281 research outputs found
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
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Low-temperature formation of polycyclic aromatic hydrocarbons in Titan’s atmosphere
The detection of benzene in Titan’s atmosphere led to the emergence of polycyclic aromatic hydrocarbons (PAHs) as potential nucleation agents triggering the growth of Titan’s orange-brownish haze layers. However, the fundamental mechanisms leading to the formation of PAHs in Titan’s low-temperature atmosphere have remained elusive. We provide persuasive evidence through laboratory experiments and computations that prototype PAHs like anthracene and phenanthrene (C14H10) are synthesized via barrierless reactions involving naphthyl radicals (C10H7•) with vinylacetylene (CH2=CH–C≡CH) in low-temperature environments. These elementary reactions are rapid, have no entrance barriers, and synthesize anthracene and phenanthrene via van der Waals complexes and submerged barriers. This facile route to anthracene and phenanthrene—potential building blocks to complex PAHs and aerosols in Titan—signifies a critical shift in the perception that PAHs can only be formed under high-temperature conditions, providing a detailed understanding of the chemistry of Titan’s atmosphere by untangling elementary reactions on the most fundamental level
Laparoscopic Roux-en-Y reconstruction in a patient with afferent loop syndrome and peptic ulcers of gastroenteroanastomosis - A first experience
This paper is devoted to the description of a currently rare clinical observation of the surgical treatment of a patient with postgastroresection syndrome (afferent loop syndrome and peptic ulcers of gastroenteroanastomosis) - resection of the stomach stump with laparoscopic Roux-en-Y reconstructio
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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
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
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
A Window on the CP-violating Phases of MSSM from Lepton Flavor Violating Processes
It has recently been shown that by measuring the transverse polarization of
the final particles in the LFV processes , and
, one can derive information on the CP-violating phases of the
underlying theory. We derive formulas for the transverse polarization of the
final particles in terms of the couplings of the effective potential leading to
these processes. We then study the dependence of the polarizations of and
in the and on the parameters of the
Minimal Supersymmetric Standard Model (MSSM). We show that combining the
information on various observables in the and
search experiments with the information on the electric dipole moment of the
electron can help us to solve the degeneracies in parameter space and to
determine the values of certain phases.Comment: 16 pages, 8 figure
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