Artificial Light-Harvesting Metallacycle System with Sequential Energy Transfer for Photochemical Catalysis.

Highly efficient light-harvesting systems with the sequential energy transfer process are significant for utilizing solar energy in photosynthesis. Herein, we report a quadrilateral platinum(II) metallacycle containing tetraphenylethylene (M1) as a light-harvesting platform. The M1 assembly serves as an ideal donor because of the aggregation-induced emission (AIE) effect, realizing two-step sequential energy transfer from the M1 assembly to eosin Y (ESY) and then to sulforhodamine (SR101) with high efficiency. ESY was used as a bridge in a relay mode during this process. To better mimic natural photosynthesis, the M1-ESY-SR101 system was utilized as photochemical catalysis for alkylation of C-H bonds in aqueous solution, showing enhanced catalytic activity as compared with the M1-ESY system or ESY/SR101 alone.

Hexabenzocoronene Graphitic Nanocoils Appended with Crown Ethers: Supramolecular Chirality Induced by Host-Guest Interaction.

We have designed and synthesized two new achiral hexa-peri-hexabenzocoronene (HBC) derivatives, HBCCE and HBCTEG-CE , which bear the crown ether as the pendant for the amino acid binding site. The HBCCE self-assembled into a racemic mixture of P- and M-handed helical nanocoils, however, in the presence of chiral amino acid guests, it formed helical nanocoils with one-handed screw sense. The effects of the concentration, type and configuration of the guests on the induced circular dichroism (ICD) during the co-assembly of HBCCE with chiral amino acids were also investigated. Additionally, after complete removal of the chiral guests, the optically active nanocoils did not racemize, even in the presence of excess amino acids with the opposite configuration. In contrast, HBCTEG-CE with a long triethylene glycol (TEG) chain between the crown ether group and the HBC unit did not exhibit ICD during the co-assembly with chiral amino acids.

The effect of renal denervation on resistant hypertension: Meta-analysis of randomized controlled clinical trials.

BACKGROUND: This meta-analysis was conducted to evaluate the efficiency of renal denervation (RDN) on resistant hypertension. METHODS: PubMed, EMBASE, and the Cochrane Central database were searched for eligible randomized controlled clinical trials (RCTs). Changes from the baseline of the office blood pressure and the 24-h ambulatory blood pressure were extracted. RESULTS: Nine RCTs were included. RDN reduced the mean systolic blood pressure (SBP) and diastolic blood pressure (DBP) by -8.23 mm Hg (95%CI: -16.86, 0.39) and -3.77 mm Hg (95%CI: -7.21, -0.32), respectively, compared with the control. In the population with a baseline SBP more than 170 mm Hg, the RDN reduced SBP by -17.77 mm Hg (95%CI: -33.73, -1.82) and DBP by -7.51 mm Hg (95%CI: -12.58, -2.44). In the subgroup with no medication adjustment, the RDN reduced SBP by -15.56 mm Hg (95%CI: -26.33, -4.80) and DBP by -6.89 mm Hg (95%CI: -9.99, -3.79). The proportion of patients with SBP decrease of 10 mm Hg or more and the controlled office BP were not different between two groups. RDN reduced 24-h mean SBP and DBP by -3.34 mm Hg (95%CI: -5.30, -1.38) and -1.56 mm Hg (95%CI: -2.71, -0.41), respectively. The SBPs in the subgroups with higher baseline SBP and with no medication adjustment were significantly decreased after the HTN-3 was omitted. CONCLUSION: Radiofrequency RDN in a randomized manner did not have superiority compared with medical treatment at 6-month follow-up in general population. Current evidence provides insufficient evidence to support the use of such RDN strategy in the treatment of resistant hypertension. The result could not be used to extrapolate other strategies' effect.

Size-selective recognition by a tubular assembly of phenylene-pyrimidinylene alternated macrocycle through hydrogen-bonding interactions.

Study of artificial tubular assemblies as a useful host scaffold for size-selective recognition and release of guest molecules is an important subject in host-guest chemistry. We describe well-defined self-assembled nanotubes (NT6mer) formed from π-conjugated m-phenylene-pyrimidinylene alternated macrocycle 16mer that exhibit size-selective recognition toward a specific aromatic acid. In a series of guest molecules, a size-matched trimesic acid (G3) gives inclusion complexes (NT6mer⊃G3) in dichloromethane resulting in an enhanced and red-shifted fluorescence. (1)H nuclear magnetic resonance (NMR) titration experiments indicated that the complex was formed in a 1:1 molar ratio. Density functional theory (DFT) calculations and the binding constant value (K = 1.499 × 10(5) M(-1)) of NT6mer with G3 suggested that the complex involved triple hydrogen-bonding interactions. The encapsulated guest G3 molecules can be readily released from the tubular channel through the dissociation of hydrogen bonding by the addition of a polar solvent such as dimethylsulfoxide (DMSO). In contrast, 16mer could not form self-assembled nanotubes in CHCl3 or tetrahydrofuran (THF) solution, leading to weak or no size-selective recognizability, respectively.

Photoreversible [2] Catenane via the Host-Guest Interactions between a Palladium Metallacycle and ß-Cyclodextrin.

We report the efficient preparation of an A2D2 (A = acceptor and D = donor) metallacycle 2 = [(en)2Pd2(1)2](NO3)4, using the coordination driven self-assembly of trans-azobenzene based bispyridyl ligand 1 and (en)Pd(NO3)2 (en = ethylenediamine). In the metallacycle, the trans-azobenzene units serve both as a structural element and as sites for subsequent host-guest chemistry with ß-cyclodextrin, leading to the formation of a [2] catenane 3. This catenation process is reversible and can be switched off and on in a photocontrollable manner via the trans-cis isomerization of the azobenzene units.

Levosimendan Improves Clinical Outcomes of Refractory Heart Failure in Elderly Chinese Patients.

BACKGROUND: Levosimendan has been extensively used to treat heart failure (HF) for nearly 10 years, but data on levosimendan used in elderly patients with refractory HF remains limited. This study aimed to investigate the effects of levosimendan on elderly patients with intractable HF. MATERIAL AND METHODS: A total of 268 patients with HF (over 70 years, New York Heart Association [NYHA] classification III-IV, LVEF ≤40%, plasma NT-proBNP ≥1000 pg/mL) received conventional anti-HF therapies for 2 weeks. Such therapies include the limiting of salt intake, increasing myocardial contractility (without levosimendan), inducing urine, antagonizing aldosterone, antagonizing myocardial remodeling, and, if necessary, using antibiotics. Our study included 42 patients without symptoms whose improvement was re-evaluated and presented in NYHA class III-IV, LVEF ≤40%, plasma NT-proBNP ≥1000.0 pg/mL, and serum creatinine <110.0 µmol/L. These patients were divided into an experimental groups (n=21, treated with levosimendan) and a control group (n=21, continuously given regular treatment as before). After 1 week, 42 patients were assessed for changes in NYHA classification, LVEF, and NT-proBNP. RESULTS: No severe complications related to levosimendan were noted. Compared with the control group, NYHA classification (I-II: 1 versus 21, III-IV: 20 versus 0, P<0.05) and LVEF (30.62±6.19% versus 45.83±5.06%, P<0.05) were increased, and plasma NT-proBNP was reduced (458.35±193.16 pg/mL versus 2921.52±1395.97 pg/mL, P<0.05) in the experimental group. CONCLUSIONS: Our study showed levosimendan significantly and safely improved clinical outcomes of refractory heart failure in elderly patients.

2-[3-Meth-oxy-5-(pyrimidin-2-yl)phen-yl]pyrimidine.

The title compound, C15H12N4O, was synthesized by a standard Suzuki cross-coupling reaction. The terminal pyrim-idine rings are rotated at dihedral angles of 12.06 (4) and -13.13 (4)° with respect to the central benzene ring. In the crystal, the mol-ecules are connected by two kinds of C-H⋯N hydrogen bonds, forming zigzag chains along the c axis. Weak π-π inter-actions between the benzene and one of the pyrimidine rings are also found and stack the mol-ecules along the b axis [centroid-centroid distance = 4.112 (3) Å].

Three-step cascaded artificial light-harvesting systems with tunable efficiency based on metallacycles.

It is still challenging to develop multi-step cascaded artificial light-harvesting systems (ALHSs) with tunable efficiency. Here, we designed novel cascaded ALHSs with AIE-active metallacycles as the light-harvesting antenna, Eosin Y (ESY) and sulforhodamine 101 (SR101) as conveyors, near-infrared emissive chlorin-e6 (Ce6) as the final acceptor. The close contact and fair spectral overlap between donor and acceptor molecules at each level ensured the efficient sequential three-step energy transfer. The excited energy was sequentially and efficiently funneled to Ce6 along the cascaded line MTPEPt1 â†’ ESY â†’ SR101 â†’ Ce6. Additionally, a unique strategy for regulating the efficiency of ALHS was illustrated by adjusting hydrophilic and hydrophobic interactions.

Near-Infrared Emissive Cascaded Artificial Light-Harvesting System with Enhanced Antibacterial Efficiency.

Combination of platinum(II) metallacycles and photodynamic inactivation presents a promising antibacterial strategy. Herein, a cascaded artificial light-capturing system is developed in which an aggregation-induced emission-active platinum(II) metallacycle (PtTPEM) is utilized as the antenna, sulforhodamine 101 (SR101) as a key conveyor, and the near-infrared emissive photosensitizer Chlorin-e6 (Ce6) as the final energy acceptor. The well-dispersed Ce6 in the proximity of energy donors not only avoids self-quenching in the physiological environment but also contributes to energy transfer from donor to acceptor, thereby significantly improving the 1 O2 generation ability of the light-harvesting system under white light irradiation. By integrating the platinum(II) metallacycle and 1 O2 , a more efficient synergistic antibacterial effect is achieved at low concentrations, along with a significant decrease in dark toxicity caused by PtTPEM.

Trichlorido[4-meth-oxy-2,6-bis-(2-pyrimidin-2-yl-κN)phenyl-κC(1)]platinum(IV) acetonitrile monosolvate.

In the title complex, [Pt(C(15)H(11)N(4)O)Cl(3)]·CH(3)CN, the Pt(IV) ion adopts a distorted octa-hedral coordination geometry defined by a tridentate cyclo-metalated NCN ligand and three Cl atoms. In the crystal, individual mol-ecules are aggregated into a three-dimensional network by C-H⋯Cl hydrogen-bonding inter-actions and π-π stacking inter-actions between the tridentate ligands, the shortest ring centroid-centroid distance being 3.613 Å.

An ECG Heartbeat Classification Method Based on Deep Convolutional Neural Network.

The electrocardiogram (ECG) is one of the most powerful tools used in hospitals to analyze the cardiovascular status and check health, a standard for detecting and diagnosing abnormal heart rhythms. In recent years, cardiovascular health has attracted much attention. However, traditional doctors' consultations have disadvantages such as delayed diagnosis and high misdiagnosis rate, while cardiovascular diseases have the characteristics of early diagnosis, early treatment, and early recovery. Therefore, it is essential to reduce the misdiagnosis rate of heart disease. Our work is based on five different types of ECG arrhythmia classified according to the AAMI EC57 standard, namely, nonectopic, supraventricular ectopic, ventricular ectopic, fusion, and unknown beat. This paper proposed a high-accuracy ECG arrhythmia classification method based on convolutional neural network (CNN), which could accurately classify ECG signals. We evaluated the classification effect of this classification method on the supraventricular ectopic beat (SVEB) and ventricular ectopic beat (VEB) based on the MIT-BIH arrhythmia database. According to the results, the proposed method achieved 99.8% accuracy, 98.4% sensitivity, 99.9% specificity, and 98.5% positive prediction rate for detecting VEB. Detection of SVEB achieved 99.7% accuracy, 92.1% sensitivity, 99.9% specificity, and 96.8% positive prediction rate.

Heart Disease Prediction Based on the Embedded Feature Selection Method and Deep Neural Network.

In recent decades, heart disease threatens people's health seriously because of its prevalence and high risk of death. Therefore, predicting heart disease through some simple physical indicators obtained from the regular physical examination at an early stage has become a valuable subject. Clinically, it is essential to be sensitive to these indicators related to heart disease to make predictions and provide a reliable basis for further diagnosis. However, the large amount of data makes manual analysis and prediction taxing and arduous. Our research aims to predict heart disease both accurately and quickly through various indicators of the body. In this paper, a novel heart disease prediction model is given. We propose a heart disease prediction algorithm that combines the embedded feature selection method and deep neural networks. This embedded feature selection method is based on the LinearSVC algorithm, using the L1 norm as a penalty item to choose a subset of features significantly associated with heart disease. These features are fed into the deep neural network we built. The weight of the network is initialized with the He initializer to prevent gradient varnishing or explosion so that the predictor can have a better performance. Our model is tested on the heart disease dataset obtained from Kaggle. Some indicators including accuracy, recall, precision, and F1-score are calculated to evaluate the predictor, and the results show that our model achieves 98.56%, 99.35%, 97.84%, and 0.983, respectively, and the average AUC score of the model reaches 0.983, confirming that the method we proposed is efficient and reliable for predicting heart disease.

Synthesis and biological activity of some 1,3-dihydro-2H-3-benzazepin-2-ones with a piperazine moiety as bradycardic agents.

A series of 1,3-dihydro-2H-3-benzazepin-2-ones with a piperazine moiety were designed and synthesized by treating the common intermediate of 1,3-dihydro-7,8-dimethoxy-3-[3-(1-piperazinyl)propyl]-2H-3-benzazepin-2-ones with a variety of N-aryl-2-chloroacetamides and acyl chlorides. Their structures have been characterized by (1)H-NMR, MS, and elemental analysis. The title compounds were evaluated for their bradycardic activity in vitro. Most of the synthesized compounds exhibited some vasorelaxant activity and heart-rate-reducing activity with bradycardic potency.

Chlorogenic Acid Suppresses miR-155 and Ameliorates Ulcerative Colitis through the NF-κB/NLRP3 Inflammasome Pathway.

SCOPE: The over-activation of the nucleotide-binding domain like receptor protein 3 (NLRP3) inflammasome plays an important role in the pathogenesis of ulcerative colitis (UC). Chlorogenic acid (CGA) exposure is identified as an effective strategy for repressing inflammatory responses. METHODS AND RESULTS: In this study, the NLRP3 inflammasome model with LPS/ATP-induced RAW264.7 cells in vitro and dextran-sulfate-sodium (DSS)-induced colitis in mice are used to evaluate the effect of CGA on NLRP3 inflammasome-related signaling. The results suggest that CGA suppressed the expression of NLRP3 inflammasome-related genes (apoptosis-associated speck-like protein containing CARD (ASC), cysteine-requiring aspartate protease (Caspase)-1 p45, Caspase-1 p20, pro-/cleaved-interleukin (IL)-1ß, pro-/cleaved-IL-18), p-nuclear factor kappa B (NF-κB) protein, and miR-155 in mice with colitis. Gain- and loss-of-function studies of miR-155 are performed to elucidate its role in inflammation. Moreover, activation of the NF-κB/NLRP3 inflammasome pathway and miR-155 expression is investigated. CGA exposure in lipopolysaccharide (LPS)/adenosine triphosphate (ATP)-stimulated RAW264.7 cells leads to a decrease in p-NK-κB and NLRP3 inflammasome-related proteins, which is dependent on the downregulation of miR-155 expression. CONCLUSIONS: These findings indicate that CGA prevented colitis by downregulating miR-155 expression and inactivating the NF-κB/NLRP3 inflammasome pathway in macrophages. The current study has promising therapeutic implications in the treatment of UC.

Cardiac Denervation for Arrhythmia Treatment with Transesophageal Ultrasonic Strategy in Canine Models.

Stellate ganglion (SG) modification has been investigated for arrhythmia treatment. In this study, transesophageal SG imaging and intervention were explored using a homemade 30F integrated focused ultrasonic catheter in healthy mongrel canines in vivo. Anatomic details of SGs were ultrasonically imaged and evaluated. SG had a heterogeneous echoic structure and characteristic profiles sketched by hyper-echoic outlines in an ultrasonogram. Left SGs in the experimental group were successfully ablated through the esophagus under ultrasonic guidance provided by the catheter itself. Two weeks after the ablation, the QT and QTc of the experimental group decreased compared with those of the sham group and at baseline (both p values < 0.001). Histologic examination revealed that left SGs were destroyed. No major complications were observed. This approach may be further explored as a method for ganglia remodeling evaluation and as a strategy of ganglia modification for arrhythmia and for other diseases.

Chikusetsusaponin V Inhibits LPS-Activated Inflammatory Responses via SIRT1/NF-κB Signaling Pathway in RAW264.7 Cells.

It is becoming increasingly accepted that macrophage activation play a crucial role in many diseases associated with chronic inflammation, such as metabolic disease, including atherosclerosis, obesity, and diabetes. Recent studies have indicated that the regulation of inflammation and energy metabolism are connected together through an antagonistic crosstalk between NF-κB and SIRT1 signaling pathways. In order to investigate anti-inflammatory drugs, we investigated whether SIRT1 is implicated in the lipopolysaccharide (LPS)-stimulated NF-κB signaling pathway in macrophage RAW264.7 cells when pretreated with chikusetsusaponin V (CsV). Griess assay and enzyme-linked immunosorbent assay were used to determine the effect of CsV on LPS-induced inflammatory cytokine secretion. Western blot was used to assess the effect of CsV on LPS-induced SIRT1 and Ac-NF-κB p65 expression. Results showed that CsV suppressed LPS-induced inflammatory cytokine NO, TNF-α, and IL-1ß production in RAW264.7 cells. In addition, downregulation of SIRT1 and upregulation of Ac-NF-κB p65 induced by LPS were abolished by CsV in a dose-dependent manner in RAW264.7 cells. Meanwhile, inflammatory cytokines were regulated with CsV through SIRT1-Ac-NF-κB p65 signaling pathway. Therefore, our results demonstrate that CsV exerts an anti-inflammatory effect partly through SIRT1/NF-κB signaling pathways and SIRT1 may be a new target for anti-inflammation therapies.

Astragaloside IV inhibits Angiotensin II-stimulated proliferation of rat vascular smooth muscle cells via the regulation of CDK2 activity.

AIMS: Astragaloside IV (AS-IV) is the central active component extracted from Radix astragali, an herbal remedy widely used in traditional Chinese medicine for the treatment of cardiovascular diseases. Aberrant proliferation of vascular smooth muscle cells (VSMCs) is closely involved in the initiation and progression of cardiovascular complications, such as atherosclerosis. Here we investigated whether AS-IV inhibited agonist-induced vascular smooth muscle cells (VSMCs) proliferation and the underlying mechanism. MAIN METHODS: Quiescent cultured A10 cells (adult rat VSMCs) were treated with Angiotensin II (AngII) or AngII plus AS-IV for 48 h. The growth rate of A10 cells was analyzed by CCK8 assay. RT-PCR analysis was carried out to examine the expression of α-smooth muscle actin (α-SMA), an important phenotypic modulation marker. In addition, whether the interference of AS-IV on AngII-mediated growth of VSMCs via regulation of cell cycle was evaluated by flow cytometry. In order to explore the role of cell cycle machinery, we measured kinase activity of CDK2 by Kinase assay and the protein level of Cdc25 by western blot, respectively. KEY FINDINGS: These data suggested that AS-IV exerted beneficial effects on AngII -induced abnormal growth in rat VSMCs through disturbing cell cycle, especially block G1/S transition by attenuating CDK2 activity, which may hinder the process of pathological vascular remodeling during atherosclerosis.

Comparative study on polymer light-emitting devices based on blends of polyfluorene and 4,7-di-2-thienyl-2,1,3-benzothiadiazole with devices based on copolymer of the same composition.

The small molecule 4,7-di-2-thienyl-2,1,3-benzothiadiazole (DBT) dye has been synthesized and blended into blue-emitting polyfluorene as a host. The photophysics of the blend films and electroluminescence device performance was compared with that from polyfluorene-co-4,7-di-2-thienyl-2,1,3-benzothiadiazole (PFO-DBT) copolymer of the same molar composition, with DBT incorporated covalently into the polyfluorene backbone. The role of intra- and interpolymer chain interaction and energy transfer in the polymer light-emitting devices are discussed. On the basis of the direct comparison of blend and copolymer from the same molecular composition, we can draw the conclusion that, in conjugated polymers, intrachain energy transfer along the polymer backbone is more efficient than that via interchain interaction and plays a more important role in polymer light-emitting devices.

Reversible transformation of self-assemblies and fluorescence by protonation-deprotonation in pyrimidinylene-phenylene macrocycles.

We describe herein that the self-assembled nanoobjects based on pyrimidinylene-phenylene macrocycles, 1 and 2, which possess the capability to respond to acid-stimuli by proton binding, can undergo reversible transformation of self-assemblies and fluorescence switching by protonation-deprotonation.

Highly selective and sensitive colorimetric probe for hydrogen sulfide by a copper (II) complex of azo-dye based on chemosensing ensemble approach.

A copper (II) complex of azo-dye (Cu-1) has been synthesized by the reaction of 1-(2-pyridylazo)-2-naphthol (1) with copper (II) chloride. The complex Cu-1 is able to selectively sense hydrogen sulfide over other anions followed by the release of compound 1 to give a remarkable change of UV-vis absorption at neutral pH in aqueous solution.