Polymer Networks Assembled by Ruthenium Catalysts for Enhanced Water Splitting Performance in Calixarene Dye-Sensitized Photoelectrochemical Cells.

Metal-free photosensitizers for the construction of low-cost and eco-friendly dye-sensitized photoelectrochemical cells (DSPECs) have recently been greatly improved, but the optimization of water oxidation catalysts (WOCs) used in DSPECs based on metal-free dyes has received little attention. Herein, a series of polymer networks (RuTPA, RuCz, RuPr and RuTz) assembled by ruthenium WOCs (RuCHO) with various organic donors are constructed and combined with calixarene dyes to prepare DSPEC devices. The FTO|TiO|C4BTP+RuTPA photoanode shows the best performance with 85 % Faraday efficiency for oxygen production and 477 μA cm photocurrent density after 200 s chopping irradiation at 0 V vs.

[Main components in different varieties of Xihuangcao by UPLC-Q-TOF-MS and UPLC-DAD].

This study established an ultra-high performance liquid chromatography coupled with quadrupole-time-of-flight mass spectrometry(UPLC-Q-TOF-MS) method to analyze the main components in different varieties of Xihuangcao and established a UPLC-DAD method to simultaneously determine the five active components(caffeic acid, rosmarinic acid, schaftoside, isoschaftoside, and oridonin).The chromatographic separation was performed on a Waters ACQUITY UPLC BEH C_(18) column(2.1 mm×100 mm, 1.

Robust Heterogeneous Photocatalyst for Visible-Light-Driven Hydrogen Evolution Promotion: Immobilization of a Fluorescein Dye-Encapsulated Metal-Organic Cage on TiO.

The design of artificial photocatalytic devices that simulates the ingenious and efficient photosynthetic systems in nature is promising. Herein, a metal-organic cage [Pd(NPyCzPF)] (MOC-PC6) integrating 12 organic ligands NPyCzBP and 6 Pd catalytic centers is designed, which is well defined to include organic dye fluorescein (FL) for constructing a supramolecular photochemical molecular device (SPMD) FL@MOC-PC6. Photoinduced electron transfer (PET) between MOC-PC6 and the encapsulated FL has been observed by steady-state and time-resolved emission spectroscopy.

Curcumin attenuates Adriamycin-resistance of acute myeloid leukemia by inhibiting the lncRNA HOTAIR/miR-20a-5p/WT1 axis.

Acute myeloid leukemia (AML) is a common subtype of leukemia, and a large proportion of patients with AML eventually develop drug resistance. Curcumin exerts cancer suppressive effects and increases sensitivity to chemotherapy in several diseases. This study aimed to investigate the mechanism by which curcumin affects the resistance of AML to Adriamycin by regulating HOX transcript antisense RNA (HOTAIR) expression.

A Robust Photocatalytic Hybrid Material Composed of Metal-Organic Cages and TiO for Efficient Visible-Light-Driven Hydrogen Evolution.

The design of photochemical molecular devices (PMDs) for photocatalytic H production from water is a meaningful but challenging subject currently. Herein, a Pd L type metal-organic cage (denoted as MOC-Q2) is designed as a PMD, which consists of two catalytic centers (Pd ) and four photosensitive ligands (L-2) with four pyridine anchoring groups. Subsequently, the MOC-Q2 is combined with TiO to form TiO -MOC-Q2 hybrid materials with different MOC-Q2 contents by a facile sol-gel method, which have micro/mesoporous structures and large surface areas.

Constructing Heterogeneous Direct Z-Scheme Photocatalysts Based on Metal-Organic Cages and Graphitic-CN for High-Efficiency Photocatalytic Water Splitting.

The development of artificial devices that mimic the highly efficient and ingenious photosystems in nature is worthy of in-depth study. A metal-organic cage (MOC) Pd(M-4)(BF), denoted as MOC-Q1, integrating four organic photosensitized ligands M-4 and two Pd catalytic centers is designed for a photochemical molecular device (PMD). MOC-Q1 is successfully immobilized on graphitic carbon nitride (g-CN) by hydrogen bonds to obtain a robust heterogeneous direct Z-scheme g-CN/MOC-Q1 photocatalyst for H generation under visible light.

Photocatalytic H Production from Water by Metal-free Dye-sensitized TiO Semiconductors: The Role and Development Process of Organic Sensitizers.

The utilization of solar energy to produce hydrogen from water is showing increased importance and desirability in the field of artificial photosynthesis to produce clean and sustainable fuels. In a typical three-component dye-sensitized semiconductor system for photocatalysis, the dye sensitizer plays an essential role of energy antenna for harvesting visible light and promoting the reduction reaction to generate hydrogen. In recent decades, a lot of attention has focused on metal-free organic sensitizers, which have the advantages of low cost, high molar extinction coefficient, good modifiability and, most importantly, ability to avoid the use of noble metal ions.

Photocatalysts for H Generation from Starburst Triphenylamine/Carbazole Donor-Based Metal-Free Dyes and Porous Anatase TiO Cube.

A series of novel triphenylamine/carbazole-based D-D-π-π-A dyes DH1-4 and a mesoporous anatase cubic "microcage" TiO material (denoted as MC-TiO ) were synthesized and combined to obtain dye-sensitized photocatalysts (denoted as DHn/Pt/MC-TiO , n=1-4). These catalysts showed better performances in visible-light-driven H evolution from water than DHn/Pt/P25-TiO catalysts based on commercial P25-TiO bulk semiconductor under similar conditions. Compared with P25-TiO particles, the porous MC-TiO had a large Brunauer-Emmett-Teller surface area, porosity, and exposed {0 0 1} crystal plane, which greatly contributed to the photocatalytic activity.

Cage Based Crystalline Covalent Organic Frameworks.

The first two cage based crystalline covalent organic frameworks, cage-COF-1 and cage-COF-2, were constructed from a prism-like three-aldehyde-containing molecular cage. The cage contains two horizontal phloroglucinol and three vertical triazine moieties forming three identical V-shaped cavities. By reacting with p-phenylenediamine and 4,4'-biphenyldiamine, the two cage-COFs were formed with a hexagonal skeleton and possess a unique structure.

Networked Cages for Enhanced CO Capture and Sensing.

It remains a great challenge to design and synthesize a porous material for CO capture and sensing simultaneously. Herein, strategy of "cage to frameworks" is demonstrated to synthesize fluorescent porous organic polymer (pTOC) by using tetraphenylethylene-based oxacalixarene cage (TOC) as the monomer. The networked cages (pTOC) have improved porous properties, including Brunauer-Emmett-Teller surface area and CO capture compared with its monomer TOC, because the polymerization overcomes the window-to-arene packing modes of cages and turns on their pores.

A fluorescent calixarene-based dimeric capsule constructed a M-terpyridine interaction: cage structure, inclusion properties and drug release.

Two analogues of capsule-like fluorescent cages have been constructed by dimerization of terpyridine-containing calixarene derivatives utilizing a M-terpyridine (M = Zn and Cd) interaction. H NMR spectral studies show that the self-assembled molecular capsules ZnL1 and CdL1 have a highly symmetrical -structure. The encapsulation of the anticancer drug mercaptopurine in their cavities has been documented by NMR, ESI-TOF-MS, fluorescence switching, and molecular simulation, indicating that strong S-π and π-π interactions between drug and cage are of importance for the host-guest binding.

Pathological Changes in APP/PS-1 Transgenic Mouse Models of Alzheimer's Disease Treated with Ganoderma Lucidum Preparation.

Objective To explore the efficacy of ganoderma lucidum preparation(Ling Zhi) in treating APP/PS-1 transgenic mouse models of Alzheimer's disease(AD).Methods APP/PS-1 transgenic mice of 4 months were randomly divided into model group,ganoderma lucidum treatment groups,including high [2250 mg/(kg·d)] and middle [750 mg/(kg·d)] dose groups,i.e.

Regio- and Enantioselective Photodimerization within the Confined Space of a Homochiral Ruthenium/Palladium Heterometallic Coordination Cage.

The photoinduced regio- and enantioselective coupling of naphthols and derivatives thereof is achieved in the confined chiral coordination space of a Ru metalloligand based cage. The racemic or enantiopure cages encapsulate naphthol guests, which then undergo a regiospecific 1,4-coupling, rather than the normal 1,1-coupling, to form 4-(2-hydroxy-1-naphthyl)-1,2-napthoquinones; moderate stereochemical control is achieved with homochiral cages. The photoreactions proceed under both aerobic and anaerobic conditions but through distinct pathways that nevertheless involve the same radical intermediates.

Molecular Barrel by a Hooping Strategy: Synthesis, Structure, and Selective CO Adsorption Facilitated by Lone Pair-π Interactions.

A sophisticated molecular barrel 5 was efficiently constructed by hooping a 63-membered loop around a D-symmetric, shape-persistent bis(tetraoxacalix[2]arene[2]triazine) core. The hooping strategy involved 3-fold ring-closing metathesis (RCM) reactions of six branched olefin arms which were preanchored on the inner core. Through hooping, the loop tightens the cage structure and significantly enhances its stability toward nucleophilic decomposition.

An Approach to Optically Pure Bridging Chiral p-tert-Butylcalix[4]arenes through a Homologous Anionic Ortho-Fries Rearrangement.

A novel efficient approach to optically pure bridging chiral calix[4]arenes through a homologous anionic ortho-Fries rearrangement of inherently chiral calix[4]arenes was presented for the first time. As a result, two pairs of N,N'-dimethylformamidyl-substituted bridging chiral p-tert-butylcalix[4]arene enantiomers were facilely obtained. Their absolute configurations were determined through ROESY analysis, ECD comparison, and X-ray crystallographic analysis.

Microporous Polymers from a Carbazole-Based Triptycene Monomer: Synthesis and Their Applications for Gas Uptake.

Two kinds of novel organic microporous polymers TCPs (TCP-A and TCP-B) were prepared by two cost-effective synthetic strategies from the monomer of tricarbazolyltriptycene (TCT). Their structure and properties were characterized by FT-IR, solid (13) C NMR, powder XRD, SEM, TEM, and gas absorption measurements. TCP-B displayed a high surface area (1469 m(2)  g(-1) ) and excellent H2 storage (1.

Dye-sensitized solar cells with improved performance using cone-calix[4]arene based dyes.

Three cone-calix[4]arene-based sensitizers (Calix-1-Calix-3) with multiple donor-π-acceptor (D-π-A) moieties are designed, synthesized, and applied in dye-sensitized solar cells (DSSCs). Their photophysical and electrochemical properties are characterized by measuring UV/Vis absorption and emission spectra, cyclic voltammetry, and density functional theory (DFT) calculations. Calix-3 has excellent thermo- and photostability, as illustrated by thermogravimetric analysis (TGA) and dye-aging tests, respectively.

Qualitative analysis of the helical electronic energy of inherently chiral calix[4]arenes: an approach to effectively assign their absolute configuration.

For all microhelices on aromatic rings of inherently chiral calix[4]arene, an expression was derived from one approximation and one hypothesis on the basis of the electron-on-a-helix model of Tinoco and Woody as follows: 1/E = μ(H - KΔα2), where μ = 1 for the right-handed microhelix and μ = -1 for the left-handed microhelix; and H and K are constant and greater than zero. The expression correlates microhelical electronic energy (E) with the atom polarizability difference (Δα) on both microhelix ends, which intuitively and clearly shows the impact of helical substituent polarizability on helical electronic energy. The case analysis almost entirely proves that the qualitative analysis of the helical electronic energy of inherently chiral calix[4]arenes with the expression is scientific and can be used to effectively assign their absolute configuration.

Influence of the selective EDTA derivative phenyldiaminetetraacetic acid on the speciation and extraction of heavy metals from a contaminated soil.

The development of more selective chelators for the washing of heavy metal contaminated soil is desirable in order to avoid excessive dissolution of soil minerals. Speciation and mobility of Cu, Zn, Pb, and Ni in a contaminated soil washed with phenyldiaminetetraacetic acid (PDTA), a derivative of EDTA, were investigated by batch leaching test using a range of soil washing conditions followed by sequential extraction. With appropriate washing conditions, PDTA significantly enhanced extraction of Cu from the contaminated soil.

[Relationships between typical vegetations, soil salinity, and groundwater depth in the Yellow River Delta of China].

Soil salinity and groundwater depth are the two important factors affecting the vegetation growth and distribution in the Yellow River Delta. Through field investigation and statistical analysis, this paper studied the relationships between the typical vegetations (Suaeda heteroptera-Tamarix chinensis, Robinia pseudoacacia, Phragmites australis, and cotton) , soil salinity, and groundwater depth in the Delta. In the study area, groundwater depth had significant effects on soil salinity, with the average influence coefficient being 0.

Chelant extraction of heavy metals from contaminated soils using new selective EDTA derivatives.

Soil washing is one of the few permanent treatment alternatives for removing metal contaminants. Ethylenediaminetetraacetic acid (EDTA) and its salts can substantially increase heavy metal removal from contaminated soils and have been extensively studied for soil washing. However, EDTA has a poor utilization ratio due to its low selectivity resulting from the competition between soil major cations and trace metal ions for chelation.

Starburst triarylamine based dyes bearing a 3,4-ethylenedioxythiophene linker for efficient dye-sensitized solar cells.

Starburst triarylamine-based organic dyes (D1, D2, and D3) have been synthesized. For the three designed dyes, the starburst triarylamine group, thiophene (or 3,4-ethylenedioxythiophene), and cyanoacetic acid take the role of electron donor, π-conjugation bridge, and electron acceptor, respectively. These compounds are characterized by photophysical, electrochemical, and theoretical computational methods.

Simultaneous extraction of Cr(VI) and Cu(II) from humic acid with new synthesized EDTA derivatives.

Soil washing is one of the few permanent treatment alternatives for removing metal contaminants. Ethylenediaminetetraacetic acid and its salts (EDTA) is very effective at removing cationic metals and has been utilized globally. However it is ineffective for anionic metal contaminants or metals bound to soil organic matter.

Construction of 0D to 3D cadmium complexes from different pyridyl diimide ligands.

Four semirigid ditopic ligands, N,N'-bis(3-pyridylmethyl)-pyromellitic diimide (L(1)), N,N'-bis(4-pyridylmethyl)-pyromellitic diimide (L(2)), N,N'-bis(3-pyridylmethyl)-naphthalene diimide (L(3)), and N,N'-bis(4-pyridylmethyl)-naphthalene diimide (L(4)), reacted with Cd(NO(3))(2) to result in four cadmium(II) complexes, namely, {[Cd(2)(L(1))(2)(NO(3))(4)(CH(3)OH)(4)]·H(2)O} (1), [Cd(L(2))(NO(3))(2)(CH(3)OH)(2)·Cd(2)(L(2))(3)(NO(3))(4)]·{4(HCCl(3))·2H(2)O}(n) (2), {[Cd(L(3))(2)(NO(3))(2)]}(n) (3), and {[Cd(L(4))(2)(NO(3))(2)]·2(CHCl(3))}(n) (4). These complexes have been characterized by elemental analyses, powder X-ray diffraction, thermogravimetric (TG) analyses, IR spectroscopy, and single-crystal X-ray diffraction. Structural analyses show that four types of structures are formed: (1) a discrete M(2)L(2) ring with two Cd ions and two cis-L(1) ligands comprising a zero-dimensional molecular rectangle (0D), (2) an unusual zigzag linear chain and a one-dimensional ladder existing simultaneously in the crystal lattice (1D), (3) a two-dimensional network of the (4,4) net structure (2D), and (4) an unusual chiral three-dimensional framework with 5-fold interpenetrating diamond (dia) topology (3D).