Predicting polycyclic aromatic hydrocarbon formation with an automatically generated mechanism for acetylene pyrolysis

Using Reaction Mechanism Generator (RMG), we have automatically constructed a detailed mechanism for acetylene pyrolysis, which predicts formation of polycyclic aromatic hydrocarbons (PAHs) up to pyrene. To improve the data available for formation pathways from naphthalene to pyrene, new high‐pressure limit reaction rate coefficients and species thermochemistry were calculated using a combination of electronic structure data from the literature and new quantum calculations. Pressure‐dependent kinetics for the CH potential energy surface calculated by Zádor et al. were incorporated to ensure accurate pathways for acetylene initiation reactions. After adding these new data into the RMG database, a pressure‐dependent mechanism was generated in a single RMG simulation which captures chemistry from C to C. In general, the RMG‐generated model accurately predicts major species profiles in comparison to plug‐flow reactor data from the literature. The primary shortcoming of the model is that formation of anthracene, phenanthrene, and pyrene are underpredicted, and PAHs beyond pyrene are not captured. Reaction path analysis was performed for the RMG model to identify key pathways. Notable conclusions include the importance of accounting for the acetone impurity in acetylene in accurately predicting formation of odd‐carbon species, the remarkably low contribution of acetylene dimerization to vinylacetylene or diacetylene, and the dominance of the hydrogen abstraction CH addition (HACA) mechanism in the formation pathways to all PAH species in the model. This work demonstrates the improved ability of RMG to model PAH formation, while highlighting the need for more kinetics data for elementary reaction pathways to larger PAHs.     

E. Thomas Strom and Vera V. Mainz (eds): The posthumous Nobel Prize in chemistry. Volume 1. Correcting the errors and oversights of the Nobel Prize committee

Structural Chemistry -     

Carl Djerassi,structural chemist turned author/playwright,has published a new autobiography,In Retrospect: From the Pill to the Pen

The stereochemist and steroid chemist Carl Djerassi turned poet, novelist, and playwright, published another autobiography taking stock of his prolific production of science-in-fiction during the last decades. He has been successful in bridging the gap between science and art.     

Ion transmission in an electrospray ionization-mass spectrometry interface using an S-lens

We present the design and performance of an in-house built electrospray ionization-mass spectrometry (ESI-MS) interface equipped with an S-lens ion guide. The ion source was designed specifically for our ion beam experiments to investigate the chemical reactivity and deposition of the clusters and nanoparticles. It includes standard ESI-MS interface components, such as nanoelectrospray, ion transfer capillary, and the S-lens. A custom design enables systematic optimization of all relevant factors influencing ion formation and transfer through the interface. By varying the ESI voltage and flow rate, we determined the optimal operating conditions for selected silica emitters. A comparison of the pulled silica emitters with different tip inner diameters reveals that the total ion current is highest for the largest tip, whereas a tip with the smallest diameter exhibited the highest transmission efficiency through the ESI-MS interface. Ion transmission through the transfer capillary is strongly limited by its length, but the loss of ions can be reduced by increasing the capillary voltage and temperature. The S-lens was characterized over a wide range of RF frequencies and amplitudes. Maximum ion current was detected at RF amplitudes greater than 50 V peak-to-peak (p/p) and frequencies above 750 kHz, with a stable ion transmission region of about 20%. A factor of 2.6 increase in total ion current is observed for 650 kHz as RF amplitudes reach 400 V p/p. Higher RF amplitudes also focus the ions into a narrow beam, which mitigates their losses when passing through the ion guide.     

A scalable Nenitzescu synthesis of 2‐methyl‐4‐(trifluoromethyl)‐1H‐indole‐5‐carbonitrile

2‐Methyl‐4‐(trifluoromethyl)‐1H‐indole‐5‐carbonitrile is a key intermediate in the synthesis of selective androgen receptor modulators discovered in these laboratories. A practical and convergent synthesis of the title compound starting from 4‐nitro‐3‐(trifluoromethyl)phenol and tert‐butyl acetoacetate was developed, including a telescoped procedure for synthesis (without isolation) and Nenitzescu reaction of 2‐trifluoromethyl‐1,4‐benzoquinone. Conversion of the known Nenitzescu indole product to a novel triflate intermediate followed by palladium‐catalyzed cyanation afforded a penultimate carbonitrile. Removal of the C‐3 tert‐butyl ester group on the indole through a decarboxylative pathway completed the synthesis of the title compound in six steps (27% overall yield) from 4‐nitro‐3‐(trifluoromethyl)phenol (five steps, 37% overall yield from tert‐butyl acetoacetate). J. Heterocyclic Chem., (2011).     

��There is no such animal (??? ??? ???)����Lessons of a discovery

The discovery of quasicrystals by Dan Shechtman in the early 1980s was a conspicuous event in materials science not only because it led to the production of a plethora of new materials but also because it signified the demise of a dogma in the science of condensed phase materials concerning symmetry restrictions. Having the discovery recognized was not easy and it required stamina on Shechtman??s part. The story of the quasicrystal discovery offers a set of lessons that might be useful to remember in similar situations.     

In celebration of 30 years of Structural Chemistry: a “delocalized” special issue

Structural Chemistry -     

Determination of 1,4-Dichlorobenzene in Environmental Matrices

1,4-Dichlorobenzene is a frequently used lavatory deodorant although it has strong endocrine disrupting and potential carcinogenic effects. A large amount (approximately 15,000 tonnes annually worldwide) of this compound is released into the environment. This paper deals with the determination of 1,4-dichlorobenzene in a variety of environmental matrices. Various extraction and concentration methods such as charcoal absorbtion tubes and headspace sampling were applied. Sensitive and selective ion monitoring GC-MS measurements were used for determination. Significant concentrations of the compound have been identified in lavatory air, waste water, waste water sludge and human breast milk.

     

Structures and mechanisms in chemical reactions: George A. Olah’s life-long search of chemistry

The Hungarian-born American chemistry Nobel laureate George A. Olah used superacids to give longer life to carbocations. He resolved a long-standing debate on reaction mechanism in organic chemistry and, more importantly, opened new vistas in hydrocarbon chemistry to produce hosts of new compounds. The concerted utilization of organic synthesis, physical techniques, and computational methods led to spectacular achievements in hydrocarbon chemistry. Olah has always been on the lookout for the practical applications of his discoveries in fundamental chemistry. He continued his research after his Nobel award and has worked out the idea, which he labeled “the methanol economy.” Olah’s example shows that a great researcher can also be a devoted and caring human being.