4,564 research outputs found

    A study of allosteric binding behaviour of a 1,3-alternate thiacalix[4]arene-based receptor using fluorescence signal

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    A novel heteroditopic thiacalix[4]arene receptor L possessing 1,3-alternate conformation, which contains two pyrene moieties attached to the lower rim via urea linkages together with a crown ether moiety appended at the opposite side of the thiacalix[4]arene cavity, has been synthesized. The complexation behaviour of receptor L was studied by means of fluorescence spectra and ¹H NMR titration experiments in the presence of K⁺ ions and a variety of other anions. The results suggested that receptor L can complex efficiently via the urea cavity or the crown ether moiety, and a positive/negative allosteric effect operating in receptor L was observed

    Synthesis and inclusion behavior of a heterotritopic receptor based on hexahomotrioxacalix[3]arene

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    A heterotritopic hexahomotrioxacalix[3]arene receptor with the capability of binding two alkali metals and a transition metal in a cooperative fashion was synthesized. The binding model was investigated by using ¹H NMR titration experiments in CDCl₃–CD₃CN (10:1, v/v), and the results revealed that the transition metal was bound at the upper rim and the alkali metals at the lower and upper rims. Interestingly, the alkali metal ions Li⁺ and Na⁺ bind at the lower and upper rim respectively depending on the dimensions of the alkali metal ions versus the size of the cavities formed by the calix[3]arene derivative. The hexahomotrioxacalix[3]arene receptor acts as a heterotritopic receptor, binding with the transition metal ion Ag⁺ and the alkali metals ions Li⁺ and Na⁺. These findings were not applicable to other different sized alkali metals, such as K⁺ and Cs⁺

    Synthesis of a ditopic homooxacalix[3]arene for fluorescence enhanced detection of heavy and transition metal ions

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    A pyrene-appended ratiometric fluorescent chemosensor L based on a synthetic approach of insulating the fluorophore from the ionophore by a specific molecular spacer has been synthesised and characterised. The fluorescence spectra changes of L suggested that the chemosensor can detect heavy and transition metal (HTM) ions ratiometrically and with variable sensitivity according to the substituents present. ¹H NMR titration experiments indicated that the three triazole ligands prefer binding with Hg²⁺, Pb²⁺ and Zn²⁺, resulting in a conformational change that produces monomer emission of the pyrene accompanied by the excimer quenching. However, the addition of Fe³⁺, which may be accommodated by the cavity of L, makes the pyrene units move closer to each other, and a discernible increase in the emission intensity of the static excimer is observed. Therefore, it is believed that the ditopic scaffold of the calix[3]arene as a specific molecular spacer here plays an important role in the blocking of the heavy atom effect of HTM ions by insulating the fluorophore from the ionophore given the long distance between the metal cation and the pyrene moiety

    Emergent phases in a compass chain with multisite interactions

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    We study a dimerised spin chain with biaxial magnetic interacting ions in the presence of an externally induced three-site interactions out of equilibrium. In the general case, the three-site interactions play a role in renormalizing the effective uniform magnetic field. We find that the existence of zero-energy Majorana modes is intricately related to the sign of Pfaffian of the Bogoliubov-de Gennes Hamiltonian and the relevant Z2Z_2 topological invariant. In contrast, we show that an exotic spin liquid phase can emerge in the compass limit through a Berezinskii-Kosterlitz-Thouless (BKT) quantum phase transition. Such a BKT transition is characterized by a large dynamic exponent z=4z=4, and the spin-liquid phase is robust under a uniform magnetic field. We find the relative entropy and the quantum discord can signal the BKT transitions. We also uncover a few differences in deriving the correlation functions for the systems with broken reflection symmetry.Comment: 12 pages, 10 figure

    A pyrene-armed hexahomotrioxacalix[3]arene as a multi-sensor via synergistic and demetallation effects

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    A new pyrene-armed hexahomotrioxacalix[3]arene L has been synthesized, which exhibits a pronounced fluorescence enhancement response toward Cu²⁺ ions via a Zn²⁺ or Cd²⁺ triggered synergistic effect. Additionally, the L·Cu²⁺+ complex can subsequently serve as a sensor for F⁻ via anion-induced demetallation. The fluorescence responses by the input of Cu²⁺, Zn²⁺/Cd²⁺ and F⁻ can be constructed as a combinational logic gate which mimics a set of molecular traffic signals

    Fluorescent turn-on sensors based on pyrene-containing Schiff base derivatives for Cu2+ recognition: spectroscopic and DFT computational studies

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    A new fluorescent chemosensor L1, pyrene containing long chain Schiff base derivative in 1-position has been synthesized. Similarly, the receptors L2 and L3 are also designed in order to compare the binding ability for detection of Cu2+. The receptors exhibit very weak fluorescence (Φ = 0.01) due to the photoinduced electron transfer (PET). Upon addition of 10 equiv. of Cu2+, the emission intensity of ligands L1 and L2 are increased 65-fold (Φ = 0.31) and 25-fold (Φ = 0.08) in CH3CN/CH2Cl2 solvents system respectively. NMR titration experiments, spectroscopic and DFT computational studies confirmed the binding phenomena and sensitivity of Cu2+

    (2R,3R)-1-(4-Chloro­phen­yl)-2-[(S)-2-nitro-1-phenyl­eth­yl]-3-phenyl­pentan-1-one

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    The title compound, C25H24ClNO3, has three contiguous chiral centres. The absolute structure was determined by anomalous dispersion. The chloro­benzene ring is inclined to the two phenyl rings by 14.98 (9) and 59.05 (9)°. The two phenyl rings are inclined to one another by 49.51 (10)°. In the crystal, neighbouring mol­ecules are linked via C—H⋯O hydrogen bonds, forming chains propagating along [010]. There is also a C—H⋯π inter­action present that leads to the formation of a three-dimensional network

    Synthesis and evaluation of a novel fluorescent sensor based on hexahomotrioxacalix[3]arene for Zn²+ and Cd²+

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    A novel type of selective and sensitive fluorescent sensor having triazole rings as the binding sites on the lower rim of a hexahomotrioxacalix[3]arene scaffold in a cone conformation is reported. This sensor has desirable properties for practical applications, including selectivity for detecting Zn²⁺ and Cd²⁺ in the presence of excess competing metal ions at low ion concentration or as a fluorescence enhancement type chemosensor due to the cavity of calixarene changing from a ‘flattened-cone’ to a more-upright form and inhibition of PET. In contrast, the results suggested that receptor 1 is highly sensitive and selective for Cu²⁺ and Fe³⁺ as a fluorescence quenching type chemosensor due to the photoinduced electron transfer (PET) or heavy atom effect

    Aqua­[2-(3-carb­oxy-5-carboxyl­atophen­oxy)acetato-κO 1]bis­(1,10-phenanthroline-κ2 N,N′)manganese(II) dihydrate

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    In the title complex, [Mn(C10H6O7)(C12H8N2)2(H2O)]·2H2O, the MnII atom is coordinated by two O atoms from one 2-(3-carb­oxy-5-carboxyl­atophen­oxy)acetate (HOABDC2−) dianion and one water mol­ecule and by four N atoms from two 1,10-phenanthroline (phen) ligands within a distorted octa­hedral geometry. O—H⋯O hydrogen bonding between –COOH and –COO− groups of adjacent mol­ecules and between carboxyl­ate groups and coordinated and uncoordin­ated water mol­ecules leads to a three-dimensional structure which is further stabilized by weak π–π inter­actions of adjacent phen ligands with centroid–centroid separations of 4.2932 (1) Å

    The effect of experimental warming on leaf functional traits, leaf structure and leaf biochemistry in Arabidopsis thaliana

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    <p>Abstract</p> <p>Background</p> <p>The leaf is an important plant organ, and how it will respond to future global warming is a question that remains unanswered. The effects of experimental warming on leaf photosynthesis and respiration acclimation has been well studied so far, but relatively little information exists on the structural and biochemical responses to warming. However, such information is very important to better understand the plant responses to global warming. Therefore, we grew <it>Arabidopsis thaliana </it>at the three day/night temperatures of 23/18°C (ambient temperature), 25.5/20.5°C (elevated by 2.5°C) and 28/23°C (elevated by 5°C) to simulate the middle and the upper projected warming expected within the 21st century for this purpose.</p> <p>Results</p> <p>The 28/23°C treatment significantly reduced the life span, total biomass and total weight of seeds compared with the other two temperatures. Among the three temperature regimes, the concentrations of starch, chlorophyll, and proline were the lowest at 28/23°C, whereas the total weight of seeds, concentrations of chlorophyll and proline, stomatal density (SD), stomatal conductance (g<sub>s</sub>), net CO<sub>2 </sub>assimilation rate (A) and transpiration rate (E) were the highest at 25.5/20.5°C. Furthermore, the number of chloroplasts per cell and mitochondrial size were highest at 25.5/20.5°C and lowest at 28/23°C.</p> <p>Conclusions</p> <p>The conditions whereby the temperature was increased by 2.5°C were advantageous for <it>Arabidopsis</it>. However, a rise of 5°C produced negative effects, suggesting that lower levels of warming may benefit plants, especially those which belong to the same functional group as <it>Arabidopsis</it>, whereas higher levels of warming may produce negative affects. In addition, the increase in A under moderately warm conditions may be attributed to the increase in SD, chlorophyll content, and number of chloroplasts. Furthermore, starch accumulation in chloroplasts may be the main factor influencing chloroplast ultrastructure, and elevated temperature regulates plant respiration by probably affecting mitochondrial size. Finally, high SOD and CAT activities may enable plants grown at elevated temperatures to exhibit relatively high tolerance to temperature stress, thus alleviating the harmful effects of superoxide anion radicals and hydrogen peroxide.</p
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