ganglia. The analgesic effects are thought to be generated via the reduced electrical activities of the primary sensory neurons. Alternatively, these neurons project such signals to pain-relevant regions in spinal cord and/or higher centers of the brain.

Improving Ethane/Ethylene Separation Performance under Humid Conditions by Spatially Modified Zeolitic Imidazolate Frameworks.

Gas separation performances are usually degraded under humid conditions for many crystalline porous materials because of the lack of water stability and/or the competition of water vapor toward the interaction sites (e.g., open metal sites). Zeolitic imidazolate frameworks (ZIFs) are suitable candidates for practical applications in gas separation because of their excellent physical/chemical stabilities. However, the limitation of substituent positions in common ZIFs has prevented extensive pore engineering to improve their separation performance. In a type of gyroidal ZIFs with gie topology, the Schiff base moiety provides additional substituent positions, making it possible to modify the spatial arrangement of hydrophobic methyl groups. Herein, a new gyroidal ZIF, ZnBAIm (H2BAIm = 1,2-bis(1-(1H-imidazol-4-yl)ethylidene)hydrazine), is designed, synthesized, and characterized. The spatially modified ZnBAIm exhibits improved thermal/chemical/mechanical stabilities compared to ZnBIm (H2BIm = 1,2-bis((5H-imidazol-4-yl)methylene)hydrazine). ZnBAIm can remain intact up to about 480 °C in a N2 atmosphere and tolerate harsh treatments (e.g., 5 M NaOH aqueous solution at room temperature for 24 h and 190 MPa high pressure in the presence of water). Moreover, the modified pore and window sizes have improved significantly the ethane/ethylene selectivity and separation performance under humid conditions for ZnBAIm. Breakthrough experiments demonstrate efficient separation of a C2H6/C2H4 (50/50, v/v) binary gas mixture under ambient conditions; more importantly, the C2H6/C2H4 separation performance is unaffected under highly humid conditions (up to 80% RH). The separation performance is attributed to combined thermodynamic (stronger dispersion interaction with C2H6 than with C2H4) and kinetic factors (diffusion), determined by density functional theory calculations and kinetic adsorption study, respectively.

Schisandrin Protects against Norepinephrine-Induced Myocardial Hypertrophic Injury by Inhibiting the JAK2/STAT3 Signaling Pathway.

Aims. Heart failure is closely associated with norepinephrine-(NE-) induced cardiomyocyte hypertrophy. Schisandrin is derived from the traditional Chinese medicine Schisandra; it has a variety of pharmacological activities, and the mechanism of schisandrin-mediated protection of the cardiovascular system is not clear. Main Methods. NE was used to establish a cardiomyocyte hypertrophy model to explore the mechanism of action of schisandrin. An MTT assay was used for cell viability; Hoechst fluorescence staining was used to observe the cell morphology and calculate the apoptosis rate. The cell surface area was measured and the protein to DNA ratio was calculated, changes in mitochondrial membrane potential were detected, and the degree of hypertrophic cell damage was evaluated. WB, QRT-PCR, and immunofluorescence were used to qualitatively, quantitatively, and quantitatively detect apoptotic proteins in the JAK2/STAT3 signaling pathway. Key Findings. In the NE-induced model, schisandrin treatment reduced the apoptosis rate of cardiomyocytes, increased the ratio of the cell surface area to cardiomyocyte protein/DNA, and also, increased the membrane potential of the mitochondria. The expression of both JAK2 and STAT3 was downregulated, and the BAX/Bcl-2 ratio was significantly reduced. In conclusion, schisandrin may protect against NE-induced cardiomyocyte hypertrophy by inhibiting the JAK2/STAT3 signaling pathway and reducing cardiomyocyte apoptosis.

Cobalt-Based Metal-Organic Cages for Visible-Light-Driven Water Oxidation.

Water oxidation to molecular oxygen is indispensable but a challenge for splitting H2O. In this work, a series of Co-based metal-organic cages (MOCs) for photoinduced water oxidation were prepared. MOC-1 with both bis(µ-oxo) bridged dicobalt and Co-O (O from H2O) displays catalytic activity with an initial oxygen evolution rate of 80.4 mmol/g/h and a TOF of 7.49 × 10-3 s-1 in 10 min. In contrast, MOC-2 containing only Co-O (O from H2O) in the structure results in a lower oxygen evolution rate (40.8 mmol/g/h, 4.78 × 10-3 s-1), while the amount of oxygen evolved from the solution of MOC-4 without both active sites is undetectable. Isotope experiments with or without H218O as the reactant successfully demonstrate that the molecular oxygen was produced from water oxidation. Photophysical and electrochemical studies reveal that photoinduced water oxidation initializes via electron transfer from the excited [Ru(bpy)3]2+* to Na2S2O8, and then, the cobalt active sites further donate electrons to the oxidized [Ru(bpy)3]3+ to drive water oxidation. This proof-of-concept study indicates that MOCs can work as potential efficient catalysts for photoinduced water oxidation.

Iron(II) Metal-Organic Framework with unh Topology and Tetrazole-Padded Helical Channels.

A unique metal-organic framework (MOF) with tetrazole-padded helical channels has been successfully synthesized in one pot from iron(II) trifluoromethanesulfonate, 4-formylimidazole, hydrazine, and sodium azide under solvothermal conditions and features a rare unh topology and porous structure for gas adsorption. Transformations of condensation, cycloaddition, and coordination occurred during the synthetic process, in which a 1,5-disubstituted tetrazole ligand was formed in situ.

Self-assembly of a Mixed Valence Copper Triangular Prism and Transformation to Cage Triggered by an External Stimulus.

A triangular prismatic metal-organic cage based on mixed valence copper ions has been designed and synthesized by using metallocycle panels and pillar ligands. The triangular prism will be quickly transformed to a 10-nuclear cage upon an external chemical stimulus, which features a bicapped square antiprism structure. This prismatic cage can act as a catalyst for oxidation of aromatic alcohols to their corresponding aromatic aldehydes with high yields at room temperature under O2 atmosphere.

Self-assembly of mixed-valence and heterometallic metallocycles: efficient catalysts for the oxidation of alcohols to aldehydes in ambient air.

Two mixed-valence CuII/CuI and two heterometallic CuII/AgI metallocycles have been synthesized by the assembly of designed metalloligands and CuI/AgI ions, respectively. The CuII/CuI metallocycle can catalyze the oxidation of alcohols to aldehydes mediated by a co-catalyst, TEMPO (2,2,6,6-tetramethylpiperdine-1-oxyl), with ambient air as an oxidant, while the CuII/AgI metallocycle has no catalytic effect.

Coordination-driven self-assembly of M10L8 metal-organic bi-capped square antiprisms with adaptable cavities.

A family of polyhedral metal-imidazolate cages based on the flexible bi-imidazole ligand L and Cu2+ ions have been synthesized and characterized, featuring an unusual Cu10L8 bicapped square antiprism structure (or Johnson solids, J17) with an adaptable cavity. These metal-organic cages encapsulate anions, and they will expand or compress after they are filled with different-sized anions.

Assembly of Metal-Organic Frameworks of SiF62- in Situ Formed from Borosilicate Glass.

The SiF62- anions are in situ formed in the reactions of MF2 (M = Cu2+, Zn2+, Ni2+, and Co2+) salts and nitrogen-containing ligands in borosilicate glass tubes under solvothermal conditions and then used to further construct a family of metal-organic frameworks (MOFs). This in situ reaction demonstrates a new and facile strategy for the fabrication of MOFs based on SiF62-.

Immunological Evaluation of a Novel Mycobacterium tuberculosis Antigen Rv0674.

OBJECTIVE: This study aimed to characterize the diagnostic and vaccine potential of a novel Mycobacterium tuberculosis antigen Rv0674. METHODS: To evaluate the diagnostic potential and antigenicity of Rv0674, IgG was evaluated using ELISA and interferon (IFN)-γ was done by using ELISpot assay among TB patients and healthy donors. For immunogenicity evaluation, BALB/c mice were immunized with Rv0674. Cytokine production was determined by cytokine release assay using an ELISA kit, and the antibodies were tested using ELISA. RESULTS: The results of serum Elisa tests showed that Rv0674 specific immunoglobulin G (IgG) response was higher in TB patients than negative controls. And Rv0674 had good performance in serological test with sensitivity and specificity of 77.1% and 81.1%, respectively. While it shows poor sensitivity and specificity of 26.23% and 79.69% for IFN-γ tests. In BALB/c mice, Rv0674 adjuvant by DDA/Poly I:C could also induce a high level of IFN-γ, interleukin-2 and interleukin-6 as well as a high IgG titer in both high- and low-dose groups indicating that Rv0674 is essential in humoral and cellular immunity. Moreover, the cytokine profile and IgG isotype characterized Rv0674 as a Th1/Th2-mixed-type protective immunity with the predominance of Th1 cytokines. CONCLUSION: Rv0674 may be a good potential candidate for the development of TB serological diagnosis and a new TB vaccine.

Bipolar Blue Host Emitter with Unity Quantum Yield Allows Full Exciton Radiation in Single-Emissive-Layer Hybrid White Organic Light-Emitting Diodes.

Phosphorescence/fluorescence hybrid white organic light-emitting diodes (OLEDs) are highly appealing for solid-state lighting. One major challenge is how to fully utilize the electrically generated excitons for light output. Herein, an efficient strategy to realize full exciton radiation is successfully revealed by a judicious molecular design and suitable device engineering. A blue host emitter TP-PPI is designed and synthesized, exhibiting a near 100% photoluminescence quantum yield and a high triplet energy level, enabling high-performance blue fluorescence and sensitization of a yellow phosphorescent dopant. Full exciton radiation in hybrid white OLEDs is demonstrated with a single emitting layer formed by doping a yellow phosphor (PO-01) into TP-PPI. Near 100% exciton utilization and state-of-the-art external quantum efficiency of 27.5% are achieved with the high-efficiency blue-emitting host and an electron-trap engineered device architecture.

Wogonin exacerbates the cytotoxic effect of oxaliplatin by inducing nitrosative stress and autophagy in human gastric cancer cells.

BACKGROUND: Gastric cancer remains one of the leading cause of death in the world. Drug combinations are potential approaches to provide more efficient treatments that minimize side effects. PURPOSE: We investigated the pharmacological effects of the combination of wogonin with oxaliplatin on gastric cancer cells in vitro and in vivo. METHODS AND RESULTS: In the present study, we found that wogonin enhanced the cytotoxicity of oxaliplatin; the drug combination resulted in strong synergistic inhibition of the cell viability in BGC-823 cells and in a zebrafish xenograft model. Interestingly, the combined treatment of wogonin and oxaliplatin modulated the expression of phospho-JNK (Thr183/Tyr185), phospho-ULK1 (Ser555) and the formation of LC3II. Confocal imaging data consistently showed that wogonin exacerbates the oxaliplatin-induced dissipation of the mitochondrial membrane potential (ΔΨm) and formation of peroxynitrite in BGC-823 cells. Moreover, wogonin allows a reduction in oxaliplatin dose when they are combined; therefore, it is a relevant strategy for reducing the side effects of oxaliplatin while achieving the same response. CONCLUSION: These results suggest that wogonin can be a potential therapeutic candidate for enhancing the efficacy of oxaliplatin in gastric cancer treatment.

Self-Assembly of Chiral Metal-Organic Tetartoid.

Chiral coordination cages feature both chirality and defined inner space, providing advanced molecular materials. A series of chiral 20-nucleus cobalt-imidazolate cages were synthesized by self-assembly of 72 subcomponents, featuring a novel tetartoid (tetragonal pentagonal dodecahedron) structure. Spontaneous resolution of racemic tetartoidal cages (Δ and Λ) into a conglomerate of homochiral crystals are observed, while both homochiral Δ and Λ tetartoidal cages can be obtained through chiral induction of (d)- and (l)-enantiomers of menthol, respectively. The 2-methyl substituent on imidazolyl is critical to the formation of a tetartoidal cage, and the absence of such steric effect will switch the final structure to a cubic cage.

The correlation between XIAP gene polymorphisms and esophageal squamous cell carcinoma susceptibility and prognosis in a Chinese population.

OBJECTIVE: This study aims to explore the correlation between X-linked inhibitor of apoptosis protein (XIAP) gene polymorphisms (rs8371 and rs9856) with the susceptibility and prognosis of esophageal squamous cell carcinoma (ESCC), providing a potential treatment for ESCC. METHOD: A total of 170 ESCC patients (case group) and 191 healthy people (control group) were enrolled in our study. Genotyping was conducted on the basis of the ligase detection reaction (LDR). The expressions of XIAP polymorphisms were detected. The patients were followed up every three months until death or the last follow-up day. The overall survival (OS) and progression free survival (PFS) were recorded by Kaplan-Meier survival curve, and the relationship between XIAP gene polymorphism and risk and prognosis of ESCC was assessed by Cox multivariate analysis. RESULT: TT+CT genotype and T allele frequencies of XIAP rs8371 and rs9856 in the case group were significantly lower compared to those of the control group (all P<0.05), suggesting that TT+CT genotype of XIAP rs8371 and rs9856 was associated with ESCC susceptibility. XIAP rs8371 and rs9856 polymorphisms were associated with tumor node metastasis (TNM) staging, depth of invasion and lymph node metastasis. The OS and PFS of TT+CT genotype carriers of rs8371 were longer than those of CC genotype carriers. Smoking, alcohol, TNM staging, depth of invasion, and lymph node metastasis were significantly associated with the OS and PFS in ESCC patients. Higher TNM staging, depth of invasion, and presence of lymph node metastasis were independent risk factors, while XIAP rs8371 was an independent protective factor for the prognosis of ESCC patients. CONCLUSION: The present study demonstrates that XIAP rs8371 and rs9856 are associated with susceptibility to ESCC, and rs8371 polymorphisms might serve as an indicator for improved clinical efficacy and prognosis of ESCC patients.

[Efficacy of ACEI in the treatment of hypertension and the effect of secondary prevention in patients complicated with coronary heart disease and stroke].

OBJECTIVE: To investigate the efficacy of ACEI drugs in the treatment of hypertension patients and the effect of two levels of prevention of hypertension complicated with coronary heart disease and stroke. METHDOS: 210 cases of hypertension patients in our hospital from January 2012 to December 2015 were randomly divided into experimental group and control group, 105 cases in each group. According to the conventional symptomatic treatment, the experimental group was given lisinopril treatment, while control group was given the captopril treatment. Changes of blood pressure parameters and the level of baPWV in two groups were observed before and after treatment coronary heart disease and stroke, recurrence rate and death rate were compared in these two groups. RESULTS: No significant difference of SBP, DBP, PP and baPWV between two groups before treatment (P>0.05). The indexes of the two groups were significantly decreased after 1 months and 3 months, and the level of patients in the experimental group was lower than that of the control group (P<0.05). The recurrence rate in the experimental group was lower than those in the control group (P<0.05). CONCLUSIONS: ACEI drugs in the treatment of hypertension can effectively reduce the level of blood pressure, improve arterial elasticity function, reduce the recurrence rate and mortality rate of coronary heart disease and stroke. The effect of antihypertensive and two levels of prevention of hypertension complicated with coronary heart disease and stroke of lisinopril is positive.