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1.
J Am Chem Soc ; 144(35): 15911-15915, 2022 09 07.
Artigo em Inglês | MEDLINE | ID: mdl-35938930

RESUMO

Synthetic biodegradable polyesters tend to undergo slow biodegradation under ambient natural conditions and, hence, have been rejected or even banned recently in ecofriendly applications. Here, we demonstrate the preparation of polyesters exhibiting enhanced biodegradability, which were generated through a combination of old controversial macromolecules and aggregate theories. H3PO4-catalyzed diacid/diol polycondensation afforded polyester chains bearing chain-end -CH2OP(O)(OH)2 and inner-chain (-CH2O)2P(O)(OH) groups, which were subsequently treated with M(2-ethylhexanoate)2 (M = Zn, Mg, Mn, and Ca) to form ionic aggregates of polyesters. The prepared ionic aggregates of polyesters, which were constructed with fertilizer ingredients (such as M2+ and phosphate), exhibit much faster biodegradability than that of the conventional polyesters under controlled soil conditions at 25 °C, while displaying comparable or superior rheological and mechanical properties.


Assuntos
Fertilizantes , Poliésteres , Íons , Poliésteres/metabolismo
2.
Microorganisms ; 12(2)2024 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-38399795

RESUMO

Carotenoids, biotechnologically significant pigments, play crucial biological roles in marine microorganisms. While various environments have been explored to understand the diversity of carotenoids and their biosynthesis, the Antarctic Ocean remains relatively under-investigated. This study conducted a metagenomic analysis of seawater from two depths (16 and 25 m) near the King Sejong Station in the Antarctic Ocean. The analysis revealed a rich genetic diversity underlying C40 (astaxanthin, myxol, okenone, spheroidene, and spirilloxanthin), C30 (diaponeurosporene, diapolycopene, and staphyloxanthin), and C50 (C.p. 450) carotenoid biosynthesis in marine microorganisms, with notable differential gene abundances between depth locations. Exploring carotenoid pathway genes offers the potential for discovering diverse carotenoid structures of biotechnological value and better understanding their roles in individual microorganisms and broader ecosystems.

3.
Polymers (Basel) ; 16(4)2024 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-38399897

RESUMO

Poly(1,4-butylene succinate) (PBS) is a promising sustainable and biodegradable synthetic polyester. In this study, we synthesized PBS-based copolyesters by incorporating 5-20 mol% of -O2CC6H4CO2- and -OCH2CH2O- units through the polycondensation of succinic acid (SA) with 1,4-butanediol (BD) and bis(2-hydroxyethyl) terephthalate (BHET). Two different catalysts, H3PO4 and the conventional catalyst (nBuO)4Ti, were used comparatively in the synthesis process. The copolyesters produced using the former were treated with M(2-ethylhexanoate)2 (M = Mg, Zn, Mn) to connect the chains through ionic interactions between M2+ ions and either -CH2OP(O)(OH)O- or (-CH2O)2P(O)O- groups. By incorporating BHET units (i.e., -O2CC6H4CO2- and -OCH2CH2O-), the resulting copolyesters exhibited improved ductile properties with enhanced elongation at break, albeit with reduced tensile strength. The copolyesters prepared with H3PO4/M(2-ethylhexanoate)2 displayed a less random distribution of -O2CC6H4CO2- and -OCH2CH2O- units, leading to a faster crystallization rate, higher Tm value, and higher yield strength compared to those prepared with (nBuO)4Ti using the same amount of BHET. Furthermore, they displayed substantial shear-thinning behavior in their rheological properties due to the presence of long-chain branches of (-CH2O)3P=O units. Unfortunately, the copolyesters prepared with H3PO4/M(2-ethylhexanoate)2, and hence containing M2+, -CH2OP(O)(OH)O-, (-CH2O)2P(O)O- groups, did not exhibit enhanced biodegradability under ambient soil conditions.

4.
RSC Adv ; 14(7): 4702-4716, 2024 Jan 31.
Artigo em Inglês | MEDLINE | ID: mdl-38318613

RESUMO

Polylactic acid (PLA) stands as a promising material, sourced from renewables and exhibiting biodegradability-albeit under stringent industrial composting settings. A primary challenge impeding PLA's broad applications is its inherent brittleness, as it fractures with minimal elongation despite its commendable tensile strength. A well-established remedy involves blending PLA with plasticizers. In this study, a range of organic carbonates-namely, 4-ethoxycarbonyloximethyl-[1,3]dioxolan-2-one (1), 4-methoxycarbonyloximethyl-[1,3]dioxolan-2-one (2), glycerol carbonate (3), and glycerol 1-acetate 2,3-carbonate (4)-were synthesized on a preparative scale (∼100 g), using renewable glycerol and CO2-derived diethyl carbonate (DEC) or dimethyl carbonate (DMC). Significantly, 1-4 exhibited biodegradability under ambient conditions within a week, ascertained through soil exposure at 25 °C-outpacing the degradation of comparative cellulose. Further investigations revealed 1's efficacy as a PLA plasticizer. Compatibility with PLA, up to 30 phr (parts per hundred resin), was verified using an array of techniques, including DSC, DMA, SEM, and rotational rheometry. The resulting blends showcased enhanced ductility, evident from tensile property measurements. Notably, the novel plasticizer 1 displayed an advantage over conventional acetyltributylcitrate (ATBC) in terms of morphological stability. Slow crystallization, observed in PLA/ATBC blends over time at room temperature, was absent in PLA/1 blends, preserving amorphous domain dimensions and mitigating plasticizer migration-confirmed through DMA assessments of aged and unaged specimens. Nevertheless, biodegradation assessments of the blends revealed that the biodegradable organic carbonate plasticizers did not augment PLA's biodegradation. The PLA in the blends remained mostly unchanged under ambient soil conditions of 25 °C over a 6 month period. This work underscores the potential of organic carbonates as both eco-friendly plasticizers for PLA and as biodegradable compounds, contributing to the development of environmentally conscious polymer systems.

5.
Front Bioeng Biotechnol ; 9: 662979, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-34178960

RESUMO

One tetraacetylphytosphingosine (TAPS)-producing Wickerhamomyces ciferrii mutant was obtained by exposing wild-type W. ciferrii to γ-ray irradiation. The mutant named 736 produced up to 9.1 g/L of TAPS (218.7 mg-TAPS/g-DCW) during batch fermentation in comparison with 1.7 g/L of TAPS (52.2 mg-TAPS/g-DCW) for the wild type. The highest production, 17.7 g/L of TAPS (259.6 mg-TAPS/g-DCW), was obtained during fed-batch fermentation by mutant 736. Fatty acid (FA) analysis revealed an altered cellular FA profile of mutant 736: decrease in C16:0 and C16:1 FA levels, and increase in C18:1 and C18:2 FA levels. Although a significant change in the cellular FA profile was observed, scanning electron micrographs showed that morphology of wild-type and mutant 736 cells was similar. Genetic alteration analysis of eight TAPS biosynthesis-related genes revealed that there are no mutations in these genes in mutant 736; however, mRNA expression analysis indicated 30% higher mRNA expression of TCS10 among the eight genes in mutant 736 than that in the wild-type. Collectively, these results imply that the enhancement of TAPS biosynthesis in mutant 736 may be a consequence of system-level genetic and physiological alterations of a complicated metabolic network. Reverse metabolic engineering based on system-level omics analysis of mutant 736 can make the mutant more suitable for commercial production of TAPS.

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