Superoxide does react with peroxides : direct observation of the haber-weiss reaction in the gas phase

The fact that nature provides specific enzymes to selectively remove superoxide (O2.−) from aerobic organisms, namely, the superoxide dismutase enzymes,1 has led to the suggestion that this radical ion may cause the oxidative damage associated with degradative disease and aging.2 Intriguingly, however, superoxide itself is relatively unreactive toward most cellular components, which suggests that dismutase enzymes may ultimately protect the cell against more pernicious oxidants formed from superoxide. As such, there is increasing interest in the endogenous chemistry of superoxide and the pathways by which it might beget more reactive oxygen species. Protonation of superoxide to form the hydroperoxyl radical (HOO.) and dismutation of the same species to hydrogen peroxide (HOOH), with subsequent metal-catalyzed reduction to the hydroxyl radical (HO.), are well-characterized processes in which both the HOO. and HO. radicals are significantly more reactive than their common progenitor.2 Recent examples, however, have also linked superoxide to the putative production of singlet oxygen3 and ozone,4, 5 although the definitive characterization of these chemistries in the cellular milieu has proved challenging

One-pot synthesis of imines from benzyl alcohol and amines on Au/ZrO2 catalyst

Imines were synthesized from benzyl alcohol and amines by using catalysts of gold nanoparticles supported on ZrO2 (Au/ZrO2). The effects of reaction time, temperature, gold loadings and base were investigated. High yields were achieved under moderate conditions (60 °C) in the presence of KOCH3. For instance, the yield of N-benzylidenebenzylamine produced from benzyl alcohol and benzylamine on 3 wt% Au/ZrO2 is 87 %. The synthesis of imine involves two reaction steps: selective oxidation of benzyl alcohol to benzaldehyde and the coupling reaction of amines with benzaldehyde. In the first step, the base promotes the selective oxidation. The reactions of benzyl alcohol with three different amines, aniline, n-butylamine and benzylamine, were conducted to produce corresponding imines. The results show that the amine with stronger nucleophilicity has better ability to react with benzaldehyde in the second step, resulting in higher yield of the corresponding imine. We proposed a tentative mechanism for the synthesis process.

Revolute joint approach to model joint mechanism in water-filled road safety barriers

Portable water-filled road barriers (PWFB) are roadside structures placed on temporary construction zones to separate work site from traffic. Recent changes in governing standards require PWFB to adhere to strict compliance in terms of lateral displacement and vehicle redirectionality. Actual PWFB test can be very costly, thus researchers resort to Finite Element Analysis (FEA) in the initial designs phase. There has been many research conducted on concrete barriers and flexible steel barriers using FEA, however not many was done pertaining to PWFB. This research probes a new technique to model joints in PWFB. Two methods to model the joining mechanism are presented and discussed in relation to its practicality and accuracy. Moreover, the study of the physical gap and mass of the barrier was investigated. Outcome from this research will benefit PWFB research and allow road barrier designers better knowledge in developing the next generation of road safety structures.

Effect of joint mechanism on vehicle redirectional capability of water-filled road safety barrier systems

Portable water-filled barriers (PWFBs) are roadside appurtenances that prevent vehicles from penetrating into temporary construction zones on roadways. PWFBs are required to satisfy the strict regulations for vehicle re-direction in tests. However, many of the current PWFBs fail to re-direct the vehicle at high speeds due to the inability of the joints to provide appropriate stiffness. The joint mechanism hence plays a crucial role in the performance of a PWFB system at high speed impacts. This paper investigates the desired features of the joint mechanism in a PWFB system that can re-direct vehicles at high speeds, while limiting the lateral displacement to acceptable limits. A rectangular “wall” representative of a 30 m long barrier system was modeled and a novel method of joining adjacent road barriers was introduced through appropriate pin-joint connections. The impact response of the barrier “wall” and the vehicle was obtained and the results show that a rotational stiffness of 3000 kNm/rad at the joints seems to provide the desired features of the PWFB system to re-direct impacting vehicles and restrict the lateral deflection. These research findings will be useful to safety engineers and road barrier designers in developing a new generation of PWFBs for increased road safety.

The collision induced loss of carbon monoxide from deprotonated benzyl benzoate in the gas phase. An anionic 1,2-Wittig type rearrangement

The ion PhCO2--CHPh, upon collision activation, undergoes competitive losses of CO and CO2 of which the former process produces the base peak of the spectrum. Product ion and substituent effect (Hammett) studies indicate that PhCO2--CHPh cyclises to a deprotonated hydroxydiphenyloxirane which ring opens to PhCOCH(O-)Ph. This anion then undergoes an anionic 1,2-Wittig type rearrangement {through [PhCO- (PhCHO)]} to form Ph2CHO- and CO. The mechanism of the 1,2-rearrangement has been probed by an ab initio study [at MP4(SDTQ)/6-31++G(d,p) level] of the model system HCOCH2O- →; MeO- + CO The analogous system RCO2--CHPh (R = alkyl) similarly loses CO, and the migratory aptitudes of the alkyl R groups in this reaction are Bu′ > Me > Et ∼Pri). This trend correlates with the order of anion basicities (i.e. the order of ΔG○acid values of RH), supporting the operation of an anion migration process. The loss of CO2 from PhCO2--CHPh yields Ph2CH- as the anionic product: several mechanistic scenarios are possible, one of which involves an initial ipso nucleophilic substitution.

Competitive charge-remote and anion-induced fragmentations of the non-8-enoate anion. A charge-remote reaction which co-occurs with hydrogen scrambling

The non-8-enoate anion undergoes losses of the elements of C3H6, C4H8 and C6H12 on collisional activation, The mechanisms of these processes have been elucidated by a combination of product ion and labelling (H-2 and C-13) studies, together with a neutralisation reionisation mass spectrometric study. These studies allow the following conclusions to be made. (i) The loss of C3H6 involves cyclisation of the enolate anion of non-8-enoic acid to yield the cyclopentyl carboxylate anion and propene. (ii) The loss of 'C4H8' is a charge-remote process (one which proceeds remote from the charged centre) which yields the pent-4-enoate anion, butadiene and dihydrogen. This process co-occurs and competes with complex H scrambling. (iii) The major loss of 'C6H12' occurs primarily by a charge-remote process yielding the acrylate anion, hexa-1,5-diene and dihydrogen, but in this case no H scrambling accompanies the process. (iv) It is argued that the major reason why the two charge-remote processes occur in preference to anion-induced losses of but-l-ene and hex-l-ene from the respective 4- and 2-anions is that although these anions are formed, they have alternative and lower energy fragmentation pathways than those involving the losses of but-l-ene and hex-l-ene; viz. the transient 4-anion undergoes facile proton transfer to yield a more stable anion, whereas the 2-(enolate) anion undergoes preferential cyclisation followed by elimination of propene [see (i) above].

Base-induced decomposition of alkyl hydroperoxides in the gas phase. Part 3. Kinetics and dynamics in HO-+CH3OOH, C2H5OOH, and tert-C4H9OOH reactions

The E-CO(2) elimination reactions of alkyl hydroperoxides proceed via abstraction of an (x-hydrogen by a base: X- + (RRHCOOH)-R-1-H-2 -> HX + (RRC)-R-1-C-2=O + HO-. Efficiencies and product distributions for the reactions of the hydroxide anion with methyl, ethyl, and tert-butyl hydroperoxides are studied in the gas phase. On the basis of experiments using three isotopic analogues, HO- + CH3OOH, HO- + CD3OOH, and H18O- + CH3OOH. the overall intrinsic reaction efficiency is determined to be 80% or greater. The E(CO)2 decomposition is facile for these methylperoxide reactions, and predominates over competing proton transfer at the hydroperoxide moiety. The CH3CH2OOH reaction displays a similar E(CO)2 reactivity, whereas proton transfer and the formation of HOO- are the exclusive pathways observed for (CH3)(3)COOH, which has no (x-hydrogen. All results are consistent with the E-CO(2) mechanism, transition state structure, and reaction energy diagrams calculated using the hybrid density functional B3LYP approach. Isotope labeling for HO- + CH3OOH also reveals some interaction between H2O and HO- within the E(CO)2 product complex [H2O center dot center dot center dot CH2=O center dot center dot center dot HO-]. There is little evidence, however. for the formation of the most exothermic products H2O + CH2(OH)O-, which would arise from nuclephilic condensation of CH2=O and HO-. The results suggest that the product dynamics are not totally statistical but are rather direct after the E-CO(2) transition state. The larger HO- + CH3CH2OOH system displays more statistical behavior during complex dissociation.

Direct observation of the gas phase reaction of the cyclohexyl radical with dioxygen using a distonic radical ion approach

Alkylperoxyl radicals are intermediates in the oxidation Of hydrocarbons. The reactive nature of these intermediates, however, has made therin elusive to direct observation and isolation. We have employed ion trap mass spectrometry to synthesize and characterize 4-carboxylatocyclohexyl radical anions ((center dot)C(6)H(10)-CO(2)(-)) and observe their reactivity in the presence of dioxygen. The resulting reaction is facile (k = 1.8 x 10(-10) cm(3) molecule(-1) s(-1) or 30% of calculated collision rate) and results in (i) the addition Of O(2) to form stabilized 4-carboxylatocyclohexylperoxyl radical anions ((center dot)OO-C(6)H(10)-CO(2)(-)), providing the first direct observation of a cyclohexylperoxyl radical, and (ii) elimination of HO(2)(center dot) and HO(center dot) radicals consistent with recent laser-induced fluorescence studies of the reaction of neutral cyclohexyl radicals with O(2). Electronic structure calculations at the B3LYP/6-31+G(d) level of theory reveal viable pathways for the observed reactions showing that formation of the peroxyl radical is exothermic by 37 kcal mol(-1) with subsequent transition states its low as -6.6 kcal mol(-1) (formation of HO(2)(center dot)) and -9.1 kcal mol(-1) (formation of HO(center dot)) with respect to the entrance channel. The combined computational and experimental data Suggest that the structures of the reaction products correspond to cyclohexenes and epoxides from HO(2)(center dot) and HO(center dot) loss, respectively, while alternative pathways leading to cyclohexanone or ring-opened isomers ate not observed, Activation of the charged peroxyl radical (center dot)OO-C(6)H(10)-CO(2)(-) by collision induced disassociation also results in the loss Of HO(2)(center dot) and HO(center dot) radicals confirming that these products are directly connected to the peroxyl radical intermediate.

Oxidation of 4-substituted TEMPO derivatives reveals modifications at the 1-and 4-positions

Potenital pathways for the deactivation of hindered amine light stabilisers (HALS) have been investigated by observing reactions of model compounds-based on 4-substituted derivatives of 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO)-with hydroxyl radicals. In these reactions, dilute aqueous suspensions of photocatalytic nanoparticulate titanium dioxide were irradiated with UV light in the presence of water-soluble TEMPO derivatives. Electron spin resonance (ESR) and electrospray ionisation mass-spectrometry (ESI-MS) data were acquired to provide complementary structural elucidation of the odd-and even-electron products of these reactions and both techniques show evidence for the formation of 4-oxo-TEMPO (TEMPONE). TEMPONE formation from the 4-substituted TEMPO compounds is proposed to be initiated by hydrogen abstraction at the 4-position by hydroxyl radical. High-level ab initio calculations reveal a thermodynamic preference for abstraction of this hydrogen but computed activation barriers indicate that, although viable, it is less favoured than hydrogen abstraction from elsewhere on the TEMPO scaffold. If a radical is formed at the 4-position however, calculations elucidate two reaction pathways leading to TEMPONE following combination with either a second hydroxyl radical or dioxygen. An alternate mechanism for conversion of TEMPOL to TEMPONE via an alkoxyl radical intermediate is also considered and found to be competitive with the other pathways. ESI-MS analysis also shows an increased abundance of analogous 4-substituted piperidines during the course of irradiation, suggesting competitive modification at the 1-position to produce a secondary amine. This modification is confirmed by characteristic fragmentation patterns of the ionised piperidines obtained by tandem mass spectrometry. The conclusions describe how reaction at the 4-position could be responsible for the gradual depletion of HALS in pigmented surface coatings and secondly, that modification at nitrogen to form the corresponding secondary amine species may play a greater role in the stabilisation mechanisms of HALS than previously considered.

Tunable “Nano-Shearing” : A physical mechanism to displace nonspecific cell adhesion during rare cell detection

We report a tunable alternating current electrohydrodynamic (ac-EHD) force which drives lateran fluid motion within a few nanometers of an electrode surface. Because the magnitude of this fluid shear force can be tuned externally (e.g., via the application of an ac electric field), it provides a new capability to physically displace weakly (nonspecifically) bound cellular analytes. To demonstrate the utility of the tunable nanoshearing phenomenon, we present data on purpose-built microfluidic devices that employ ac-EHD force to remove nonspecific adsorption of molecular and cellular species. Here, we show that an ac-EHD device containing asymmetric planar and microtip electrode pairs resulted in a 4-fold reduction in nonspecific adsorption of blood cells and also captured breast cancer cells in blood, with high efficiency (approximately 87%) and specificity. We therefore feel that this new capability of externally tuning and manipulating fluid flow could have wide applications as an innovative approach to enhance the specific capture of rare cells such as cancer cells in blood.

Heating mechanism of self-interaction of surface polaritons at n-type semiconductor-metal interface

The influence of electron heating in the high-frequency surface polariton (SP) field on the dispersion properties of the SPs considered is investigated. High frequency SPs propagate at the interface between an n-type semiconductor with finite electron pressure, and a metal. The nonlinear dispersion relation for the SPs is derived and investigated.

Preparation of graphene oxide/epoxy nanocomposites with significantly improved mechanical properties

The effect of graphene oxide (GO) on the mechanical properties and the curing reaction of Diglycidyl Ether of Bisphenol A/F and Triethylenetetramine epoxy system was investigated. GO was prepared by oxidation of graphite flakes and characterized by spectroscopic and microscopic techniques. Epoxy nanocomposites were fabricated with different GO loading by solution mixing technique. It was found that incorporation of small amount of GO into the epoxy matrix significantly enhanced the mechanical properties of the epoxy. In particular, model I fracture toughness was increased by nearly 50% with the addition of 0.1 wt. % GO to epoxy. The toughening mechanism was understood by fractography analysis of the tested samples. The more irregular, coarse, and multi-plane fracture surfaces of the epoxy/GO nanocomposites were observed. This implies that the two-dimensional GO sheets effectively disturbed and deflected the crack propagation. At 0.5 wt. % GO, elastic modulus was ~35% greater than neat epoxy. Differential scanning calorimetry (DSC) results showed that GO addition moderately affect the glass transition temperature (Tg) of epoxy. The maximum decrease of Tg by ~7 oC was shown for the nanocomposite with 0.5 wt. % GO. DSC results further revealed that GO significantly hindered the cure reaction in the epoxy system.

Nonvolatile multilevel data storage memory device from controlled ambipolar charge trapping mechanism

The capability of storing multi-bit information is one of the most important challenges in memory technologies. An ambipolar polymer which intrinsically has the ability to transport electrons and holes as a semiconducting layer provides an opportunity for the charge trapping layer to trap both electrons and holes efficiently. Here, we achieved large memory window and distinct multilevel data storage by utilizing the phenomena of ambipolar charge trapping mechanism. As fabricated flexible memory devices display five well-defined data levels with good endurance and retention properties showing potential application in printed electronics.

New reaction paths for metal diborides at low temperature and pressure

Attention has recently focussed on MgB2 superconductors (Tc~39K) which can be formed into wires with high material density and viable critical current densities (Jc)1. However, broader utilisation of this diboride and many others is likely to occur when facile synthesis for bulk applications is developed. To date, common synthesis methods include high temperature sintering of mixed elemental powders2, combustion synthesis3, mechano-chemical mixing with high temperature sintering4 and high pressure (~GPa region) with high temperature. In this work, we report on a lower temperature, moderate (<4MPa) pressure method to synthesise metal diborides.