Methyl Branches Research Articles

A review of contamination status, emission sources, and human exposure to volatile methyl siloxanes (VMSs) in indoor environments.

Siloxanes are organo-silicon compounds containing Si-O-Si linkages and methyl branches. Depending on the structure, siloxanes can be divided into cyclic and linear compounds. Methyl siloxanes with small and medium molecular weights (molecular weights less than 500 g mol-1), are volatile under normal conditions, and hence are referred to as volatile methyl siloxanes (VMSs). VMSs are additive ingredients in many products such as plastics, rubber, personal care products, and household items. This review provides information on the distribution of VMSs in consumer products, indoor air and dust, and their implications for human exposure. VMSs have been used in personal care products and household items at concentrations on the order of hundreds to thousands of micrograms per gram which are the main sources of contamination in the indoor environments. VMSs have been found widely in indoor air and dust. A significant correlation existed between VMS concentrations in indoor air and dust. Among typical VMSs, dodecamethylcylcopentasiloxane (D5) is the major compound found in indoor environments. The human exposure doses to VMSs through dermal absorption, dust ingestion, and inhalation were compiled; Inhalation is a dominant pathway of exposure to VMSs, especially in indoor environments of occupational settings like hair salons. The human exposure doses were higher in children than in adults.

A process to convert sunflower oil into a value added branched chain oil with unique properties

The global interest in reducing the use of petroleum resources to mitigate climate change has created a need for the continuing demand for environmentally friendly systems from renewable resources to produce clean and sustainable technology. One promising approach involves the development of catalysts and process improvements to increase the efficiency of the chemical modification reactions. In this study, sunflower oil was used in the skeletal isomerization reaction to introduce methyl branching at the alkyl fatty acid chain of the oil (methyl-branched-chain triglycerides (MBC-TG)) in the presence of a modified H+-BETA zeolite catalyst. Such modification of the oil is proposed to improve its low temperature fluidity, by preventing precipitation at low temperatures. The modified catalyst was easy to handle and separate from the reaction products. The products were thoroughly characterized by common analytical instruments. To evaluate the practicality of this environmentally friendly process, a techno-economic model was constructed to estimate the production cost.

Ruthenium(II)‐Catalyzed β‐Methylation of Alcohols using Methanol as C1 Source

AbstractSelective introduction of methyl branches into the carbon chains of alcohols can be achieved with low loadings of ruthenium precatalyst [RuH(CO)(BH4)(HN(C2H4PPh2)2)] (Ru‐MACHO‐BH) using methanol both as methylating reagent and as reaction medium. A wide range of structurally divers alcohols was β‐methylated with excellent selectivity (>99 %) in fair to high yields (up to 94 %) under standard conditions, and turnover numbers up to 18,000 could be established. The overall reaction rate of the complex catalytic network appears to be governed by interconnection of the individual subcycles through availability of the reactive intermediates. The synthetic procedure opens pathways to important structural motifs following the Green Chemistry principles.

Modification of rGO by B(C6F5)3 to generated single-site Lewis Acid [tbnd]rGO-O-B(C6F5)2 as co activator of nickel complex, to produce highly disperse rGO-PE nanocomposite

We investigated the incorporation of reduced graphene oxide (rGO) into branched polyethylene, achieving nanocomposites with different rGO contents. The strategy included the direct reaction between B(C6F5)3 (BCF) with rGO (reduced graphene oxide) and demonstrated by XPS, 11B, 19F -MAS NMR, FT-IR the efficient modification of the rGO. The resulting solid contains sites -O-B(C6F5)2 capable of acting as co-catalysts in the activation of an (α-iminocarboxamidate)nickel (II) complex. The results show the efficient activation of this nickel catalyst through an exocyclic Lewis acid-base interaction and the subsequent ethylene polymerization. We achieved with this heterogeneous catalytic system activity greater than those previously reported for the BCF-Ni, homogenous system, while the characterization of the black colored polymer generated in situ, showed a complete delamination of the rGO. It became the first rGO-B(C6F5)2-Ni system fully characterized and capable of delaminate the rGO support by producing a nanocomposite rGO-LLDPE without loss of activity, compared to the homogeneous system. In addition, the polymer contains about 70% of methyl branches and a melting point higher than 125 °C.

Cooperative effect through different bridges in nickel catalysts for polymerization of ethylene

A series of mononuclear (M1 and M2) and dinuclear (C1–C6) Ni α‐diimine catalysts activated by modified methylaluminoxane were used in polymerization of ethylene. Catalyst C2 bearing the optimum bulkiness showed the highest activity (1.6 × 106 g PE (mol Ni)−1 h−1) and the lowest short‐chain branching (32.5/1000 C) in comparison to the dinuclear and mononuclear analogues. Although the mononuclear catalysts M1 and M2 polymerized ethylene to a branched amorphous polymer, the dinuclear catalysts led to different branched semicrystalline polyethylenes. Homogeneity and heterogeneity in the microstructure of the polyethylene samples was observed. Different trends for each catalyst were assigned to syn and anti stereoisomers. In addition, thermal behavior of the samples in the successive self‐nucleation and annealing technique exhibited different orders and intensities from methylene sequences and lamellae thickness in respect of each stereoisomer behavior. Higher selectivity of hexyl branches obtained by catalyst C2 showed a cooperative effect between the centers. The results also revealed that for catalysts C5 and C6, selectivity of methyl branches led to very high endotherms and crystalline sequences with melting temperatures higher than that of 100% crystalline polyethylene indicating ethylene/propylene copolymer analogues. For catalysts C3 and C4, more vinyl end groups were a result of the long distance between the Ni centers. Kinetic profiles of polymerization along with a computational study of the precatalysts and catalysts demonstrated that there is a direct relation between rate constant, energy interval of catalyst and precatalyst, and interaction energy of Et···methyl cationic active center (Et···MCC or π–Comp.). Based on this, narrow energy interval (activation energy) of precatalyst and catalyst leads to fast and higher activation rate (catalyst M2), and strong interaction of ethylene and catalyst leads to high monomer uptake and productivity (catalyst C2). Moreover, theoretical parameters including electron affinity, Mulliken charge on Ni, chemical potential and hardness, and global electrophilicity showed optimum values for C2.

Cationic para‐phenyl‐substituted α‐diimine nickel catalyzed ethylene and 4‐methyl‐1‐pentene (co)polymerizations via living/controlled chain‐walking

Upon activation with diethylaluminium chloride (Et2AlCl), a series of phenyl‐substituted α‐diimine nickel precatalysts conducted 4‐methyl‐1‐pentene (4MP) and ethylene (E) (co)polymerizations via controlled chain‐walking to generate branched amorphous polymers with high molecular weight and narrow molecular weight distribution (Mw/Mn < 1.6). The obtained poly(4MP)s were amorphous elastomers with glass transition temperature (Tg) of −10 ~ −24 °C, which are higher than that of E‐4MP copolymer (−63.0 °C). At room temperature (25 °C), 4MP polymerization proceeds in a living manner. The microstructures of the produced poly(4MP)s indicated the 2,1‐ and 1,2‐insertion followed by chain‐walking, the latter being predominant. The NMR analyses of the polymers showed that the obtained poly(4MP) possessed methyl, isobutyl, 2,4‐dimethylpentyl and 2‐methylhexyl groups, while the isobutyl and 2,4‐dimethylalkyl branches derived from 4MP were observed in the E‐4MP copolymer. The branch structures and the insertion‐type of monomer were depended on the polymerization temperature, and the content of methyl branch increased with an increase in the polymerization temperature.

(Micro)structure, thermal behavior and mechanical properties of ethylene–propylene–1-octadecene terpolymers from chain-walking polymerization of 1-octadecene

This paper reports the polymerization of 1-octadecene catalyzed by a series of α-diimine Ni(II) complex, with methyl ligand backbone and different substituents in the ortho and para aryl positions, in combination with Et2AlCl. We obtained semicrystalline ethylene–propylene–1-octadecene terpolymers with high molecular weight and narrow molecular weight distribution. The formation of such terpolymers is due to the numerous combinations of insertion and chain-walking pathways. The effect of the type of ligand and monomer feedstock concentration on the activity, regioselectivity, polymers (micro)structure, and structure/properties is thoroughly investigated by NMR, DSC, WAXD and SAXS. The thermal behavior and the crystal structure of the polymers are strongly influenced by the level of incorporation of methyl and longer alkyl branches. The chain heterogeneity of the polymers is investigated by successive self-nucleation and annealing thermal fractionation evaluating the crystallizable sequence length, and the lamellar thickness.

4+4]-Cycloaddition of Isoprene for the Production of High-Performance Bio-Based Jet Fuel.

Isoprene was efficiently converted to 1,6-dimethyl-1,5-cyclooctadiene (DMCOD) by selective [4+4]-cycloaddition with a catalyst formed by in situ reduction of [(MePI)FeCl(μ-Cl)]2 (MePI = [2-(2,6-(CH3)2-C6H3-N=C(CH3))-C4H5N]). DMCOD was isolated in 92% yield, at the preparative scale, with a catalyst loading of 0.025 mol%, and a TON of 3680. Catalytic hydrogenation of DMCOD yielded 1,4-dimethylcyclooctane (DMCO). The cyclic structure and ring strain of DMCO afforded gravimetric and volumetric net heats of combustion 2.4 and 9.2% higher, respectively, than conventional jet fuel. In addition, the presence of methyl branches at two sites resulted in a -20 °C kinematic viscosity of 4.17 mm2 s-1, 48 % lower than the maximum allowed value for conventional jet fuel. The ability to derive isoprene and related alcohols readily from abundant biomass sources, coupled with the highly efficient [Fe]-catalyzed [4+4]-cycloaddition described herein, suggests that this process holds great promise for the economical production of high-performance, bio-based jet fuel blendstocks.

Synthesis and Molecular Editing of Callyspongiolide, Part 1: The Alkyne Metathesis/trans-Reduction Strategy.

A path-scouting investigation into the highly cytotoxic marine macrolide callyspongiolide is reported that capitalizes on the selective formation of the C10-C11 alkene site. While the closure of the macrocycle by ring closing alkyne metathesis (RCAM) with the aid of a molybdenum alkylidyne complex was high yielding, the envisaged semi-reduction of the cycloalkyne to the corresponding E-alkene proved challenging. The reasons are likely steric in origin, in that the methyl branches on either side of the alkyne seem to prevent effective coordination of the substrate to the ruthenium catalyst, which must carry a bulky Cp* ligand to ensure high trans-selectivity. This notion is supported by the preparation of a callyspongiolide analogue, in which the two methyl groups in question are excised; its formation by RCAM followed by trans-hydrostannation/proto-destannation was straightforward. In parallel work the formation of the fully functional building block 54 showed that the presence of an unprotected -OH group allows even hindered substrates to be processed: the protic group adjacent to the triple bond engages with a chloride ligand on the ruthenium catalyst in hydrogen bonding and hence assists in substrate binding. Moreover, the preparation of an alkynylogous callyspongiolide analogue is described.

Controllable synthesis of transparent dispersions of monodisperse anatase-TiO2 nanoparticles and nanorods

Controllable synthesis of monodisperse nanocrystals is still a great challenge. In this study, the control strategy of alcohol medium was developed to conveniently synthesize monodisperse anatase-TiO2 nanocrystals with controllable size and shape by sol-gel method combined with solvothermal treatment. The effects of the amount of stearic acid and water, and molecular structure of alcohol on the size, the shape and the dispersity of TiO2 nanocrystals were explored. The optimum synthesis conditions were achieved. Monodisperse TiO2 nanoparticles and nanorods were obtained by using linear and branched alcohols, respectively. The size of nanoparticles decreased from 12 to 5 nm with increasing carbon number of linear alcohol. The aspect ratio of nanorods was adjusted from 1 to 5 by selecting alcohols with different locations of branched methyl group. The as-prepared monodisperse TiO2 nanocrystals could be readily dispersed in some commonly-used solvents to form transparent nanodispersions. Furthermore, a possible formation mechanism was also investigated.

Methanogenesis on Early Stages of Life: Ancient but Not Primordial.

Of the six known autotrophic pathways, the Wood-Ljungdahl pathway (WL) is the only one present in both the acetate producing Bacteria (homoacetogens) and the methane producing Archaea (hydrogenotrophic methanogens), and it has been suggested that WL is one of the oldest metabolic pathways. However, only the so-called carbonyl branch is shared by Archaea and Bacteria, while the methyl branch is different, both in the number of reactions and enzymes, which are not homologous among them. In this work we show that some parts of the methyl branch of archaeal Wood-Ljungdahl pathway (MBWL) are present in bacteria as well as in non-methanogen archaea, although the tangled evolutionary history of MBWL cannot be traced back to the Last Common Ancestor. We have also analyzed the different variants of methanogenesis (hydrogenotrophic, acetoclastic and methylotrophic pathways), and concluded that each of these pathways, and every different enzyme or subunit (in the case of multimeric enzymes), has their own intricate evolutionary history. Our study supports the scenario of hydrogenotrophic methanogenesis being older than the other variants, albeit not old enough to be present in the last archaeal common ancestor.

Synthesis, APPI Mass-Spectrometric Characterization, and Polymerization Studies of Group 4 Dinuclear Bis(ansa-metallocene) Complexes

New ligand platforms of the type p- or m-Ph{-CR(3,6-tBu2Flu)(Cp)}2 (para-, R = Me (2a), H (2b); meta-, R = Me (2c)) were synthesized via nucleophilic addition of the 3,6-tBu2-fluorenyl-anion onto the parent phenylene-bridged difulvenes (1a–c). The corresponding discrete homodinuclear zirconium and hafnium bis(dichloro ansa-metallocene) complexes, Ph[{-CR(3,6-tBu2Flu)(Cp)}MCl2]2 (p-, R = Me (3a-Zr2, 3a-Hf2), R = H (3b-Zr2); m-, R = Me (3c-Zr2), were prepared by salt metathesis reactions. An attempt to generate in situ a heterodinuclear complex 3a-Zr-Hf was also undertaken. For the first time, Atmospheric Pressure PhotoIonization (APPI) mass-spectrometric data were obtained for all dinuclear compounds and found to be in excellent agreement with the simulated ones. Preliminary studies on the catalytic performances of these dinuclear complexes, upon activation with MAO, in ethylene homopolymerization and ethylene/1-hexene copolymerization revealed a few differences as compared to those of the monometallic analogues. In particular, slightly lower molecular weights and a greater formation of short methyl and ethyl branches were obtained with the dinuclear systems.

Symbiodinolactone A, a new 12-membered macrolide from symbiotic marine dinoflagellate Symbiodinium sp.

A new 12-membered macrolide, symbiodinolactone A, was isolated from the culture broth of symbiotic marine dinoflagellate Symbiodinium sp. The gross structure of symbiodinolactone A was elucidated by spectroscopic analyses, and the relative configuration was elucidated by the J-based configuration analysis and density-functional theory calculations. Symbiodinolactone A is the new 12-membered macrolide possessing an E double bond between C-4 and C-5, a branched methyl group at C-7, and a 1,2,3-trihydroxybutyl group at C-11. Symbiodinolactone A is the first usual size macrolide and the first non-nitrogen-containing macrolide from dinoflagellate Symbiodinium sp. Symbiodinolactone A might be generated by the unexplained dinoflagellate polyketide biosynthetic machinery.

Influence of Branching on the Conformational Space: Case Study of Tri- sec-butyl Phosphate Using Matrix Isolation Infrared Spectroscopy and DFT Computations.

The conformational analysis of long chain phosphates poses a serious challenge due to the presence of rotationally flexible multiple alkyl groups. Tri- sec-butyl phosphate (TsBP) is an interesting example, in which branching can be expected to influence the conformational landscape. To solve the conformational problem of TsBP systematically, the conformations of model dimethyl- sec-butyl phosphate (DMsBP), a molecule possessing a single secondary butyl strand, were analyzed. On the basis of the analysis of the energy profile of DMsBP, a few conformational bunches were eliminated. The presence of branched methyl group appears to completely influence the conformational space of TsBP and as a result, the number of conformations is drastically reduced in comparison to its structural isomer, tri- n-butyl phosphate (TBP). B3LYP level of theory in association with 6-311++G(d,p) basis set was used for computing all the conformer geometries. Experimentally, the conformations of TsBP were studied using infrared spectroscopy by trapping the molecule in N2 and Ar matrixes at low temperatures, which were correlated well with the computational results.

Silsesquioxane‐Supported Chromium Catalyst for Insight into Phillips‐Type Ethylene Polymerization

AbstractTo investigate the Phillips catalyst for ethylene polymerization, a family of silsesquioxane‐supported chromium catalysts with a bipodal structure have been synthesized from trivalent or hexavalent chromium precursor and fully characterized by 1H/13C/29Si NMR, FT‐IR, and UV–vis spectroscopies. Upon activation with tri‐n‐octylaluminum or butylated hydroxytoluene (BHT) modified TIBA following the “TIBA‐BHT”, all the silsesquioxane‐supported chromium catalysts display moderate activities (50–523 g‐PE•g‐cat−1·h−1) for ethylene polymerization, producing polyethylene (PE) with high methyl branching level (0.1–1.3/1000C) and a clear bimodal molecular weight distribution (MWD). Catalysts with hexavalent chromium precursor exhibit higher activities than trivalent ones. The type of activator and coordination environments of the active site play a key role in the MWD of obtained PE.

Effect of Alcohol Structure on the Kinetics of Etherification and Dehydration over Tungstated Zirconia.

Linear and branched ether molecules have attracted recent interest as diesel additives and lubricants that can be produced from biomass-derived alcohols. In this study, tungstated zirconia was identified as a selective and green solid acid catalyst for the direct etherification of primary alcohols in the liquid phase, achieving ether selectivities of >94 % for C6 -C12 linear alcohol coupling at 393 K. The length of linear primary alcohols (C6 -C12 ) was shown to have a negligible effect on apparent activation energies for etherification and dehydration, demonstrating the possibility to produce both symmetrical and asymmetrical linear ethers. Reactions over a series of C6 alcohols with varying methyl branch positions indicated that substituted alcohols (2°, 3°) and alcohols with branches on the β-carbon readily undergo dehydration, but alcohols with branches at least three carbons away from the -OH group are highly selective to ether. A novel model compound, 4-hexyl-1dodecanol, was synthesized and tested to further demonstrate this structure-activity relationship. Trends in the effects of alcohol structure on selectivity were consistent with previously proposed mechanisms for etherification and dehydration, and help to define possible pathways to selectively form ethers from biomass-derived alcohols.

Cleaning Efficiency of Amino-Acid Surfactants with Polyoxyethylene Ether and Isopropanol in Liquid Carbon Dioxide

Although anionic surfactants have a distinct positive influence on the removal of particulate soil, the removal of particulate soils is insufficient in CO2 compared to perchloroethylene. A series of amino-acid surfactants was selected as main surfactants to study the influence of polyoxyethylene ether and cosolvent on the cleaning effect. Glu-C12 and C16(3) gave the best cleaning results, which increased from a detergency value of 4.6 when no surfactants were used to 8.32 when surfactants were used. In all experiments, charged anionic surfactant particles were formed, which are responsible for the removal of particulate soil from fabric by electrostatic repulsion. The use of a cosolvent (Isopropanol [IPA]) had a positive effect on the removal of particulate soil when using Glu-C12 and TX-45. However, for other compounding combinations, the addition of IPA had a negative effect on particulate soil removal. Of the cosolvents investigated, IPA was the most suitable. With the polarity of the system increasing after adding IPA, the ethylene oxide groups of TX-45 were partially extended to CO2. Through the steric effects of branched methyl groups, the cleaning effect was improved.

Direct All-Atom Molecular Dynamics Simulations of the Effects of Short Chain Branching on Polyethylene Oligomer Crystal Nucleation

Using all-atom molecular dynamics (MD) simulations, we demonstrate that short alkyl branches can hinder the nucleation of polyethylene (PE) oligomers. Although one methyl and ethyl branch in a 50-carbon oligomer may only slow the nucleation kinetics mildly, bulkier side chains, such as propyl, butyl, and hexyl branches, disturb the arrangement of neighboring backbone atoms, preventing these atoms from joining a growing crystal, and therefore significantly suppress the nucleation of PE crystals, with no clear evidence of nucleation being observed over a 20 ns simulation run when hexyl side chains are present. The degrees of branching and the distributions of short alkyl groups on PE backbones can also affect the crystallization kinetics, with well-spaced branches having a greater impact on crystallization than branches that are grouped within a shorter distance along the backbone that is similar to or shorter than the length of the branch. We show that the linear portions of PE crystallize first and the br...

Rakicidins G - I, cyclic depsipeptides from marine Micromonospora chalcea FIM 02-523

Rakicidins G-I (1–3), three new cyclic depsipeptides including a long aliphatic chain without terminal methyl branching were isolated from culture broth of Micromonospora chalcea FIM 02–523, along with rakicidin E (4). Their structures were elucidated by extensive NMR and HR-ESI-MS analyses. Compounds 1–4 were evaluated for their cytotoxic activities against HCT-8 and PANC-1 human tumor cell lines under the hypoxic and normoxic conditions. They were approximately 18.2–20.3-fold more cytotoxic under hypoxic than under normoxic conditions on PANC-1, and compared with 7.4–8.7-fold more cytotoxic under hypoxic than under normoxic conditions on HCT-8. Meanwhile, compounds 1–3 were also tested inhibitory activities against gram positive anaerobic bacteria and the results exhibited MIC values in the range of 0.125–8 μg/mL.

Probing the Flexibility of an Iterative Modular Polyketide Synthase with Non-Native Substrates in Vitro.

In the search for molecular machinery for custom biosynthesis of valuable compounds, the modular type I polyketide synthases (PKSs) offer great potential. In this study, we investigate the flexibility of BorM5, the iterative fifth module of the borrelidin synthase, with a panel of non-native priming substrates in vitro. BorM5 differentially extends various aliphatic and substituted substrates. Depending on substrate size and substitution BorM5 can exceed the three iterations it natively performs. To probe the effect of methyl branching on chain length regulation, we engineered a BorM5 variant capable of incorporating methylmalonyl- and malonyl-CoA into its intermediates. Intermediate methylation did not affect overall chain length, indicating that the enzyme does not to count methyl branches to specify the number of iterations. In addition to providing regulatory insight about BorM5, we produced dozens of novel methylated intermediates that might be used for production of various hydrocarbons or pharmaceuticals. These findings enable rational engineering and recombination of BorM5 and inform the study of other iterative modules.