The Structure and C=C Vibrational Frequencies of the all- trans Polyenes C2nH2n+2(n=2-15), C2nH2n(Me)2(n=2-13), and C2nH2n(tert-Butyl)2(n=2-5): Computational Results

Carbon-carbon bond lengths and C=C vibrational frequencies are reported for the linear, all-trans unsubstituted C2nH2n+2 (n=2-15), methyl capped C2nH2nMe2 (n=2-13), and tert-butyl capped C2nH2n(tert-butyl)2 (n=2-5) polyenes (C2h) calculated at the B3LYP/6-311++G(d,p) level. The C=C/C-C bond length alternation remains evident at this level for the unsubstituted and methyl capped polyenes as the chain length increases; the center-most difference in the length of the C-C/C=C bonds is ~0.06 Å for C30H32 and C26H26Me2. The Ag, in-phase, harmonic C=C Raman frequency for the unsubstituted polyenes decreases from 1699.2 cm-1 (n = 2) to 1528.9 cm-1 (n=15); the anharmonic frequency decreases from 1651.5 cm-1 (n = 2) to 1547.7 cm-1 (n = 8). The harmonic C=C frequency for the methyl capped polyenes decreases from 1717.9 cm-1 (n = 2) to 1539.6 cm- 1 (n= 13), and the anharmonic C=C frequency decreases from 1675.0 cm-1 (n = 2) to 1562.8 cm-1 (n = 7)

Structures and Stabilities of Carbon Chain Clusters Influenced by Atomic Antimony

The C-C bond lengths of the linear magnetic neutral CnSb, CnSb+ cations and CnSb− anions are within 1.255–1.336 Å, which is typical for cumulene structures with moderately strong double-bonds. In this report, we found that the adiabatic ionization energy (IE) of CnSb decreased with n. When comparing the IE~n relationship of CnSb with that of pure Cn, we found that the latter exhibited a stair-step pattern (n ≥ 6), but the IE~n relationship of CnSb chains took the shape of a flat curve. The IEs of CnSb were lower than those of corresponding pure carbon chains. Different from pure carbon chains, the adiabatic electron affinity of CnSb does not exhibit a parity effect. There is an even-odd alternation for the incremental binding energies of the open chain CnSb (for n = 1–16) and CnSb+ (n = 1–10, when n > 10, the incremental binding energies of odd (n) chain of CnSb+ are larger than adjacent clusters). The difference in the incremental binding energies between the even and odd chains of both CnSb and pure Cn diminishes with the increase in n. The incremental binding energies for CnSb- anions do not exhibit a parity effect. For carbon chain clusters, the most favorable binding site of atomic antimony is the terminal carbon of the carbon cluster because the terminal carbon with a large spin density bonds in an unsaturated way. The C-Sb bond is a double bond with Wiberg bond index (WBI) between 1.41 and 2.13, which is obviously stronger for a carbon chain cluster with odd-number carbon atoms. The WBI of all C-C bonds was determined to be between 1.63 and 2.01, indicating the cumulene character of the carbon chain. Generally, the alteration of WBI and, in particular, the carbon chain cluster is consistent with the bond length alteration. However, the shorter C-C distance did not indicate a larger WBI. Rather than relying on the empirical comparison of bond distance, the WBI is a meaningful quantitative indicator for predicting the bonding strength in the carbon chain

Influence of monomer structure and catalyst concentration on topological transition and dynamic properties of dicarboxylic acid‐epoxy vitrimers

This study delineates the dependence of thermophysical behavior of acid‐epoxy vitrimers on their formulation. The stress relaxation due to the bond exchange reaction and the glass transition temperature of acid epoxy vitrimers are investigated, with respect to the influence of catalyst content and acid chain length. This is carried out for a range of dicarboxylic acids and catalyst concentrations formulated and characterized using calorimetry and dynamic mechanical analysis. The influence of acid chain length on the bond exchange rate, topological transition, and glass transition temperatures of the vitrimers is found to be significant. The activation energy of the exchange reaction varies over a wide range from 73 to 104 kJ/mol and the topology freezing temperature from 66 to 136°C with the behavior governed by the interplay between crosslinking density, network flexibility and density and distance of functional groups, with an increase of catalyst concentration leading to lower topological transition temperature and the dependence on chain length showing non‐monotonic behavior. The glass transition decreases by about 30°C as the carbon chain length increases from 6 to 14 carbons due to enhanced monomer flexibility and is not affected by the concentration of catalyst

Functionalization and Hydrogenation of Carbon Chains Derived from CO

Selective reactions that combine H 2 , CO and organic electrophiles (aldehyde, ketones, isocyanide) to form hydrogenated C 3 and C 4 carbon chains are reported. These reactions proceed by CO homologation mediated by [W(CO) 6 ] and an aluminum(I) reductant, followed by functionalization and hydrogenation of the chain ends. A combination of kinetics (rates, KIEs) and DFT calculations has been used to gain insight into a key step which involves hydrogenation of a metallocarbene intermediate. These findings expand the extremely small scope of systems that combine H 2 and CO to make well-defined products with complete control over chain length and functionality

Per- and polyfluoroalkyl substance (PFAS) retention by colloidal activated carbon (CAC) using dynamic column experiments

Developing effective remediation methods for per- and polyfluoroalkyl substance (PFAS)-contaminated soils is a substantial step towards counteracting their widespread occurrence and protecting our ecosystems and drinking water sources. Stabilisation of PFAS in the subsurface using colloidal activated carbon (CAC) is an innovative, yet promising technique, requiring better understanding. In this study, dynamic soil column tests were used to assess the retardation of 10 classical perfluoroalkyl acids (PFAAs) (C-5-C-11 perfluoroalkyl carboxylic acids (PFCAs) and C-4, C-6, C-8 perfluoroalkane sulfonates (PFSAs)) as well as two alternative PFAS (6:2 and 8:2 fluorotelomer sulfonates) using CAC at 0.03% w/w, to investigate the fate and transport of PFAS under CAC treatment applications. Results showed high retardation rates for long-chain PFAS and eight times higher retardation for the CAC-treated soil compared to the non-treated reference soil for the Sigma PFAS. Replacement of shorter chain perfluorocarboxylic acids (PFCAs), such as perfluoropentanoic acid (PFPeA), by longer chained PFAS was observed, indicating competition effects. Partitioning coefficients (K-d values) were calculated for the CAC fraction at similar to 10(3)-10(5) L kg(-1) for individual PFAS, while there was a significant positive correlation (p < 0.05) between perfluorocarbon chain length and K-d. Mass balance calculations showed 37% retention of Sigma PFAS in treated soil columns after completion of the experiments and 99.7% higher retention rates than the reference soil. Redistribution and elution of CAC were noticed and quantified through organic carbon analysis, which showed a 23% loss of carbon during the experiments. These findings are a step towards better understanding the extent of CAC's potential for remediation of PFAS-contaminated soil and groundwater and the limitations of its applications

Chain-length dependent ultrasonic degradation of perfluoroalkyl substances

Per- and polyfluoroalkyl substances (PFAS) have been found all over the world and are particularly persistent, potentially carcinogenic, and bioaccumulative in the environment. Degradation of short-chain perfluorinated carboxylic acids of varying carbon chain lengths (from 4 to 8 carbons), higher-chain perfluoro carboxylic acids of varying carbon chain lengths (from 9 to 14 carbons), and perfluorosulfonic acids of varying carbon chain lengths (6 and 8 carbons) were tested in a flow through ultrasonic cavitation reactor to determine the efficacy of the high frequency ultrasound process. Temperature, frequency, power density, pH, sodium chloride, and sodium bicarbonate concentrations are examined as process parameters. The frequency and length of the PFAS chain were found to be vital components in the sonolytic degradation process. Degradation of all PFAS was shown to be particularly rapid at room temperature, basic pH, and a power density of 252 W/L. At a power density of 144 W/L, all of the PFAS were degraded by more than 97% in 8 h, with the exception of perfluorobutonic acid (83%) and perfluorohexanoic acid (94%). The bond dissociation energy of C-F bonds was found to be much higher than experimental sonolytic activation energies, supporting cavitation bubble as a catalyst for thermolytic destruction of PFAS compounds. Optimizing the reactor geometry has the potential to make this approach even more appealing for treating small volumes of concentrated wastes

Dilute gas viscosity of n-alkanes represented by rigid Lennard-Jones chains

The shear viscosity in the dilute gas limit has been calculated by means of the classical trajectory method for a gas consisting of chain-like molecules. The molecules were modelled as rigid chains made up of spherical segments that interact through a combination of site-site Lennard-Jones 12-6 potentials. Results are reported for chains consisting of 2, 3, 4, 6, 8, 12 and 16 segments in the reduced temperature range of 0.3 – 50 for site-site separations of 0.25 , 0.333 , 0.40 , 0.60 and 0.80 , where is the Lennard-Jones length scaling parameter. The results were used to determine the shear viscosity of n-alkanes in the zerodensity limit by representing an n-alkane molecule as a rigid linear chain consisting of c − 1 spherical segments, where c is the number of carbon atoms. We show that for a given n-alkane molecule, the scaling parameters ε and σ are not unique and not transferable from one molecule to another. The commonly used site-site Lennard-Jones 12-6 potential in combination with a rigid-chain molecular representation can only accurately mimic the viscosity if the scaling parameters are fitted. If the scaling parameters are estimated from the scaling parameters of other n-alkanes, the predicted viscosity values have an unacceptably high uncertainty

DETECTIONS OF LONG CARBON CHAINS CH3CCCCH, C6H, LINEAR-C6H2 AND C7H IN THE LOW-MASS STAR FORMING REGION L1527

Carbon chains in the warm carbon chain chemistry (WCCC) region has been searched in the 42--44 GHz region by using Green Bank 100 m telescope. Long carbon chains C$_{7}$H, C$_{6}$H, CH$_{3}$CCCCH, and linear-C$_{6}$H$_{2}$ and cyclic species C$_{3}$H and C$_{3}$H$_{2}$O have been detected in the low-mass star forming region L1527, performing the WCCC. C$_{7}$H was detected for the first time in molecular clouds. The column density of C$_{7}$H is derived to be $6.2 times 10^{10}$ cm$^{-2}$ by using the detected $J$ = 24.5--23.5 and 25.5--24.5 rotational lines. The $^{2}Pi_{1/2}$ electronic state of C$_{6}$H, locating 21.6 K above the $^{2}Pi_{3/2}$ electronic ground state, and the $K_a$ = 0 line of the para species of linear-C$_{6}$H$_{2}$ were also detected firstly in molecular clouds. The column densities of the $^{2}Pi_{1/2}$ and $^{2}Pi_{3/2}$ states of C$_{6}$H in L1527 were derived to be $1.6 times 10^{11}$ and $1.1 times 10^{12}$ cm$^{-2}$, respectively. The total column density of linear-C$_{6}$H$_{2}$ is obtained to be $1.86 times 10^{11}$ cm$^{-2}$. While the abundance ratios of carbon chains in between L1527 and the starless dark cloud Taurus Molecular Cloud-1 Cyanopolyyne Peak (TMC-1 CP) have a trend of decrease by extension of carbon-chain length, column densities of CH$_{3}$CCCCH and C$_{6}$H are on the trend. However, the column densities of linear-C$_{6}$H$_{2}$, and C$_{7}$H are as abundant as those of TMC-1 CP in spite of long carbon chain, i.e., they are not on the trend. The abundances of linear-C$_{6}$H$_{2}$ and C$_{7}$H show that L1527 is rich for long carbon chains as well as TMC-1 CP

Effect of chemical structure on the sonochemical degradation of perfluoroalkyl and polyfluoroalkyl substances (PFASs)

Perfluoroalkyl surfactants include chemicals characterized by a fully fluorinated carbon chain (hydrophobic and oleophobic tail) bound to a hydrophilic head (a carboxyl or sulfonic group). These compounds are toxic and highly resistant to chemical/biological attack, and some are known to be bio-accumulative. This study investigates the sonochemical degradation at 500 kHz of different carboxylic and sulfonic perfluoroalkyl and polyfluoroalkyl substances (PFASs, 1.7 mM total organic fluorine) to assess the effect of chain length, functional head group, and substituents (–CH2–CH2– moiety and ether group) on the degradation rate. Under these conditions, the rates of defluorination determined for two widely used perfluoroalkyl substances, perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA), were 3.5 to 3.7 μM F− min−1, respectively. The degradation rate of perfluoroalkyl sulfonates decreased with the perfluorocarbon chain length as indicated by the 1.3 and 1.9-fold lower defluorination rates for perfluorohexane- and perfluorobutane sulfonate than that of PFOS. A similar trend was observed during the sonolysis of perfluoroalkyl carboxylate analogs with 6, 5 or 3 carbon atoms which had 1.1-, 1.8-, and 2.3-fold lower defluorination rates, respectively, than that of PFOA. Furthermore, perfluoroalkyl compounds appeared more amenable to sonolysis than the polyfluoroalkyl analogues with the same number of C atoms (defluorination rate of PFOS/6 : 2 fluorotelomer sulfonate ≈ 2.3). The results demonstrate that sonolysis is a promising approach to treat PFASs in aqueous streams. Furthermore, they underscore that the chemical structure of PFASs has a marked effect on the rate at which they undergo sonochemical degradation

Residues at the Active Site of the Esterase 2 fromAlicyclobacillus acidocaldarius Involved in Substrate Specificity and Catalytic Activity at High Temperature

The recently solved three-dimensional structure of the thermophilic esterase 2 from Alicyclobacillus acidocaldarius allowed us to have a snapshot of an enzyme-sulfonate complex, which mimics the second stage of the catalytic reaction, namely the covalent acyl-enzyme intermediate. The aim of this work was to design, by structure-aided analysis and to generate by site-directed and saturation mutagenesis, EST2 variants with changed substrate specificity in the direction of preference for monoacylesters whose acyl-chain length is greater than eight carbon atoms. Positions 211 and 215 of the polypeptide chain were chosen to introduce mutations. Among five variants with single and double amino acid substitutions, three were obtained, M211S, R215L, and M211S/R215L, that changed the catalytic efficiency profile in the desired direction. Kinetic characterization of mutants and wild type showed that this change was achieved by an increase in k(cat) and a decrease in K(m) values with respect to the parental enzyme. The M211S/R215L specificity constant for p-nitrophenyl decanoate substrate was 6-fold higher than the wild type. However, variants M211T, M211S, and M211V showed strikingly increased activity as well as maximal activity with monoacylesters with four carbon atoms in the acyl chain, compared with the wild type. In the case of mutant M211T, the k(cat) for p-nitrophenyl butanoate was 2.4-fold higher. Overall, depending on the variant and on the substrate, we observed improved catalytic activity at 70 degrees C with respect to the wild type, which was a somewhat unexpected result for an enzyme with already high k(cat) values at high temperature. In addition, variants with altered specificity toward the acyl-chain length were obtained. The results were interpreted in the context of the EST2 three-dimensional structure and a proposed catalytic mechanism in which k(cat), e.g. the limiting step of the reaction, was dependent on the acyl chain length of the ester substrate