N-取代N′-苯基哌嗪类化合物与硫杂蒽酮体系光诱导电子转移引发聚合体系的研究

本工作对N-苯基-N'-乙基呱嗪作为酮/胺光引发体系中组分之一的作用机制进行了研究。发现该特殊的胺类化合物虽包括二甲基苯胺和三乙胺两个部分,但它和酮类相组合形成的光引发体系只有较低的尤引发速率。对上述现象进行了讨论,并通过加入酸类化合物使其中一个胺发生季胺盐化,用以改进光引发效率来进一步证实文中所讨论的机制。     

Electron-transfer reduction of selected alcohols with alkalide K, K(15-crown-5)2 via organometallic intermediates

The course of the reaction of alkalide K⁻, K⁺(15-crown-5)₂1 with selected alcohols depends on the kind of alcohol and the mode of substrate delivery. In the case of methanol, potassium methoxide formed initially undergoes destruction at the excess of 1. It results in potassium oxide and methylpotassium. The latter opens the crown ether ring giving potassium tetraethylene glycoxide vinyl ether and methane. A similar course of the process is observed for propanol. Potassium glycidoxide is the main product formed in the reaction of 1 with glycidol. Its oxirane ring is opened at the excess of 1. Organopotassium alkoxides, i.e., potassium potassiomethoxide and dipotassium potassiopropane-1,2-dioxide are intermediate products of this reaction. They react then with the crown ether. Potassium methoxide, potassium enolate of acetaldehyde, dipotassium propane-1,2-dioxide and potassium tetraethylene glycoxide vinyl ether are the final products of this process.     

Paramagnetic ruthenium(III) cyclometallated complex. Synthesis, spectroscopic studies and electron-transfer properties

The reaction of Ru^II(PPh₃)₃X₂ (X = Cl, Br) with o-(OH)C₆H₄C(H)=N-CH₂C₆H₅ (HL) under aerobic conditions affords Ru^II(L)₂(PPh₃)₂, 1, in which both the ligands (L) are bound to the metal center at the phenolic oxygen (deprotonated) and azomethine nitrogen and Ru^III(L¹)(L²)(PPh₃), 2, in which one L is in bidentate N,O form like in complex 1 and the other ligand is in tridentate C,N,O mode where cyclometallation takes place from the ortho carbon atom (deprotonated) of the benzyl amine fragment. The complex 1 is unstable in solution, and undergoes spontaneous oxidative internal transformation to complex 2. In solid state upon heating, 1 initially converts to 2 quantitatively and further heating causes the rearrangement of complex 2 to the stable RuL₃ complex. The presence of symmetry in the diamagnetic, electrically neutral complex 1 is confirmed by ¹H and ³¹P NMR spectroscopy. It exhibits an Ru^II → L, MLCT transition at 460 nm and a ligand based transition at 340 nm. The complex 1 undergoes quasi-reversible ruthenium(II)—ruthenium(III) oxidation at 1.27V vs. SCE. The one-electron paramagnetic cyclometallated ruthenium(III) complex 2 displays an L → Ru^III, LMCT transition at 658 nm. The ligand based transition is observed to take place at 343 nm. The complex 2 shows reversible ruthenium(III)—ruthenium(IV) oxidation at 0.875V and irreversible ruthenium(III)—ruthenium(II) reduction at −0.68V vs. SCE. It exhibits a rhombic EPR spectrum, that has been analysed to furnish values of axial (6560 cm⁻¹) and rhombic (5630 cm⁻¹) distortion parameters as well as the energies of the two expected ligand field transitions (3877 cm⁻¹ and 9540 cm⁻¹) within the t₂ shell. One of the transitions has been experimentally observed in the predicted region (9090 cm⁻¹). The first order rate constants at different temperatures and the activation parameter ΔH^#/ΔS^# values of the conversion process of 1 → 2 have been determined spectrophotometrically in chloroform solution.     

Simulations of Redox Mediation within Bioactive Hydrogels of Amperometric Biosensors

Highly hydrated bioactive hydrogels containing immobilized oxidoreductase enzymes and immobilized redox mediators were simulated as the biorecognition layer of amperometric biosensors. The linear dynamic range of the amperometric response of mediated biosensors increases and moves to higher concentration brackets with an increase in the concentration of mediator. This informs the design of biosensors that target the same analyte but possesses several independently addressable electrodes modified with hydrogels that contain different concentrations of mediator. Increases in enzyme concentration increase the linear dynamic range but does not alter the sensitivity of amperometric biosensors. Both sensitivity and linear dynamic range of mediated amperometric enzyme biosensors may be “tuned” by varying the concentrations of the enzyme and the mediator. Simulations effectively guide the initial domains of study of complex systems such as implantable biosensors.     

Enzymetically Regulating the Self‐Healing of Protein Hydrogels with High Healing Efficiency

Enzyme‐mediated self‐healing of dynamic covalent bond‐driven protein hydrogels was realized by the synergy of two enzymes, glucose oxidase (GOX) and catalase (CAT). The reversible covalent attachment of glutaraldehyde to lysine residues of GOX, CAT, and bovine serum albumin (BSA) led to the formation and functionalization of the self‐healing protein hydrogel system. The enzyme‐mediated protein hydrogels exhibit excellent self‐healing properties with 100 % recovery. The self‐healing process was reversible and effective with an external glucose stimulus at room temperature.     

Electrochemical Sensing of Ovalbumin Based on the Interaction between Lysozyme Origin/Tyrosine‐rich Peptides Modified on Magnetic Beads and Oligothreonine/Ovalbumin‐origin Peptide

We developed a highly sensitive electrochemical system for the sensing of ovalbumin (OVA). Lysozyme origin/tyrosine‐rich peptides (RNRCKGTDVQAWY₄C) were immobilized on magnetic beads, and the competitive reaction between OVA and oligothreonine/OVA origin peptide probe (T₈VLLPDEVSG) could then be measured. In a previous study, the detection of OVA at the 10^?13 M level was achieved using RNRCKGTDVQAWY₄C‐modified beads via a cross‐linker. To improve the sensitivity to OVA, this system uses T₈VLLPDEVSG peptide probe to measure the interaction to RNRCKGTDVQAWY₄C immobilized on magnetic beads. The peak of Y₄C actually was an electron‐transfer peptide, which represented the oxidation of a phenolic hydroxyl group. First, we confirmed that the oxidation response of Y₄C was increased based on an improvement in the electron transfer accessibility by oligothreonine. Next, T₈VLLPDEVSG peptide probe was used for the electrochemical sensing of OVA in solutions that contained consistent amounts of RNRCKGTDVQAWY₄C on magnetic beads. As a result, the peak current decreased as the concentration of OVA increased. The sensitivity to OVA was improved compared with the use of only RNRCKGTDVQAWY₄C on magnetic beads. The OVA detection level was 10^?14 M, which approximates the results from antibody‐antigen reactions. Consequently, the proposed system is a powerful new concept in protein sensing.     

Metal ion mediated molecularly imprinted polymer for selective capturing antibiotics containing beta-diketone structure

A new molecularly imprinted polymer (MIP) targeting to quinolones (Qs) and tetracyclines (TCs) was synthesized using itaconic acid (ITA) and ciprofloxacin (CIP) as a functional monomer and template molecule, respectively. Factors affecting the overall performance of MIP were investigated, and the results showed that Fe(3+) ion play a vital role in the formation of MIP with high molecular imprinting effect. Meanwhile, the chelating ability of monomer, species of template molecule, as well as the molar ratio of monomer and template also contribute to the performance of the obtained MIP. Cyclic voltammetry verified that, with the participation of Fe(3+) ions, a ternary complex of ITA-Fe(3+)-CIP could be formed before polymerization. Compared with conventional MIP prepared from commonly used monomer, methacrylic acid (MAA), the new MIP show significantly enhanced molecular imprinting effect and higher capacity for specific adsorption of target compounds as revealed by static and dynamic binding experiments. The MIP was successfully used as solid-phase extraction (SPE) adsorbent for enriching a broad spectrum of antibiotics containing beta-diketone structure from surface water sample. HPLC detection showed that high recovery rate (78.6-113.6%) was found in these spiked antibiotics, whereas recovery rate for the non structurally related drugs, epinephrine (EP) and dopamine (DOPA), was very low (4.7-7.6%) on the MIP cartridges. The results demonstrate that the MIP prepared by the strategy proposed in this work, could specifically target to a series of structurally related antibiotics containing beta-diketone structure.     

A possible interpretation of CDF dijet mass anomaly and its realization in supersymmetry

Recently, the CDF Collaboration reports an anomaly in dijet mass distribution in association with a lepton and missing energy. We discuss a possibility that the origin of the lepton and missing energy comes not from a W boson but a new boson particle, which is also responsible for the dijet mass peak. We show that such a situation can be realized in the framework of the minimal supersymmetric standard model and the dijet anomaly can be explained.     

A review of electron-capture and electron-transfer dissociation tandem mass spectrometry in polymer chemistry

Mass spectrometry (MS)-based studies of synthetic polymers often characterise detected polymer components using mass data alone. However when mass-based characterisations are ambiguous, tandem MS (MS/MS) offers a means by which additional analytical information may be collected. This review provides a synopsis of two particularly promising methods of dissociating polymer ions during MS/MS: electron-capture and electron-transfer dissociation (ECD and ETD, respectively). The article opens with a summary of the basic characteristics and operating principles of ECD and ETD, and relates these techniques to other methods of dissociating gas-phase ions, such as collision-induced dissociation (CID). Insights into ECD- and ETD-based MS/MS, gained from studies into proteins and peptides, are then discussed in relation to polymer chemistry. Finally, ECD- and ETD-based studies into various classes of polymer are summarised; for each polymer class, ECD- and ETD-derived data are compared to CID-derived data. These discussions identify ECD and ETD as powerful means by which unique and diagnostically useful polymer ion fragmentation data may be generated, and techniques worthy of increased utilisation by the polymer chemistry community.     

A Facile Method for the Synthesis of Chloroiodomethane from Diiodomethane Under Aluminum Mediation

In the presence of iodine and at room temperature, a stirred mixture of diiodomethane, dichloromethane and aluminum powder gave chloroiodomethane ClCH₂I (III) in excellant yield (90%).