Long-chain Diacids Research Articles

Alpine snowpit profiles of polar organic compounds from Mt. Tateyama central Japan: Atmospheric transport of organic pollutants with Asian dust

Snowpit samples (n = 10) were collected (19 April 2008) from the snowpit sequences (depth 6.60 m) at the Murodo-Daira site (36.58°N, 137.60°E, elevation of 2450 m a.s.l.) of Mt. Tateyama (3015 m a.s.l.), central Japan. The first time, low molecular weight diacids, ω-oxoacids, pyruvic acid, and α-dicarbonyls were measured for this snowpit sequence. Higher concentrations of short-chain diacids (C2–C5) are observed in dusty snow than non-dusty snow samples. Longer chain diacids (C7–C12) are significant in granular and dusty snow samples. Aromatic and aliphatic unsaturated diacids showed higher concentrations in the slightly dusty layer deposited in winter. Except for a clean layer, molecular distributions of diacids are characterized by the predominance of oxalic acid (C2, ave, 20 ± 22 ng/g-snow) followed by succinic (C4, 7.2 ± 5.9 ng/g -snow), and malonic acids (C3, 3.3 ± 2.9 ng/g -snow) for all the snow layers. Lower C3/C4 ratios (0.46) suggest that organic aerosols are rather fresh without serious photochemical aging during the long-range transport over central Japan. The higher concentrations of the secondary species in dusty snow than non-dusty samples were mainly attributed to the heterogeneous reaction. The strong correlations of incloud oxidation products of isoprene, aromatic acids, and fatty acids suggest that condensation, oxidation, and photolysis are important reaction mechanisms for the formation of diacids. Chinese Loess (Kosa particles) and Mongolian Gobi desert's dust provided the surface area for polar organic compounds, traveled to several thousand kilometers in the lower troposphere, and snow metamorphism altered the chemical composition of diacids and related compounds.

Properties of Novel Polyesters Made from Renewable 1,4-Pentanediol.

Novel polyester polyols were prepared in high yields from biobased 1,4‐pentanediol catalyzed by non‐toxic phosphoric acid without using a solvent. These oligomers are terminated with hydroxyl groups and have low residual acid content, making them suitable for use in adhesives by polyurethane formation. The thermal behavior of the polyols was studied by differential scanning calorimetry, and tensile testing was performed on the derived polyurethanes. The results were compared with those of polyurethanes obtained with fossil‐based 1,4‐butanediol polyester polyols. Surprisingly, it was found that a crystalline polyester was obtained when aliphatic long‐chain diacids (>C12) were used as the diacid building block. The low melting point of the C12 diacid‐based material allows the development of biobased shape‐memory polymers with very low switching temperatures (<0 °C), an effect that has not yet been reported for a material based on a simple binary polyester. This might find application as thermosensitive adhesives in the packaging of temperature‐sensitive goods such as pharmaceuticals. Furthermore, these results indicate that, although 1,4‐pentanediol cannot be regarded as a direct substitute for 1,4‐butanediol, its novel structure expands the toolbox of the adhesives, coatings, or sealants formulators.

Cellular and metabolic engineering of oleaginous yeast Yarrowia lipolytica for bioconversion of hydrophobic substrates into high-value products.

The non-conventional oleaginous yeast Yarrowia lipolytica is able to utilize both hydrophilic and hydrophobic carbon sources as substrates and convert them into value-added bioproducts such as organic acids, extracellular proteins, wax esters, long-chain diacids, fatty acid ethyl esters, carotenoids and omega-3 fatty acids. Metabolic pathway analysis and previous research results show that hydrophobic substrates are potentially more preferred by Y. lipolytica than hydrophilic substrates to make high-value products at higher productivity, titer, rate, and yield. Hence, Y. lipolytica is becoming an efficient and promising biomanufacturing platform due to its capabilities in biosynthesis of extracellular lipases and directly converting the extracellular triacylglycerol oils and fats into high-value products. It is believed that the cell size and morphology of the Y. lipolytica is related to the cell growth, nutrient uptake, and product formation. Dimorphic Y. lipolytica demonstrates the yeast-to-hypha transition in response to the extracellular environments and genetic background. Yeast-to-hyphal transition regulating genes, such as YlBEM1, YlMHY1 and YlZNC1 and so forth, have been identified to involve as major transcriptional factors that control morphology transition in Y. lipolytica. The connection of the cell polarization including cell cycle and the dimorphic transition with the cell size and morphology in Y. lipolytica adapting to new growth are reviewed and discussed. This review also summarizes the general and advanced genetic tools that are used to build a Y. lipolytica biomanufacturing platform.

Rapid access with diversity to enantiopure flexible PNA monomers following asymmetric orthogonal strategies

Different synthetic procedures are described in the rapid elaboration of flexible PNA monomers based on the 6-amino-8-base-octanoate and 5-amino-7-base-heptanoate scaffolds. Asymmetric Aza-Michael monoaddition is successfully applied to starting materials derived from sebacic/azelaic long-chain diacids and 6-membered oxacyclohexane commercial derivatives. Chain length, orthogonality of the ester functionalities, and Z/E isomerism of these prime substrates yielded high-valuable multifunctional intermediates through this asymmetric conjugate addition. Key features are the diversity toward PNA monomer synthesis, orthogonal chemoselective transformations, and Mitsunobu nucleobase substitution as an exceptional approach to introduce nucleobases in the final step.

Synthesis and structure–property evaluation of cellulose ω-carboxyesters for amorphous solid dispersions

The use of amorphous solid dispersions (ASDs) is an effective and increasingly widely used approach for solubility enhancement of drugs and drug candidates with poor aqueous solubility. Successful molecular dispersion of drugs in polymer matrices requires new polymers that are designed to meet all ASD requirements, including drug release and prevention of drug recrystallization in storage or from solution. We describe herein design and synthesis of a new series of cellulose ω-carboxyalkanoates for ASDs, by reaction of cellulose with long-chain diacids that have been monoprotected as benzyl esters at one end, and monoactivated as acid chlorides at the other. Glass transition temperatures (Tg) of these cellulose ω-carboxyesters exceed ambient temperature by at least 50°C, providing a sufficient ΔT to prevent drug mobility and crystallization. Cellulose acetate suberates and sebacates prepared in this way are extraordinary solution crystal growth inhibitors for the poorly soluble anti-HIV drug ritonavir. These new cellulose ω-carboxyesters have strong potential as ASD polymers for enhancement of drug solubility and bioavailability.

Lipids as renewable resources: current state of chemical and biotechnological conversion and diversification

Oils and fats are the most important renewable raw materials of the chemical industry. They make available fatty acids in such purity that they may be used for chemical conversions and for the synthesis of chemically pure compounds. Oleic acid (1) from "new sunflower," linoleic acid (2) from soybean, linolenic acid (3) from linseed, erucic acid (4) from rape seed, and ricinoleic acid (5) from castor oil are most important for chemical transformations offering in addition to the carboxy group one or more C-C-double bonds. New plant oils containing fatty acids with new and interesting functionalities such as petroselinic acid (6) from Coriandrum sativum, calendic acid (7) from Calendula officinalis, alpha-eleostearic acid (8) from tung oil, santalbic acid (9) from Santalum album (Linn.), and vernolic acid (10) from Vernonia galamensis are becoming industrially available. The basic oleochemicals are free fatty acids, methyl esters, fatty alcohols, and fatty amines as well as glycerol as a by-product. Their interesting new industrial applications are the usage as environmentally friendly industrial fluids and lubricants, insulating fluid for electric utilities such as transformers and additive to asphalt. Modern methods of synthetic organic chemistry including enzymatic and microbial transformations were applied extensively to fatty compounds for the selective functionalization of the alkyl chain. Syntheses of long-chain diacids, omega-hydroxy fatty acids, and omega-unsaturated fatty acids as base chemicals derived from vegetable oils were developed. Interesting applications were opened by the epoxidation of C-C-double bonds giving the possibility of photochemically initiated cationic curing and access to polyetherpolyols. Enantiomerically pure fatty acids as part of the chiral pool of nature can be used for the synthesis of nonracemic building blocks.

Fine and coarse modes of dicarboxylic acids in the Arctic aerosols collected during the Polar Sunrise Experiment 1997

Fine (&lt;1 μm) and coarse (&gt;1 μm) aerosol particles were collected at Alert, Canada (82°27′N, 62°30′W), during the Arctic spring as part of the Polar Sunrise Experiment 1997 and were analyzed for low molecular weight dicarboxylic acids (C2–C11) using gas chromatography with flame ionization detector (GC‐FID) and GC/mass spectrometry (GC/MS). More than 80% of total diacids were detected in the fine fraction, suggesting the production by gas‐to‐particle conversion in the Arctic. In both fractions, oxalic acid was the dominant diacid species followed by succinic and malonic acids. Shorter chain diacids (C2–C5) showed the concentration maximum on 5–7 April; however, longer chain diacids (&lt;C6) did not show a clear peak in the same periods. A significant depletion of ozone was observed during the experiment, where an anticorrelation was found between the concentrations of ozone and shorter chain diacids (C2–C5) in both fine and coarse aerosols. During this event, we also observed the enhanced concentration of filterable bromine in both modes. Peaks of dicarboxylic acids in both coarse and fine aerosols during ozone depletion events indicate that heterogeneous reactions are occurring on coarse particle and possibly on fine particles as well. Dicarboxylic acids may be produced by the oxidation of precursor compounds such as glyoxal and glyoxylic and other ω‐oxocarboxylic acids that contain aldehyde (hydrated form) group, being involved with ozone and halogen chemistry in the Arctic marine boundary layer.