Kinetic model for formation of DMPO-OH in water under ultrasonic irradiation using EPR spin trapping method

The rate of the formation of the 2-hydroxy-5,5-dimethyl-1-pyrrolidinyloxy (DMPO-OH) radical in water during ultrasonic irradiation was evaluated both experimentally and theoretically. The hydroxyl radical (OH radical) was indirectly detected using 5,5-dimethyl-1-pyrroline N-oxide (DMPO) as the spin trapping compound, and the generated DMPO-OH by the reaction between the OH radical and DMPO was measured by an electron paramagnetic resonance. The rate of change in the concentration of the DMPO-OH decreased with time, suggesting that not only the formation reaction of DMPO-OH but also the degradation reaction would take place by ultrasonic irradiation. The formation rate of the DMPO-OH was higher with ultrasonic power intensity and lower with reaction temperature. Based on the experimental results, a kinetic model for the formation of the DMPO-OH was proposed by considering the formation reaction, the ultrasonic degradation, and spontaneous degradation of DMPO-OH. The model well described the effect of the ultrasonic power intensity and the reaction temperature on the formation rate of DMPO-OH. The rate of the formation of the DMPO-OH was evaluated with the aid of the kinetic model.     

Preparation of THP‐Ester‐Derived Pyridinium‐Type Salts and their Reactions with Various Nucleophiles

Nucleophilic substitution at the anomeric positions of tetrahydropyranyl (THP) and related carbohydrate‐derived esters that proceeded through pyridinium‐type salt intermediates have been developed. Treatment of the 6‐substituted α‐acetoxy‐tetrahydropyrans with TMSOTf (TMS=trimethylsilyl) and 2‐substitutited pyridines, such as 2‐p‐tolylpyridine and 2‐methoxypyridine, led to the efficient generation of cis‐pyridinium‐type salts. These salts reacted with various nucleophiles, such as alcohols, azides, and organozinc reagents, to form nucleophilic‐substitution products. A characteristic feature of these processes was that they took place under mild conditions, which did not affect acid‐labile protecting groups. Furthermore, the reactions that employed azides and C‐nucleophiles generated 2,6‐trans products with high degrees of stereoselectivity.     

Experimental Validation of Intermediate Termination in RAFT Polymerization with Dithiobenzoate via Comparison of Miniemulsion and Bulk Polymerization Rates

To understand if either of two controversial models for the retardation by RAFT agents is applicable, styrene polymerization using dithiobenzoate as the RAFT agent is carried out in both bulk and miniemulsion systems with the same rates of radical generation and the same RAFT agent concentrations. Miniemulsion polymerization with average diameters of the miniemulsion droplets of ≈107 nm is by far faster than in bulk, and the obtained rate of polymerization agrees well with the calculated results assuming a bimolecular termination between propagating radical and intermediate radical, generated by the addition reaction of propagating radical to the RAFT agent, which shows that the intermediate termination is the major reason for rate retardation by the RAFT agent.

     

Exceptionally strong Bragg diffraction from a mesoporous silica film pretreated with chlorotrimethylsilane toward application in X-ray optics

Exceptionally strong Bragg diffraction from a mesoporous silica film is achieved by exposing the as-deposited film to vapor of chlorotrimethylsilane (Me(3)SiCl) before extracting the surfactant. The intensity of the X-ray diffraction peak increased 7 times after the surfactant removal and it approached 30% reflectivity. This large increase of diffraction intensity cannot be explained simply by the improved contrast of the electron density, and rearrangement of the pore wall during the Me(3)SiCl vapor treatment is suggested. It is shown by infrared spectroscopy that Me(3)SiCl with a high grafting reactivity effectively caps the silanol groups and prevents the following condensation, which causes the structural degradation. The substitution of the hydrogen atom of hydroxyl groups with trimethylsilyl groups should help the improvement of the structural regularity by reducing the hydrogen bonds in the pore wall. The achieved strong diffraction opens the gate for the application of these regular mesoporous films prepared by a self-assembly process to optical elements in the X-ray region.     

LSI-based amperometric sensor for bio-imaging and multi-point biosensing

We have developed an LSI-based amperometric sensor called "Bio-LSI" with 400 measurement points as a platform for electrochemical bio-imaging and multi-point biosensing. The system is comprised of a 10.4 mm × 10.4 mm CMOS sensor chip with 20 × 20 unit cells, an external circuit box, a control unit for data acquisition, and a DC power box. Each unit cell of the chip contains an operational amplifier with a switched-capacitor type I-V converter for in-pixel signal amplification. We successfully realized a wide dynamic range from ±1 pA to ±100 nA with a well-organized circuit design and operating software. In particular, in-pixel signal amplification and an original program to control the signal read-out contribute to the lower detection limit and wide detection range of Bio-LSI. The spacial resolution is 250 μm and the temporal resolution is 18-125 ms/400 points, which depends on the desired current detection range. The coefficient of variance of the current for 400 points is within 5%. We also demonstrated the real-time imaging of a biological molecule using Bio-LSI. The LSI coated with an Os-HRP film was successfully applied to the monitoring of the changes of hydrogen peroxide concentration in a flow. The Os-HRP-coated LSI was spotted with glucose oxidase and used for bioelectrochemical imaging of the glucose oxidase (GOx)-catalyzed oxidation of glucose. Bio-LSI is a promising platform for a wide range of analytical fields, including diagnostics, environmental measurements and basic biochemistry.     

Hg(II) ion specifically binds with T:T mismatched base pair in duplex DNA

Metal-mediated base pair formation, resulting from the interaction between metal ions and artificial bases in oligonucleotides, has been developed for its potential application in nanotechnology. We have recently found that the T:T mismatched base pair binds with Hg(II) ions to generate a novel metal-mediated base pair in duplex DNA. The thermal stability of the duplex with the T-Hg-T base pair was comparable to that of the corresponding T:A or A:T. The novel T-Hg-T base pair involving the natural base thymine is more convenient than the metal-mediated base pairs involving artificial bases due to the lack of time-consuming synthesis. Here, we examine the specificity and thermodynamic properties of the binding between Hg(II) ions and the T:T mismatched base pair. Only the melting temperature of the duplex with T:T and not of the perfectly matched or other mismatched base pairs was found to specifically increase in the presence of Hg(II) ions. Hg(II) specifically bound with the T:T mismatched base pair at a molar ratio of 1:1 with a binding constant of 10(6) M(-1), which is significantly higher than that for nonspecific metal ion-DNA interactions. Furthermore, the higher-order structure of the duplex was not significantly distorted by the Hg(II) ion binding. Our results support the idea that the T-Hg-T base pair could eventually lead to progress in potential applications of metal-mediated base pairs in nanotechnology.     

Extremal Problems for Mappings with Generalized Parametric Representation in $${{\mathbb {C}}}^{n}$$

In this paper we are concerned with the family \(\widetilde{S}^t_A(\mathbb {B}^n)\) (\(t\ge 0\)) of normalized biholomorphic mappings on the Euclidean unit ball \(\mathbb {B}^n\) in \({\mathbb {C}}^n\) that can be embedded in normal Loewner chains whose normalizations are given by time-dependent operators \(A\in \widetilde{\mathcal {A}}\), where \(\widetilde{\mathcal {A}}\) is a family of measurable mappings from \([0,\infty )\) into \(L({\mathbb {C}}^n)\) which satisfy certain natural assumptions. In particular, we consider extreme points and support points associated with the compact family \(\widetilde{S}^t_A(\mathbb {B}^n)\), where \(A\in \widetilde{\mathcal {A}}\). We prove that if \(f(z,t)=V(t)^{-1}z+\cdots \) is a normal Loewner chain such that \(V(s)f(\cdot ,s)\in \mathrm{ex}\,\widetilde{S}^s_A(\mathbb {B}^n)\) (resp. \(V(s)f(\cdot ,s)\in \mathrm{supp}\,\widetilde{S}^s_A(\mathbb {B}^n)\)), then \(V(t)f(\cdot ,t)\in \mathrm{ex}\, \widetilde{S}^t_A(\mathbb {B}^n)\), for all \(t\ge s\) (resp. \(V(t)f(\cdot ,t)\in \mathrm{supp}\,\widetilde{S}^t_A(\mathbb {B}^n)\), for all \(t\ge s\)), where V(t) is the unique solution on \([0,\infty )\) of the initial value problem: \(\frac{d V}{d t}(t)=-A(t)V(t)\), a.e. \(t\ge 0\), \(V(0)=I_n\). Also, we obtain an example of a bounded support point for the family \(\widetilde{S}_A^t(\mathbb {B}^2)\), where \(A\in \widetilde{\mathcal {A}}\) is a certain time-dependent operator. We also consider the notion of a reachable family with respect to time-dependent linear operators \(A\in \widetilde{\mathcal {A}}\), and obtain characterizations of extreme/support points associated with these families of bounded biholomorphic mappings on \(\mathbb {B}^n\). Useful examples and applications yield that the study of the family \(\widetilde{S}^t_A(\mathbb {B}^n)\) for time-dependent operators \(A\in \widetilde{\mathcal {A}}\) is basically different from that in the case of constant time-dependent linear operators.     

Vanishing N = 20 shell gap: study of excited states in (27,28)Ne

This Letter reports on the (1)H((28)Ne, (28)Ne) and (1)H((28)Ne, (27)Ne) reactions studied at intermediate energy using a liquid hydrogen target. From the cross section populating the first 2(+) excited state of (28)Ne, and using the previously determined BE(2) value, the neutron quadrupole transition matrix element has been calculated to be M(n)=13.8 +/- 3.7 fm(2). In the neutron knockout reaction, two low-lying excited states were populated in (27)Ne. Only one of them can be interpreted by the sd shell model while the additional state may intrude from the fp shell. These experimental observations are consistent with the presence of fp shell configurations at low excitation energy in (27,28)Ne nuclei caused by a vanishing N=20 shell gap at Z=10.