Oligonucleotide Containing 8-Trifluoromethyl-2'-Deoxyguanosine as a Z-DNA Probe.

Z-DNA structure is a noncanonical left-handed alternative form of DNA, which has been suggested to be biologically important and is related to several genetic diseases and cancer. Therefore, investigation of Z-DNA structure associated with biological events is of great importance to understanding the functions of these molecules. Here, we described the development of a trifluoromethyl labeled deoxyguanosine derivative and employed it as a 19F NMR probe to study Z-form DNA structure in vitro and in living cells.

Composite capillary carbon tube Nb18W16O93as advanced anode material for aqueous ion capacitors.

Niobium-tungsten bimetal oxides have received wide attention due to their excellent lattice properties. In this work, Nb18W16O93(NbWO) with a tetragonal tungsten bronze structure was synthesized by simple hydrothermal method. NbWO was modified to provide high specific surface area via combining with hollow carbon nanotubes. Meanwhile, NbWO grows along the tube wall of carbon nanotubes, thus buffering the volume effect of NbWO particles. Also, the migration distance of Li-ion is effectively shortened, as well as the improved ion transfer efficiency and the reaction kinetics. In addition, carbon tube can enhance conductivity of NbWO, contributing to outstanding charge storage capacity and rate energy. Precisely, NbWO@C as electrode possesses large specific capacity (249.6 F g-1at 0.5 A g-1) and good rate performance (55.9% capacity retention from 0.5 to 2 A g-1). The aqueous Li-ion capacitor presents the advantages of high safety, low cost and good environmental friendliness. An asymmetric aqueous capacitor AC//NbWO@C, based on 'water-in-salt' electrolyte with high concentration lithium acetate, exhibits a large energy density of 43.2 Wh kg-1and a power density of 9 kW kg-1. Generally, NbWO@C as anode materials shows superior application perspective.

Study on nanocellulose isolated from waste chilli stems processing as dietary fiber in biscuits.

In order to expand the high added value of waste chilli stems and the recycling of green resources, cellulose in chilli stems was extracted by nitric acid-ethanol method, and nanocellulose was prepared by sulfuric acid hydrolysis method. The results showed that the cellulose content was between 15% and 34.5%. Under the optimum experimental conditions of 60% sulfuric acid concentration, 60°C reaction temperature and 120 min reaction time, the average yield of nanocellulose was 36.42% ±1.36%. Prepared cellulose and nanocellulose had been characterized using scanning electron microscopy, fourier-transform infrared, and x-ray diffraction analysis. The research indicated that the biscuits with acceptable overall quality could be prepared by using the dosage of nanocellulose (7%), and the corresponding biscuits had regular appearance and relatively smooth surface. The total dietary fiber content was positively correlated with different nanocellulose content. Through mice experiments, it was found that the consumption of biscuits containing nanocellulose could significantly reduce the food intake of mice and inhibit the weight growth of mice. Therefore, the research showed that whole wheat biscuits with nanocellulose could be regarded as food rich in dietary fiber. These results provided a basis for exploring the green resource recycling of chilli stems in food processing.

ADAR1 masks the cancer immunotherapeutic promise of ZBP1-driven necroptosis.

Only a small proportion of patients with cancer show lasting responses to immune checkpoint blockade (ICB)-based monotherapies. The RNA-editing enzyme ADAR1 is an emerging determinant of resistance to ICB therapy and prevents ICB responsiveness by repressing immunogenic double-stranded RNAs (dsRNAs), such as those arising from the dysregulated expression of endogenous retroviral elements (EREs)1-4. These dsRNAs trigger an interferon-dependent antitumour response by activating A-form dsRNA (A-RNA)-sensing proteins such as MDA-5 and PKR5. Here we show that ADAR1 also prevents the accrual of endogenous Z-form dsRNA elements (Z-RNAs), which were enriched in the 3' untranslated regions of interferon-stimulated mRNAs. Depletion or mutation of ADAR1 resulted in Z-RNA accumulation and activation of the Z-RNA sensor ZBP1, which culminated in RIPK3-mediated necroptosis. As no clinically viable ADAR1 inhibitors currently exist, we searched for a compound that can override the requirement for ADAR1 inhibition and directly activate ZBP1. We identified a small molecule, the curaxin CBL0137, which potently activates ZBP1 by triggering Z-DNA formation in cells. CBL0137 induced ZBP1-dependent necroptosis in cancer-associated fibroblasts and reversed ICB unresponsiveness in mouse models of melanoma. Collectively, these results demonstrate that ADAR1 represses endogenous Z-RNAs and identifies ZBP1-mediated necroptosis as a new determinant of tumour immunogenicity masked by ADAR1. Therapeutic activation of ZBP1-induced necroptosis provides a readily translatable avenue for rekindling the immune responsiveness of ICB-resistant human cancers.

A Unique Fe-N4 Coordination System Enabling Transformation of Oxygen into Superoxide for Photocatalytic CH Activation with High Efficiency and Selectivity.

Selective oxidation of CH bonds is one of the most important reactions in organic synthesis. However, activation of the α-CH bond of ethylbenzene by use of photocatalysis-generated superoxide anions (O2 •- ) remains a challenge. Herein, the formation of individual Fe atoms on polymeric carbon nitride (CN), that activates O2  to create O2 •- for facilitating the reaction of ethylbenzene to form acetophenone, is demonstrated. By utilizing density functional theory and materials characterization techniques, it is shown that individual Fe atoms are coordinated to four N atoms of CN and the resultant low-spin Fe-N4  system (t2g 6 eg 0 ) is not only a great adsorption site for oxygen molecules, but also allows for fast transfer of electrons generated in the CN framework to adsorbed O2 , producing O2 •- . The oxidation reaction of ethylbenzene triggered by O2 •- ions turns out to have a high conversion rate of 99% as well as an acetophenone selectivity of 99%, which can be ascribed to a novel reaction pathway that is different from the conventional route involving hydroxyl radicals and the production of phenethyl alcohol. Furthermore, it possesses great potential for other CH activation reactions besides ethylbenzene oxidation.

UiO-66-NH-(AO) MOFs with a New Ligand BDC-NH-(CN) for Efficient Extraction of Uranium from Seawater.

Metal-organic frameworks (MOFs) with a high surface area and excellent stability are potential candidates for uranium (U) adsorption. Amidoxime (AO) is the most widely used functional group to extract U, which is usually introduced into MOFs by two-step post-synthetic methods (PSMs). Herein, MOF UiO-66-NH-(AO) was obtained by a one-step PSM with amidoximation from UiO-66-NH-(CN), which was synthesized by a new organic ligand of 2-cyano-terephthalic acid and whose morphology was octahedron and could be well controlled with the new ligand. The one-step PSM can greatly maintain the octahedron of the MOFs. What is more, UiO-66-NH-(AO) showed good adsorption performance for U, the adsorption equilibrium was obtained within 1500 min, and the adsorption capacity of U was calculated to be 134.1 mg/g according to the Langmuir model. It also had excellent selectivity for U in the presence of high concentrations of vanadium (V), ferrum (Fe), magnesium (Mg), calcium (Ca), and zirconium (Zr). The adsorption capacity of U in natural seawater was determined to be 5.2 mg/g within 8 days. The recyclability of UiO-66-NH-(AO) in simulated seawater was demonstrated for at least four adsorption/desorption cycles. The binding mechanism was investigated by the extended X-ray absorption fine structure spectroscopy, revealing that U binding occurs in a fashion η2 motif. This study provides a reliable idea for the modification of MOFs and the potential for MOF-based materials to extract U from seawater.

Selective Capture Mechanism of Radioactive Thorium from Highly Acidic Solution by a Layered Metal Sulfide.

Thorium as a potential nuclear fuel for the next-generation thorium-based molten salt reactors holds significant environmental and economic promise over the current uranium-based nuclear reactors. However, because thorium (Th4+) usually coexists with other rare earth elements, alkali or alkaline earth metals in minerals, or highly acidic radioactive waste, seeking acid-resistant sorbents with excellent selectivity, high capacity, and fast removal rate for Th4+ is still a challenging task. In this work, we investigated a robust layered metal sulfide (KInSn2S6, KMS-5) for Th4+ removal from strong acidic solutions. We report that KMS-5 could capture Th4+ from a 0.1 M HNO3 solution with extremely high efficiency (∼99.9%), fast sorption kinetics (equilibrium time < 10 min), and large distribution coefficient (up to 1.5 × 106 mL/g). Furthermore, KMS-5 exhibited excellent sorption selectivity towards Th4+ in the presence of large amounts of competitive metal ions like Eu3+, Na+, and Ca2+. This extraordinary capture property for Th4+ is attributed to the facile ion exchange of Th4+ with K+ in the interlayers and subsequent formation of a stable coordination complex via Th-S bonds. These results indicate that KMS-5 is a promising functional sorbent for the effective capture of Th4+ from highly acidic solutions.

Efficiently immobilizing uranium (VI) by oxidized carbon foam.

Oxidized carbon foam (oxidized CF) was prepared by using a facile chemical oxidation treatment at relatively low temperature of 450 °C and applied to capture uranyl cation [U(VI)] from aqueous solutions. The effects of pH, contact time, initial U(VI) concentration, and temperature on the U(VI) absorption performance of oxidized CF were investigated by batch experiments. The oxidized CF was illustrated to exhibit fast sorption kinetics (92% removal within 15 min and 98% removal in 2 h) and high sorption capacity (305.77 mg g-1 at pH 5) toward U(VI). Integrated analyses combining energy-dispersive X-ray spectroscopy and Fourier transform infrared spectroscopy were applied on the U(VI)-loaded oxidized CF, showing the introduction of carboxyl groups as U(VI) sorption sites on the surface of CF after oxidation treatment. Furthermore, extended X-ray absorption fine structure spectroscopy was employed to identify the binding modes of U(VI) indicating that each UO22+ cation is coordinated with one or two carboxyl groups on the equatorial plane. Notably, the low content of U(VI) in wastewater can be efficiently immobilized by the oxidized CF, and the immobilized U(VI) can be further concentrated and converted into Na2U2O7 or U3O8 by a simple sintering step. These findings presented in this work suggest the potential of using oxidized CF for further treatment of low concentration wastewater containing U(VI).

Systematic Approach to DNA Aptamer Design Using Amino Acid-Nucleic Acid Hybrids (ANHs) Targeting Thrombin.

Chemical modifications of innate DNA/RNA aptamers facilitate the improvement of their function. Herein, we report our modular strategy to manipulate a thrombin-binding DNA aptamer (TBA) to improve its anticoagulation activity and binding affinity. A set of amino acid conjugates, termed amino acid-nucleic acid hybrids or ANHs, was synthesized and incorporated into a TBA loop sequences. We found that substitutions with hydrophobic amino acids in the loop region possessed significantly enhanced antithrombin activity, up to 3-fold higher than the native TBA. We investigated the correlations between thrombin-binding affinity and the features of our amino-acid conjugates using experimental techniques including circular dichroism spectroscopy, surface plasmon resonance assay, and molecular modeling. The present study demonstrates a systematic approach to aptamer design based on amino-acid characteristics, allowing the development of advanced aptamers.

Observation of Z-DNA Structure via the Synthesis of Oligonucleotide DNA Containing 8-Trifluoromethyl-2-Deoxyguanosine.

This article contains detailed synthetic protocols for the preparation of DNA oligonucleotides containing 8-trifluoromethyl-2'-deoxyguanosine (CF3 dG) and their application to observe Z-DNA structure in vitro and in living HeLa cells. First, using a catalytic system consisting of FeSO4 , H2 SO4 , and H2 O2 in DMSO, we achieved a one-step synthesis of CF3 dG through a radical reaction between deoxyguanosine (dG) and CF3 I, with a yield of 45%. We then obtained the 3'-phosphoramidite of CF3 dG through a routine three-step procedure. Next, we employed the CF3 dG phosphoramidite monomer in the synthesis of oligonucleotides on a solid-phase DNA synthesizer. Finally, we used the CF3 dG-modified DNA oligonucleotides to observe Z-DNA structure in vitro and in living HeLa cells through 19 F NMR spectroscopy. © 2021 Wiley Periodicals LLC. Basic Protocol 1: Synthesis of CF3 dG phosphoramidites Basic Protocol 2: Preparation of CF3 dG-modified DNA oligonucleotides Basic Protocol 3: Evaluation of CF3 dG stabilization of Z-DNA structure by CD spectroscopy Basic Protocol 4: Investigation of Z-DNA structure in vitro and in HeLa cells with CF3 dG-modified DNA oligonucleotides and 19 F NMR spectroscopy.

Metal-organic frameworks loaded on phosphorus-doped tubular carbon nitride for enhanced photocatalytic hydrogen production and amine oxidation.

It is still a challenge to evolve visible light photocatalysts that possess both efficient oxidation and reduction capabilities. In this paper, phosphorus-doped tubular carbon nitride@UiO-66-NH2 (p-TCN@U6-X) composites were prepared by in-situ load of UiO-66-NH2 on the surface of p-TCN based on solvothermal method, which exhibit excellent photocatalytic oxidation and reduction ability. As a result, under visible light irradiation (λ > 420 nm), the photocatalytic H2 production performance of p-TCN@U6-3 reached 2628 µmol g-1h-l, which was 8.19 and 5.36 times higher than that of p-TCN and UiO-66-NH2, respectively. Meanwhile, p-TCN@U6-3 also exhibited well selectivity rate (99%) and conversion rate (98%) for oxidative coupling of amine compounds. The high photocatalytic activities can be assigned to the improved visible light adsorption resulted from the tubular structure of p-TCN and enhanced electrical conductivity because of the phosphorus doping in p-TCN. Furthermore, UiO-66-NH2 plays the role of co-catalyst and active centers in the photocatalytic system to synergistically catalyze the reactions. Transient photocurrent spectra, steady-state photoluminescence (PL) and time-resolved photoluminescence (TRPL) further prove the more effective charge separation and transfer happened in the p-TCN@U6-X system compared with sole p-TCN and UiO-66-NH2, respectively. This work provides an effective method for creating novel carbon nitride-based photocatalytic systems with efficient capability for photocatalytic oxidation and reduction.

Achieving UV and X-ray Dual Photochromism in a Metal-Organic Hybrid via Structural Modulation.

Rational design and synthesis of new photochromic sensors have been active research areas of inquiry, particularly on how to predict and tailor their properties and functionalities. Herein, two thulium 2,2':6',2''-terpyridine-4'-carboxylate (TPC)-functionalized metal-organic hybrids, Tm(TPC)2(HCOO)(H2O) (TmTPC-1) and Tm(TPC)(HCOO)2 (TmTPC-2) with different photochromic response behaviors, have been successfully prepared, allowing for straightforward investigations of the structure-property correlation. Single-crystal X-ray diffraction and electron paramagnetic resonance analyses revealed that the incorporation of a unique dangling decorating TPC unit in TmTPC-1 offers a shorter and more accessible π-π interaction pathway between the adjacent TPC moieties than that in TmTPC-2. Such a structural feature leads to the production of radical species via a photoinduced intermolecular electron-transfer (IeMCT) process upon UV or X-ray irradiation, which ultimately endows TmTPC-1 with a rather unusual UV and X-ray dual photochromism. A linear relationship between the change of UV-vis absorbance intensity and X-ray dose was established, making TmTPC-1 a promising dosimeter for X-ray radiation with an extremely high energy threshold (30 kGy). To advance the development for real-world application, we have fabricated polyvinylidene fluoride (PVDF) membranes incorporating TmTPC-1 for functioning either as a UV imager or as an X-ray radiation indicator. Lastly, TmTPC-1 exhibits high thermal stability (up to 400 °C) and radioresistance (at least 900 kGy), and also excellent reversibility of photochromic transformation (at least 5 cycles).

A cationic thorium-organic framework with triple single-crystal-to-single-crystal transformation peculiarities for ultrasensitive anion recognition.

Single-crystal-to-single-crystal transformation of metal-organic frameworks has been met with great interest, as it allows for the creation of new materials in a stepwise manner and direct visualization of structural transitions when subjected to external stimuli. However, it remains a peculiarity among numerous metal-organic frameworks, particularly for the ones constructed from tetravalent metal cations. Herein, we present a cationic thorium-organic framework displaying unprecedented triple single-crystal-to-single-crystal transformations in organic solvents, water, and NaIO3 solution. Notably, both the interpenetration conversion and topological change driven by the SC-SC transformation have remained elusive for thorium-organic frameworks. Moreover, the single-crystal-to-single-crystal transition in NaIO3 solution can efficiently and selectively turn the ligand-based emission off, leading to the lowest limit of detection (0.107 µg kg-1) of iodate, one of the primary species of long-lived fission product 129I in aqueous medium, among all luminescent sensors.

Improving Thermodynamic Stability and Anticoagulant Activity of a Thrombin Binding Aptamer by Incorporation of 8-trifluoromethyl-2'-deoxyguanosine.

In this study, we incorporated 8-trifluoromethyl-2'-deoxyguanosine (FG) into a thrombin binding aptamer (TBA). Circular dichroism, nuclear magnetic resonance (NMR), electrophoresis, and prothrombin time (PT) assay were performed to investigate the structure, thermodynamic stability, biological stability, and anticoagulant activity of the FG-modified TBA sequences. We found that the replacement of FG into TBA sequences led to a remarkable improvement in the melting temperature up to 30 °C compared with the native sequence. The trifluoromethyl group allowed us to investigate the TBA G-quadruplex structure by 19F NMR spectroscopy. Furthermore, PT assays showed that the modified sequences can significantly improve the anticoagulant activity in comparison with the native TBA. Finally, we demonstrated that the trifluoromethyl-modified TBA sequence could function as an anticoagulant reagent in live rats. Our results strongly suggested that FG is a powerful nucleoside derivative to increase the thermodynamic stability and anticoagulant activity of TBA.

Tuning of the Network Dimensionality and Photoluminescent Properties in Homo- and Heteroleptic Lanthanide Coordination Polymers.

Targeted synthesis, through a heteroleptic methodology, has resulted in three types of lanthanide (Ln) coordination polymers (CPs) with tailored dimensionality, tunable photoluminescent colors, and distinct luminescence quenching upon UV and X-ray irradiation. The homoleptic Ln(tpbz)(NO3)2 [CP-1; tpbz = 4-(2,2':6',2″-terpyridin-4'-yl)benzoate] is assembled from Ln cations and bridging tpbz ligands, accompanied by the decoration of NO3- anions, forming a one-dimensional (1D) chain structure. The presence of ancillary dicarboxylate linkers, 1,4-benzenedicarboxylate (bdc) and 2,5-thiophenedicarboxylate (tdc), promotes additional bridging between 1D chains to form a two-dimensional layer and a three-dimensional framework for Ln(tpbz)(bdc) (CP-2) and Ln(tpbz)(tdc) (CP-3), respectively. The multicolor and luminescence properties of the obtained CPs were investigated, displaying typical red EuIII-based and green TbIII-based emissions. The SmIII-bearing CP-1-CP-3, however, exhibit diverse ratiometric LnIII- and ligand-based emissions, with the photoluminescent colors varying from pink to orange to cyan. Notably, the TbIII-containing CP-1-CP-3 display distinct luminescence quenching upon continuous exposure to UV and X-ray irradiation. To our best knowledge, CP-2-Tb represents one of the most sensitive UV dosage probes (3.2 × 10-7 J) among all CPs.

Structural Complexity and Magnetic Orderings in a Large Family of 3d-4f Heterobimetallic Sulfates.

The synthesis of a large family of heterobimetallic lanthanide copper sulfates was realized via stoichiometric hydrothermal reactions among Ln2O3, CuO, and H2SO4, giving rise to four distinct phases, namely Ln2Cu(SO4)2(OH)4 (Ln = Sm-Ho) (LnCuSO4-1), Ln4Cu(SO4)2(OH)10 (Ln = Tm-Lu) (LnCuSO4-2), LnCu(SO4)(OH)3 (Ln = Nd-Gd, except Pm) (LnCuSO4-3), and LnCu(SO4)(OH)3 (Ln = Dy-Lu) (LnCuSO4-4), with completely different topologies. The passage from LnCuSO4-1 and LnCuSO4-3 to LnCuSO4-2 and LnCuSO4-4 across the 4f series, respectively, can be ascribed to the effect of lanthanide contraction, which progressively induces shrinking of the Ln-O distance, reduction in the Ln coordination number, and eventually structural transitions. The incorporation of identical 3d-4f metal ions into different spin-lattices, in conjunction with substitution of diverse Ln3+ cations within the same spin-lattice, gives rise to tunable magnetic properties varying from ferromagnetic ordering in GdCuSO4-3 and HoCuSO4-4 to antiferromagnetic ordering in YbCuSO4-4, and to paramagnetic correlations found in GdCuSO4-1 and YbCuSO4-2.

A Promoted Charge Separation/Transfer System from Cu Single Atoms and C3 N4 Layers for Efficient Photocatalysis.

Establishing highly effective charge transfer channels in carbon nitride (C3 N4 ) for enhancing its photocatalytic activity is still a challenging issue. Herein, for the first time, the engineering of C3 N4 layers with single-atom Cu bonded with compositional N (CuNx ) is demonstrated to address this challenge. The CuNx is formed by intercalation of chlorophyll sodium copper salt into a melamine-based supramolecular precursor followed by controlled pyrolysis. Two groups of CuNx are identified: in one group each of Cu atoms is bonded with three in-plane N atoms, while in the other group each of Cu atoms is bonded with four N atoms of two neighboring C3 N4 layers, thus forming both in-plane and interlayer charge transfer channels. Importantly, ultrafast spectroscopy has further proved that CuNx can greatly improve in-plane and interlayer separation/transfer of charge carriers and in turn boost the photocatalytic efficiency. Consequently, the catalyst exhibits a superior visible-light photocatalytic hydrogen production rate (≈212 µmol h-1 /0.02 g catalyst), 30 times higher than that of bulk C3 N4 . Moreover, it leads to an outstanding conversion rate (92.3%) and selectivity (99.9%) for the oxidation of benzene under visible light.

Oligonucleotides DNA containing 8-trifluoromethyl-2'-deoxyguanosine for observing Z-DNA structure.

Z-DNA is known to be a left-handed alternative form of DNA and has important biological roles as well as being related to cancer and other genetic diseases. It is therefore important to investigate Z-DNA structure and related biological events in living cells. However, the development of molecular probes for the observation of Z-DNA structures inside living cells has not yet been realized. Here, we have succeeded in developing site-specific trifluoromethyl oligonucleotide DNA by incorporation of 8-trifluoromethyl-2'-deoxyguanosine (FG). 2D NMR strongly suggested that FG adopted a syn conformation. Trifluoromethyl oligonucleotides dramatically stabilized Z-DNA, even under physiological salt concentrations. Furthermore, the trifluoromethyl DNA can be used to directly observe Z-form DNA structure and interaction of DNA with proteins in vitro, as well as in living human cells by19F NMR spectroscopy for the first time. These results provide valuable information to allow understanding of the structure and function of Z-DNA.

Telomeric DNA-RNA-hybrid G-quadruplex exists in environmental conditions of HeLa cells.

In the present study, we employed a 19F NMR approach to study the association of telomere RNA and DNA in vitro and in living human cells. We successfully characterized the DNA-RNA hybrid G-quadruplex (HQ) structure formed by telomeric DNA and RNA. We further demonstrated for the first time that an HQ conformation can exist in the environmental conditions of HeLa cells.

The physical chemistry of uranium (VI) immobilization on manganese oxides.

Manganese oxides show strong affinity towards uranium, and have a promising application in uranium immobilization in environmental protection. We successfully synthesized a series of Mn oxide materials of different structures and investigated their U(VI) immobilization performances. The results showed that all Mn oxides share similar sorption capacities per unit surface area, implying similar physical chemistry during immobilization. Among these Mn oxides, α-MnO2 shows the most outstanding performance for uranium uptake (280 mg/g). More detailed studies on interfacial properties of U(VI) on α-MnO2 were performed to elucidate the binding mechanism. The uptake was largely influenced by acidity, but less impacted by ionic strength, indicative of an inner-sphere binding mode. The selectivity for uranium is much higher than other selected metal ions, i.e. Co2+, Ni2+, Eu3+, etc. ATR-FTIR, and EXAFS results showed that in both mild acidic and neutral conditions, U(VI) formed bidentate binuclear structure on α-MnO2, as evidenced by υas(O = U=O) at 912 cm-1 and the number of Mn in U coordination shell. UO2(OH)2 precipitate was found at the molecular level in neutral condition (pH 7-8). The results reveal the physical chemistry in uranium immobilization process on manganese oxide surfaces and helps to better understand the uranium environmental migration. Furthermore, it provides an alternative approach for radioactive water purification.