Expanding the substrate scope of ugi five-center,four-component reaction U-5C-4CR): ketones as coupling partners for secondary amino acids

Various symmetrical and unsymmetrical ketones were successfully coupled with secondary amino acids in the course of Ugi five-center, four-component reaction (U-5C-4CR), thus expanding the molecular diversity possible to be achieved by the reaction. The chemical yields depended on the degree of hindrance of the components employed and were satisfactory in view of possible steric interactions in the U-5C-4CR zwitterionic intermediate. The sense of diastereoinduction for reactions employing unsymmetrical ketones was examined by converting the resulting Ugi adducts into the corresponding rigid 2,6-diketopiperazine derivatives.     

Wells–Dawson heteropolyacid supported on silica: a highly efficient catalyst for synthesis of 2,4,5-trisubstituted and 1,2,4,5-tetrasubstituted imidazoles

Heteropolyacid H₆P₂W₁₈O₆₂·24H₂O (WD) supported on silica (WD/SiO₂) has been used as an effective catalytic system for the synthesis of various 1,2,4,5-tetrasubstituted imidazoles by four-component condensation of benzil, aldehydes, amines and ammonium acetate under solvent-free conditions. This approach can be useful for three-component synthesis of 2,4,5-trisubstituted imidazoles. The same reactions were repeated by using benzoin instead of benzil.     

Cross section and resonance strength measurements of 19F(p, αγ)16O at Ep= 200–800 keV

An excitation function of the ¹⁹F(p, αγ)¹⁶O reaction has been measured over the proton beam energy range E_p= 200–800 keV using a 4 π NaI summing spectrometer. A new resonance was found at E_R= 237 keV and its properties Γ_R, σ_R and ωγ have been extracted. The strengths of all resonances at E_p= 200–800 keV have been also extracted. The importance of the 1⁺ resonance at E_R= 11 keV is discussed and its width has been estimated taking into account interference effects with the strong 1⁺ resonance at E_R= 340 keV. The reaction rates have been calculated over a wide range of temperatures and compared with the rates of the (p, α₀) and (p, α_π) branches of the ¹⁹F(p, α)¹⁶O reaction. Received: 21 June 1999 / Revised version: 30 September 1999     

A diffusion model of chain-branching reaction of the explosive decomposition of heavy metal azides

A diffusion model of a solid-phase chain reaction of explosive decomposition of heavy metal azides was developed. The dimensional effects of initiation of the reaction were examined: the dependence of the critical fluence of initiation on the microcrystal size H(R) and on the irradiated zone diameter H(d). It was demonstrated that the diffusion model of the chain reaction closely describes the measured H(R) dependence at diffusion coefficients of D ∼ 0.2–0.3 cm²/s, values that correspond to experimentally measured mobility of electronic charge carriers of μ ∼ 10 cm²/(V s). To account for the measured H(d) dependence and the reaction front propagation velocity (V = 1.2 km/s), it is necessary that the diffusion coefficient be three orders of magnitude higher than the experimentally determined value. That the H(R) and H(d) dependences cannot be quantitatively described simultaneously is indicative of the underlying mechanisms of energy transfer being different.     

An investigation of distribution parameters for fluorine ion implantation in indium-tin-oxide films

Implanted-fluorine profiles in ITO films have been accurately measured using the ¹⁹F(p,αγ)¹⁶O resonance nuclear reaction at E_R=872.1 keV, with width Γ=4.2 keV. A proper deconvolution calculation method was used to extract the true distribution of fluorine from the experimental excitation yield curves. The experimental range distribution parameters, R_p and ΔR_p, were compared with those obtained from Monte Carlo simulation codes. PACS 61.72.Ww; 68.55.Ln     

The change of conductivity of erbium films caused by the sorption of hydrogen and oxygen

Films of erbium were evaporated onto the inside wall of a pyrex glass reaction vessel at 1O^?9 torr. Their mean thickness (200–600 Å) was deduced from their mass and geometrical area. Estimates of their surface areas were made from the physical adsorption of krypton at 78 °K (BET method) giving a mean specific surface area of 71 m^?2 g^?1. The number of surface sites was calculated from a relationship given by Brennan et al.¹⁾. The sorption of hydrogen and oxygen was studied separately, by measuring the changes in the electrical resistance of the films as a function of the amount of pure gas admitted to the reaction vessel in measured doses ～ 10¹⁸ atoms per dose. The experiments were repeated at 295 °K, 200 °K, 130–140 °K for both gases (measurements at 78 °K were not reproducible, probably because of a magnetic phase change). Hydrogen at 295 °K [as reported²⁾] caused an initial increase ΔR in the original resistance R to a maximum $\text{ΔR}\text{R}$ ～ 20 %, which was followed by a decrease to $\text{ΔR}\text{R}\text{= 0}$ and then to $\text{ΔR}\text{R}\text{< 0.}$ A similar pattern of resistance changes was observed at 200°K and 130–140°K with smaller changes of $\text{ΔR}\text{R}$, i.e. 16 % and 8 % respectively, but no significant differance in surface (θ) and bulk atomic ratios at which the maxima occurred, e.g. $\text{ΔR}\text{R}$ was a maximum for 1.6?θ?1.9.     

A study of nuclear transmutation of Th and <Superscript>nat</Superscript>U with neutrons produced in a Pb target and U blanket irradiated by 1.6 GeV deuterons

The spallation lead target in the “Energy plus Transmutation” set-up, covered with uranium blanket, was irradiated by the 1.6GeV deuteron beam from the Nuclotron accelerator at the Joint Institute for Nuclear Research in Dubna. The neutrons generated in the subcritical uranium blanket are used to activate the radioactive uranium and thorium samples outside the blanket. Rates of the (n,g \gamma) , (n, f) and (n, 2n) reactions are determined for some residual nuclei. The ratio of the reaction rates R(n, 2n)/R(n, f) is estimated to be 27(9)%. Contributions of the neutrons with energy E _n > 20 MeV to the (n, f) reaction rate is ∼ 57% for ²³²Th and ∼ 37% for ^natU , respectively. To compare with the experimental results, the reaction rates are simulated by generating the neutron fluxes employing two different models, the beam shapes by the MCNPX 2.6.c code and making use of the appropriate libraries of cross-sections. The transmutation power of the set-up is estimated using the average (n,g \gamma) and (n, 2n) reaction rates and compared with some of the results of the TARC experiment.     

Spectroscopic Study of 2-(2-pyridyliminomethyl)phenol as a Novel Fluorescent Probe for Superoxide Anion Radicals and Superoxide Dismutase Activity

A novel spectrofluorometric method, using 2-(2-pyridyliminomethyl)phenol as a fluorescent probe, was developed for the determination of superoxide anion radical (O₂ ^•−) and superoxide dismutase activity (SOD). The new fluorescent probe was synthesized and characterized with elemental analysis and IR spectra. It was oxidized by O₂ ^•− to form a less fluorescence product. Based on this reaction, a spectrofluorometric method was proposed and successfully used to determine superoxide anion radicals and SOD activity. The effects of interferences were studied. The reaction was simple, precise and sensitive. It was applied to determine SOD activity in garlic, papaya and spinach successfully.     

Synthesis of novel 4H-pyrimido[1,6-a]pyrimidines via a one-pot three-component condensation

Abstract  

Highly substituted novel 4H-pyrimido[1,6-a] pyrimidines were prepared by a trifluoromethanesulfonic acid catalyzed one-pot three-component condensation of 4-aminopyrimidines, aldehydes, and β-ketoesters. A preliminary feasibility study was undertaken on these compounds, to assess the potential production of a library of further diversified compounds by nucleophilic replacement of Cl (R¹) or by reaction of electrophiles with the NH₂ (R²) group.     

Green synthesis and characterization of novel 1,2,4,5-tetrasubstituted imidazole derivatives with eco-friendly red brick clay as efficacious catalyst

Use of cheaper and recyclable materials contributes positively to economic growth with environmental sustainability. We report the prospect of utilizing red brick clay as catalyst, which exhibited excellent activity in rapid one-pot four-component condensation of 1,2,4,5-tetrasubstituted imidazoles with high conversion and yields (91–96%) in aqueous medium at 60 °C in short reaction times (25–40 min). The red brick clay material was fully characterized by XRD, FT-IR, SEM, TEM, EDX and BET analyses. Red brick clay consisted of oxides of Si (20.38%), Fe (19.55%), Al (14.30%) and minor amounts of Ca (3.60%) and Mg (1.68%). The slate-like-shaped structure morphology and flaky appearance of inexpensive solid clay material proved competent material for the synthesis of 15 novel 1,2,4,5-tetrasubstituted imidazole derivatives. In addition, the advantages of the eco-friendly method are non-toxicity and re-usability of the catalyst. Reaction offers 78% atom economy and 84% carbon capture.

     

Steric effects on the mechanism of reaction of nucleophilic substitution of β‐substituted alkoxyvinyl trifluoromethyl ketones with four secondary amines

The kinetics of the reaction of β‐substituted β‐alkoxyvinyl trifluoromethyl ketones R¹O‐CR²?CH‐COCF₃ ( 1a – e ) [( 1a ), R¹?C₂H₅, R²?H; ( 1b ), R¹?R²?CH₃; ( 1c ), R¹?C₂H₅, R²?C₆H₅; ( 1d ), R¹?C₂H₅, R²?V^?pNO₂C₆H₄; ( 1e ), R¹?C₂H₅, R²?C(CH₃)₃] with four aliphatic amines ( 2a – d ) [( 2a ), (C₂H₅)₂NH; ( 2b ), (i‐C₃H₇)₂NH; ( 2c ), (CH₂)₅NH; ( 2d ), O(CH₂CH₂)₂NH] was studied in two aprotic solvents, hexane and acetonitrile. The least reactive stereoisomeric form of ( 1a – d ) was the most populated ( E‐s‐Z‐o‐Z ) form, whereas in ( 1e ), the more reactive form ( Z‐s‐Z‐o‐Z ) dominated. The reactions studied proceeded via common transition state formation whose decomposition occurred by ‘uncatalyzed’ and/or ‘catalyzed’ route. Shielding of the reaction centre by bulky β‐substituents lowered abruptly both k′ (‘uncatalyzed’ rate constant) and k″ (‘catalyzed’ rate constant) of this reaction. Bulky amines reduced k″ to a greater extent than k′ as a result of an additional steric retardation to the approach of the bulky amine to its ammonium ion in the transition state. An increase in the electron‐withdrawing ability of the β‐substituent increased ‘uncatalyzed’ k′ due to the acceleration of the initial nucleophile attack (k₁) and ‘uncatalyzed’ decomposition of transition state (k₂) via promoting electrophilic assistance (through transition state 8 ). The amine basicity determined the route of the reaction: the higher amine basicity, the higher k₃/k₂ ratio (a measure of the ‘catalyzed’ route contribution as compared to the ‘uncatalyzed’ process) was. ‘Uncatalyzed’ route predominated for all reactions; however in polar acetonitrile the contribution of the ‘catalyzed’ route was significant for amines with high pK_a and small bulk. Copyright © 2007 John Wiley & Sons, Ltd.     

Isotope effects in the enzymatic oxidation of tryptamine to 3-indolyl-acetaldehyde

The reaction mechanisms of the enzymatic deamination of tryptamine catalysed by the enzyme monoamine oxidase (MAO, EC 1.4.3.4) were investigated using the kinetic isotope effect and solvent isotope effect methods. The numerical values of these deuterium effects in the (1S) and (1R) positions of tryptamine were determined using the non-competitive spectrophotometry. The deuterium-labelled isotopologue [(1S)-²H]tryptamine was obtained in two steps by enzymatic coupling of indole with S-methyl-l-cysteine in a deuterated medium followed by enzymatic decarboxylation of the resulting [2-²H]-l-tryptophan. [(1R)-²H]tryptamine was obtained by enzymatic decarboxylation of l-tryptophan in the fully deuterated medium.     

Ultrasound promoted the synthesis of N-propargylic β-enaminones

The synthesis of 14 novel N-propargylic β-enaminones from the reaction of β-alkoxy vinyltrihalomethyl[carboxyethyl] ketones [R³C(O)CHC(R¹)OMe, where R³ = CF₃, CCl₃, CO₂Et and R¹ = Me, Et, Pr, Bu, i-Pent, CH₂CH₂CO₂Me] with propargyl amines [R²NHCH₂CCH, where R² = Pr, PhCH₂] is reported. Yields, solvents and reaction times needed for reaction completion, by microwave irradiation (MW), conventional thermal heating (TH) and under ultrasound irradiation (US) are compared. The best results were obtained under US irradiation in good to excellent yields (70-93%).     

Extrapolation of astrophysical <Emphasis Type="Italic">S</Emphasis> factors for the reaction <Superscript>14</Superscript>N((<Emphasis Type="Italic">p, γ</Emphasis>) <Superscript>15</Superscript>O to near-zero energies

The astrophysical S factors for the radiative-capture reaction ¹⁴N(p, γ)¹⁵O in the region of ultralow energies were calculated on the basis of the R-matrix approach. The values of the radiative and protonic widths were fitted to new experimental data. The contribution of direct radiative capture to bound states of the ¹⁵O nucleus was determined with the aid of asymptotic normalization coefficients, whose values were refined in the present study on the basis of the results obtained from an analysis of the reaction ¹⁴N(³He, d)¹⁵O at three different energies of incident helium ions. A value of S(0) = 1.79 ± 0.31 keV b was obtained for the total astrophysical S factor, and the reaction rate was determined for the process ¹⁴N(p, γ)¹⁵O.     

Enhancement of antibacterial effect of quaternary ammonium with inorganic nanosheets against <Emphasis Type="Italic">Enterobacter cloacae</Emphasis>

To suppress nosocomial infections, numerous studies of quaternary ammonium cations (R₄N⁺) to improve the antibiotic properties have been investigated. However, most of them reported developments of novel organic or polymeric materials with R₄N⁺. To pioneer antibacterial inorganic materials hybridized with R₄N⁺, a colloidal solution of metal oxide nanosheets, which have a small particle size (typically less than 10 nm), is considered to be a suitable option because oxide nanosheets with a negative surface charge strongly interact R₄N⁺. Herein, we demonstrate for the first time that the high antibacterial/bactericidal effects of titanate nanosheets (TNS) adsorbing tetramethylammonium (TMA-TNS) or tetrabultylammonium ions (TBA-TNS). Their antibacterial effects against Enterobacter cloacae were evaluated using a colony forming unit (CFU) counting method. The results showed that the synthesized TNS composites had superior antibacterial and bactericidal effects to those of free R₄N⁺ and TBA-TNS exhibited the strongest effect (69% CFU reduction compared with that of free TBA⁺ and 98% CFU reduction compared with the control) among the samples examined. Dark incubation was employed to ensure that photocatalytic reaction of semiconducting TNS did not contribute to the process. Compared with TiO₂ spherical particles, such high bactericidal effect would be induced by a synergistic function of TBA⁺ and TNS, which physically damages bacteria due to long hydrophobic alkyl chains and an anisotropic nanocrystalline structure with sharp edges, respectively.     

Measurements of the6Li(n, α) T cross section in the keV energy range

The⁶Li(n, α) cross section was measured in the 90–1500 keV energy range with uncertainties of 3–5%. A lithium glass scintillation detector was used for the measurement of the (n, α)-reaction rate. Flat response neutron detectors were used to monitor the neutron flux. A calibrated vanadium bath was employed to obtain absolute values. The results were analysed in terms of the single-level multi-channelR-matrix theory.     

AstrophysicalS(E) factor of8Li (α,n 0)11B and inhomogeneous Big Bang nucleosynthesis

The cross section of the¹¹B(n, α)⁸Li reaction has been measured atE _n=7.6 to 12.6 MeV. The neutron beam was produced via theD(d, n)³He reaction and aBF ₃ counter (with naturalB isotopic composition) served both as target for the¹¹B nuclides and as detector for the observation of the delayedα-activity of⁸Li. The data match well with previous results obtained atE _n =12.5 to 20.0 MeV. Using the principle of detailed balance the data were converted to the case of the⁸Li(α, n ₀)¹¹B reaction. The associated astrophysicalS(E) factor is dominated by a resonance atE _R=0.58 MeV of widthΓ _R =200 keV, withS(E _R )=8400 MeV b. ThisS (E _R ) value for the n₀ channel alone is already three times higher than the constantS(E) factor assumed previously and, thus, strengthens the significance of inhomogeneous Big Bang nucleosynthesis.     

Nuclear asymptotic normalization coefficients for <Superscript>14</Superscript>N → <Superscript>13</Superscript>C + <Emphasis Type="Italic">p</Emphasis> configurations and astrophysical <Emphasis Type="Italic">S</Emphasis> factor for radiative proton capture

Empirical values of the asymptotic normalization coefficient for proton bound states in the ¹⁴N nucleus for the first five levels were obtained from an analysis of the experimental differential cross sections known from our measurements and from the literature for the reaction ¹³C(³He, d)¹⁴N in the projectile-energy range between about 15 and 40 MeV. The values obtained in this way were used to calculate the astrophysical S factors for the reaction ¹³C(p, γ)¹⁴N in the case of the population of the first five levels of the 14N nucleus. The calculations were based on the R-matrix approach. The calculated values are in good agreement with the experimental astrophysical S factor at energies below 1 MeV.     

Implanted-fluorine depth profiles in silver gallium diselenide

Range distributions for fluorine ions in ¹⁹F⁺-implanted silver gallium diselenide (AgGaSe₂) in an energy range of 80–350 keV were measured by using the ¹⁹F(p, )¹⁶O resonant nuclear reaction at E_R=872.1 keV with width =4.2 keV. A proper convolution calculation method was used to extract the true distributions of fluorine from the experimental excitation-yield curves. The experimental range-distribution parameters, R_p and R_p, were compared with those obtained from Monte Carlo simulation codes. PACS 79.20.Rf; 66.30.Jt; 61.72.Ww