A Unified Mechanism on the Formation of Acenes, Helicenes, and Phenacenes in the Gas Phase.

A unified low-temperature reaction mechanism on the formation of acenes, phenacenes, and helicenes-polycyclic aromatic hydrocarbons (PAHs) that are distinct via the linear, zigzag, and ortho-condensed arrangements of fused benzene rings-is revealed. This mechanism is mediated through a barrierless, vinylacetylene mediated gas-phase chemistry utilizing tetracene, [4]phenacene, and [4]helicene as benchmarks contesting established ideas that molecular mass growth processes to PAHs transpire at elevated temperatures. This mechanism opens up an isomer-selective route to aromatic structures involving submerged reaction barriers, resonantly stabilized free-radical intermediates, and systematic ring annulation potentially yielding molecular wires along with racemic mixtures of helicenes in deep space. Connecting helicene templates to the Origins of Life ultimately changes our hypothesis on interstellar carbon chemistry

Measurements of Platinum Electrode Potential in Blood and Blood Plasma and Serum

The method of electrochemical pretreatment of platinum electrode with the goal of standardizing the initial state of electrode surface and its open-circuit potential (OCP) in the blood and other biological media is proposed. The platinum electrode potential is measured in 0.14 M Na2SO4 aqueous solution, in the blood and blood plasma and serum. By the examples of OCP measured in the blood serum of patients with acute poisoning, acute cerebral pathology and patients treated by the method of hyperbaric oxygenation, it was found that the values of blood serum OCP were different for studied pathological states and healthy people

Gas-Phase Synthesis of Triphenylene (C18 H12 ).

For the last decades, the hydrogen-abstraction-acetylene-addition (HACA) mechanism has been widely invoked to rationalize the high-temperature synthesis of PAHs as detected in carbonaceous meteorites (CM) and proposed to exist in the interstellar medium (ISM). By unravelling the chemistry of the 9-phenanthrenyl radical ([C14 H9 ]. ) with vinylacetylene (C4 H4 ), we present the first compelling evidence of a barrier-less pathway leading to a prototype tetracyclic PAH - triphenylene (C18 H12 ) - via an unconventional hydrogen abstraction-vinylacetylene addition (HAVA) mechanism operational at temperatures as low as 10 K. The barrier-less, exoergic nature of the reaction reveals HAVA as a versatile reaction mechanism that may drive molecular mass growth processes to PAHs and even two-dimensional, graphene-type nanostructures in cold environments in deep space thus leading to a better understanding of the carbon chemistry in our universe through the untangling of elementary reactions on the most fundamental level

Open Circuit Potential Shifts of Activated Carbon in Aqueous Solutions During Chemical and Adsorption Interactions

Interaction of certain inorganic and organic compounds with activated carbon and the effect of such interaction on open circuit potential of activated carbon were studied. Open circuit potential shifts were observed for an overwhelming majority of the substances and brands of activated carbons investigated. Both negative and positive potential shifts were observed. It was shown that open circuit potential shifts for organic substances depend on degree of coverage of the activated carbon surface. Whereas adsorption of investigated organic compound on activated carbon led to positive potential shifts, desorption of adsorbates from the activated carbon surface led to potential shifts in the opposite direction. Furthermore, time dependencies of open circuit potential shifts were similar for different carbon brands. The magnitude of the shifts depended on the adsorbate, adsorption activity of the adsorbent, and the steric configuration of potential-determinative pores and adsorbate molecules

Activated Carbon Open Circuit Potential Shifts in Aqueous Solutions

Interaction of certain organic compounds with activated carbon and its effect on the carbon open circuit potentials were studied. It was shown that shifts in open circuit potentials depended on the filling of the activated carbon surface. Whereas adsorption of the investigated compounds on the carbon led to positive potential shifts, their elimination (desorption) from carbon surface led to shifts in the opposite direction. It was also observed that the time dependence of potential shifts is similar for different carbon brands. The magnitude of shifts depended on adsorption activity and porometric characteristics of the carbon adsorbent, as well as the nature of the adsorbate

Complex Reactive Acids from Methanol and Carbon Dioxide Ice: Glycolic Acid (HOCH2COOH) and Carbonic Acid Monomethyl Ester (CH3OCOOH)

The formation of complex organic molecules by simulated secondary electrons generated in the track of galactic cosmic rays was investigated in interstellar ice analogs composed of methanol and carbon dioxide. The processed ices were subjected to temperature-programmed desorption to mimic the transition of a cold molecular cloud to a warmer star-forming region. Reaction products were detected as they sublime using photoionization reflectron time-of-flight mass spectrometry. By employing isotopic labeling, tunable photoionization and computed adiabatic ionization energies isomers of C _2 H _4 O _3 were investigated. Product molecules carbonic acid monomethyl ester (CH _3 OCOOH) and glycolic acid (HOCH _2 COOH) were identified. The abundance of the reactants detected in analog interstellar ices and the low irradiation dose necessary to form these products indicates that these molecules are exemplary candidates for interstellar detection. Molecules sharing a tautomeric relationship with glycolic acid, dihydroxyacetaldehyde ((OH) _2 CCHO), and the enol ethenetriol (HOCHC(OH) _2 ), were not found to form despite ices being subjected to conditions that have successfully produced tautomerization in other ice analog systems

A Unified Mechanism on the Formation of Acenes, Helicenes, and Phenacenes in the Gas Phase.

A unified low-temperature reaction mechanism on the formation of acenes, phenacenes, and helicenes-polycyclic aromatic hydrocarbons (PAHs) that are distinct via the linear, zigzag, and ortho-condensed arrangements of fused benzene rings-is revealed. This mechanism is mediated through a barrierless, vinylacetylene mediated gas-phase chemistry utilizing tetracene, [4]phenacene, and [4]helicene as benchmarks contesting established ideas that molecular mass growth processes to PAHs transpire at elevated temperatures. This mechanism opens up an isomer-selective route to aromatic structures involving submerged reaction barriers, resonantly stabilized free-radical intermediates, and systematic ring annulation potentially yielding molecular wires along with racemic mixtures of helicenes in deep space. Connecting helicene templates to the Origins of Life ultimately changes our hypothesis on interstellar carbon chemistry