Polyenes

多烯
  • 文章类型: Journal Article
    Prymensiumparvum是有害的藻类,会导致大量环境鱼类死亡。他们的聚酮聚醚毒素,普米尼辛,是自然界中最大的非聚合化合物之一,并且具有生物合成起源,40多年来一直是神秘的。在这项工作中,我们报告了“PKZILLA”,“大量的P.parvum聚酮合成酶(PKS)基因逃避了先前的检测。PKZILLA-1和-2编码具有140和99个酶结构域的4.7和3.2兆道尔顿的巨大蛋白质产物。他们预测的多烯产物与90碳骨架A型普米尼辛的拟议pre-prymnesin前体相匹配。我们进一步表征了来自P.parvumRCC3426的变体PKZILLA-B1,该变体负责较短的B型类似物prymnesin-B1,从而建立了haptophyte聚醚生物合成逻辑的一般模型。这项工作扩展了生物学中对遗传和酶大小限制的期望。
    Prymnesium parvum are harmful haptophyte algae that cause massive environmental fish kills. Their polyketide polyether toxins, the prymnesins, are among the largest nonpolymeric compounds in nature and have biosynthetic origins that have remained enigmatic for more than 40 years. In this work, we report the \"PKZILLAs,\" massive P. parvum polyketide synthase (PKS) genes that have evaded previous detection. PKZILLA-1 and -2 encode giant protein products of 4.7 and 3.2 megadaltons that have 140 and 99 enzyme domains. Their predicted polyene product matches the proposed pre-prymnesin precursor of the 90-carbon-backbone A-type prymnesins. We further characterize the variant PKZILLA-B1, which is responsible for the shorter B-type analog prymnesin-B1, from P. parvum RCC3426 and thus establish a general model of haptophyte polyether biosynthetic logic. This work expands expectations of genetic and enzymatic size limits in biology.
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  • 文章类型: Journal Article
    最近的研究表明,超级蠕虫(Zophobasatratus的幼虫)能够降解聚乙烯(PE),聚苯乙烯(PS),聚氯乙烯(PVC),和聚丙烯(PP)在他们的消化系统。这项研究旨在比较超级蠕虫在30天内降解上述四种聚烯烃塑料的能力。在这项研究中,PE的降解率最高,以及超级蠕虫的最终平均重量,以及它们最终消耗的塑料质量损失,显著增加(73.38%和52.33%,分别)当PE用麦麸(1:1[w/w])喂养时。FTIR和TGA表明,四种聚烯烃塑料在暴露于超级蠕虫时发生了氧化和生物降解过程。此外,在PE喂养的超级蠕虫中,排泄的聚合物残留物的分子量(Mw和Mn)分别下降了3.1%和2.87%,表明PE的解聚作用并不完全依赖于肠道微生物群落。对肠道微生物群落的分析表明,每种塑料的优势微生物群落都不同。结果表明,超级蠕虫的肠道微生物组对降解各种类型的塑料表现出显著的适应性,不同塑料的摄入偏好和效率与不同的优势微生物群落物种有关。
    Recent studies have demonstrated superworms (larvae of Zophobas atratus) ability to degrade polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC), and polypropylene (PP) within their digestive system. This study aimed to compare the ability of superworms to degrade the above four polyolefin plastics over a duration of 30 days. In this study, the degradation rate of PE was the highest, and the final average weight of superworms, as well as the final plastic mass loss consumed by them, significantly increased (73.38 % and 52.33 %, respectively) when PE was fed with wheat bran (1:1 [w/w]). FTIR and TGA indicated the occurrence of oxidation and biodegradation processes in the four polyolefin plastics when exposed to superworms. In addition, the molecular weights (Mw and Mn) of excreted polymer residues decreased by 3.1 % and 2.87 % in PE-fed superworms, suggesting that the depolymerization of PE was not entirely dependent on the gut microbial community. The analysis of the gut microbial communities revealed that the dominant microbial community were different for each type of plastic. The results indicate that the gut microbiome of superworms exhibited remarkable adaptability in degrading various types of plastics, and the intake preferences and efficiency of different plastics are associated with different dominant microbial community species.
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  • 文章类型: Journal Article
    塑料垃圾,尤其是被称为聚烯烃的正浮力聚合物,是海洋环境中漂浮碎片的主要组成部分。虽然海洋微生物的塑料定植从环境样本中得到了很好的证明,在较长的时间尺度(>>1个月)和不同类型和形状的塑料碎片之间,海洋微生物群落结构的演替不太确定。我们分析了漂浮在夏威夷流通海水罐中的聚烯烃碎片上的生物膜上的16SrRNA和18SrRNA扩增子基因序列,以评估不同塑料形状的聚丙烯(PP)和高密度聚乙烯(HDPE)和低密度聚乙烯(LDPE)的微生物演替差异(棒,薄膜和立方体)在相同的环境条件下持续1年。无论类型或形状,所有塑料碎片都以真核硅藻Nitzschia为主,随着时间的推移,只有塑料类型对细菌群落结构显着重要(p=0.005)。与20种细菌和8种真核生物类群的PP相比,PE塑料具有更高的差异丰度,包括已知的塑料降解细菌分类群Hyphomonas(p=0.01)。我们的研究结果提供了经验证据,表明在相似条件下,塑料类型对于细菌比真核微生物群落演替对聚烯烃污染更重要。
    Plastic waste, especially positively buoyant polymers known as polyolefins, are a major component of floating debris in the marine environment. While plastic colonisation by marine microbes is well documented from environmental samples, the succession of marine microbial community structure over longer time scales (> > 1 month) and across different types and shapes of plastic debris is less certain. We analysed 16S rRNA and 18S rRNA amplicon gene sequences from biofilms on polyolefin debris floating in a flow-through seawater tank in Hawai\'i to assess differences in microbial succession across the plastic types of polypropylene (PP) and both high-density polyethylene (HDPE) and low-density polyethylene (LDPE) made of different plastic shapes (rod, film and cube) under the same environmental conditions for 1 year. Regardless of type or shape, all plastic debris were dominated by the eukaryotic diatom Nitzschia, and only plastic type was significantly important for bacterial community structure over time (p = 0.005). PE plastics had higher differential abundance when compared to PP for 20 bacterial and eight eukaryotic taxa, including the known plastic degrading bacterial taxon Hyphomonas (p = 0.01). Results from our study provide empirical evidence that plastic type may be more important for bacterial than eukaryotic microbial community succession on polyolefin pollution under similar conditions.
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  • 文章类型: Journal Article
    背景:由于合成低维材料的进步,找到有效描述在1D和2D域上运动的量子粒子的波动方程是一个挑战。Jensen,Koppe和DaCosta独立地引入了一种限制势形式主义,表明有效的约束动力学受到标量几何形状引起的势的影响;对于曲线的限制,电势取决于曲线的曲率函数。
    方法:为了表征多烯中的π电子,我们遵循两种方法。首先,我们利用与螺旋曲线相关的减弱的库仑电势。具有Dirichlet边界条件的Schrödinger方程的解产生贝塞尔函数,光谱是通过分析获得的。我们在第二种方法中采用了盒子里的粒子模型,纳入有效质量校正。多烯的π-π*跃迁的计算与两种方法的实验吻合良好,虽然有不同的波函数。
    BACKGROUND: Due to advances in synthesizing lower-dimensional materials, there is the challenge of finding the wave equation that effectively describes quantum particles moving on 1D and 2D domains. Jensen and Koppe and Da Costa independently introduced a confining potential formalism showing that the effective constrained dynamics is subjected to a scalar geometry-induced potential; for the confinement to a curve, the potential depends on the curve\'s curvature function.
    METHODS: To characterize the π electrons in polyenes, we follow two approaches. First, we utilize a weakened Coulomb potential associated with a spiral curve. The solution to the Schrödinger equation with Dirichlet boundary conditions yields Bessel functions, and the spectrum is obtained analytically. We employ the particle-in-a-box model in the second approach, incorporating effective mass corrections. The π - π ∗ transitions of polyenes were calculated in good experimental agreement with both approaches, although with different wave functions.
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  • 文章类型: Journal Article
    多重耐药真菌的出现令人严重关切,其感染是导致免疫功能低下患者大量死亡的原因。真菌感染的治疗主要依赖于临床一类抗生素,包括唑类,多烯,棘白菌素,聚酮化合物,和核苷酸类似物。然而,随着人类和植物真菌感染的治疗与抗真菌药物重叠,真菌感染的发生率正在增加。对作用于不同于已知靶标的靶标的新抗真菌剂的需求是不可否认的。此外,不能破坏真菌对抗生素敏感性丧失的速度。真菌可以通过几种模式产生对抗生素的抗性,包括减少药物摄取,药物靶点改变,以及由于活性挤出和生物膜形成而导致的药物细胞浓度降低。真菌外排泵的过度表达主要将抗生素的浓度降低至亚致死浓度,从而负责开发抗性真菌菌株。几种策略用于检查多药耐药真菌的抗生素耐药性,包括合成抗生素类似物和在联合疗法中给予抗生素。其中外排泵蛋白抑制剂被认为是抗生素的潜在佐剂,可以通过抑制外排泵蛋白转运蛋白来阻断抗生素的外排。此外,它可以使抗真菌药物对具有过度表达的外排泵蛋白的多药耐药真菌敏感。这篇综述讨论了天然铅分子,可重复使用的药物,和制定策略来克服真菌中的外排泵活性。
    The emergence of multidrug-resistant fungi is of grave concern, and its infections are responsible for significant deaths among immunocompromised patients. The treatment of fungal infections primarily relies on a clinical class of antibiotics, including azoles, polyenes, echinocandins, polyketides, and a nucleotide analogue. However, the incidence of fungal infections is increasing as the treatment for human and plant fungal infections overlaps with antifungal drugs. The need for new antifungal agents acting on different targets than known targets is undeniable. Also, the pace at which loss of fungal susceptibility to antibiotics cannot be undermined. There are several modes by which fungi can develop resistance to antibiotics, including reduced drug uptake, drug target alteration, and a reduction in the cellular concentration of the drug due to active extrusions and biofilm formation. The efflux pump\'s overexpression in the fungi primarily reduced the antibiotic\'s concentration to a sub-lethal concentration, thus responsible for developing resistant fungus strains. Several strategies are used to check antibiotic resistance in multi-drug resistant fungi, including synthesizing antibiotic analogs and giving antibiotics in combination therapies. Among them, the efflux pump protein inhibitors are considered potential adjuvants to antibiotics and can block the efflux of antibiotics by inhibiting efflux pump protein transporters. Moreover, it can sensitize the antifungal drugs to multi-drug resistant fungi with overexpressed efflux pump proteins. This review discusses the natural lead molecules, repurposable drugs, and formulation strategies to overcome the efflux pump activity in the fungi.
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  • 文章类型: Journal Article
    Psittacofulvins是多烯醛染料,负责为鹦鹉羽毛着色并保护它们免受光氧化,有害的自由基,和细菌降解。为了解释这些化合物的不寻常性质,热力学和全球化学活性描述符描述了四种天然和三种合成的鹦鹉,以及它们的羟基,羧基和二醛衍生物,决心。为了这个目标,采用B3LYP/QZVP理论水平的DFT方法和C-PCM溶剂化模型。这些计算使得能够选择具有最大生物活性和潜在适用性的预计化合物作为药物中的多功能成分,化妆品,补充剂,和食物,它们可以作为防腐剂发挥三重作用,自由基清除剂,和着色剂。获得的结果为鉴定鹦鹉羽毛色素中的第五种鹦鹉黄霉素提供了依据,以十个共轭双键(docosadecaenal)为特征。
    Psittacofulvins are polyenal dyes responsible for coloring parrot feathers and protecting them against photo-oxidation, harmful radicals, and bacterial degradation. To explain the unusual properties of these compounds, the thermodynamic and global chemical activity descriptors characterizing four natural and three synthetic psittacofulvins, as well as their hydroxyl, carboxyl and dialdehyde derivatives, were determined. To this aim, the DFT method at the B3LYP/QZVP theory level and the C-PCM solvation model were used. The calculations enabled the selection of the projected compounds for the greatest bioactivity and potential applicability as multifunctional ingredients in medicines, cosmetics, supplements, and food, in which they may play a triple role as preservative, radical scavenger, and coloring agent. The results obtained provide arguments for the identification of a fifth psittacofulvin within the parrot feather pigment, characterized by ten conjugated double bonds (docosadecaenal).
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  • 文章类型: Journal Article
    将三种不同直链淀粉含量的淀粉与聚丁二酸丁二醇酯(PBS)酯化共混,得到酯化甘露聚糖淀粉/PBS(EMS/PBS),酯化玉米淀粉/PBS(ECS/PBS),和酯化的蜡质玉米淀粉/PBS(EWS/PBS)复合材料。具有高直链淀粉含量的EMS/PBS和ECS/PBS复合材料显示出典型的V型晶体结构。EWS的原始晶体,直链淀粉含量低,在酯化过程中被破坏。EWS表现出与PBS的最强相互作用和最有利的界面相容性。热解温度的顺序为EMS/PBS Three types of starch with different amylose content were esterified and blended with polybutylene succinate (PBS) to obtain esterified manioc starch/PBS (EMS/PBS), esterified corn starch/PBS (ECS/PBS), and esterified waxy corn starch/PBS (EWS/PBS) composites. The EMS/PBS and ECS/PBS composites with high amylose content displayed typical V-type crystal structures. The original crystals of EWS, which had low amylose content, were disrupted during the esterification process. EWS exhibited the strongest interaction with PBS and the most favorable interface compatibility. The pyrolysis temperature was in order of EMS/PBS < ECS/PBS < EWS/PBS. The elongation at break of the three blends was higher than that of pure PBS. The esterification and plasticization of the EWS/PBS composite were the most comprehensive. The EWS/PBS composite showed the lowest storage modulus (G\') and complex viscosity (η*). The interfacial bonding force of the composite materials increased with more amylopectin, decreasing intermolecular forces and destroying crystal structures, which decreased G\' and η* and increased toughness. The EWS/PBS composite, with the least amylose content, had the best hydrophobicity and degradation performance.
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  • 文章类型: Journal Article
    提高有机染料敏化太阳能电池(DSSC)效率的一种有用技术是在供体(D)和受体(A)单元之间延伸π-共轭桥。本研究使用DFT和TD-DFT技术来研究延长供体N之间的多烯桥的影响,N-二甲基苯胺基和受体二氰基乙烯基。计算的关键属性的结果并不都符合预期。平面结构与增加π-共轭接头有关,意味着从供体到受体的有效电子转移。较小的能量间隙,更大的振荡器强度值,当多烯单元的数量增加时,也观察到了红移的电子吸收。然而,一些结果表明,当多烯桥延伸时,所述染料作为有效的染料敏化太阳能电池的潜力是有限的。增加多烯单元会导致HOMO水平上升,直到超过电解质的氧化还原电位,这延迟了再生并阻碍了电子传输循环的完成。随着共轭单元数量的增加,HOMO和LUMO的末端裂片继续缩小,这影响了染料中分子内电荷转移的难易程度。当评估电子注入和再生的效率时,较小的多烯链长度产生了最有利的结果。这意味着半导体的导带和电解质之间的电荷转移机制没有通过延伸多烯桥而得到改善。开路电压(VOC)从1.23降至0.70V。随着多烯单元数从n=1增加到n=10,激发态持续时间(τ)从1.71下降到1.23ns。这些发现与DSSC的功率转换效率要求不兼容。因此,多烯桥在这种D-π-A构型中的伸长排除了其在太阳能电池器件中的应用。
    One useful technique for increasing the efficiency of organic dye-sensitized solar cells (DSSCs) is to extend the π-conjugated bridges between the donor (D) and the acceptor (A) units. The present study used the DFT and TD-DFT techniques to investigate the effect of lengthening the polyene bridge between the donor N, N-dimethyl-anilino and the acceptor dicyanovinyl. The results of the calculated key properties were not all in line with expectations. Planar structure was associated with increasing the π-conjugation linker, implying efficient electron transfer from the donor to the acceptor. A smaller energy gap, greater oscillator strength values, and red-shifted electronic absorption were also observed when the number of polyene units was increased. However, some results indicated that the potential of the stated dyes to operate as effective dye-sensitized solar cells is limited when the polyene bridge is extended. Increasing the polyene units causes the HOMO level to rise until it exceeds the redox potential of the electrolyte, which delays regeneration and impedes the electron transport cycle from being completed. As the number of conjugated units increases, the terminal lobes of HOMO and LUMO continue to shrink, which affects the ease of intramolecular charge transfer within the dyes. Smaller polyene chain lengths yielded the most favorable results when evaluating the efficiency of electron injection and regeneration. This means that the charge transfer mechanism between the conduction band of the semiconductor and the electrolyte is not improved by extending the polyene bridge. The open circuit voltage (VOC) was reduced from 1.23 to 0.70 V. Similarly, the excited-state duration (τ) decreased from 1.71 to 1.23 ns as the number of polyene units increased from n = 1 to n = 10. These findings are incompatible with the power conversion efficiency requirements of DSSCs. Therefore, the elongation of the polyene bridge in such D-π-A configurations rules out its application in solar cell devices.
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  • 文章类型: Journal Article
    硅橡胶组织扩张器和乳房植入物与慢性炎症有关,导致纤维胶囊的形成。如果炎症得不到治疗,纤维囊可以变得硬而脆,并导致包膜挛缩的形成。当发生包膜挛缩时,植入失败和再次手术是不可避免的。比较了医用级硅橡胶乳房植入物的纤维胶囊形成和附着在硅橡胶上的基于聚异丁烯的静电纺丝纤维垫,有无抗炎治疗剂。基于线性聚异丁烯(PIB)的热塑性弹性体目前用作聚合物涂层,用于在冠状动脉支架上释放药物以减少再狭窄。最近的工作已经从基于PIB的材料创建了一种药物释放电纺纤维垫。对这项研究很重要,用扎鲁司特(ZAF)电纺丝聚(别罗辛烯-b-异丁烯-b-别罗辛烯)(AIBA)。ZAF是一种抗炎药,能够减少胶囊形成和硅胶乳房植入物的并发症。纤维垫对于局部药物递送是有利的,因为它们的高孔隙率和用于药物释放的表面积。主要假设是ZAF从AIBA的局部释放将在体内90天后降低炎症信号传导并导致囊膜形成。静电纺AIBA垫在本地发布ZAF,与医用级硅橡胶相比,降低炎症和纤维胶囊的发展。局部和口服释放的ZAF导致了类似的结果,但前者的浓度要低得多,这凸显了局部分娩的治疗潜力。从AIBA纤维垫释放的ZAF减轻了炎症,并作为现有临床方法的替代方案。
    Silicone rubber tissue expanders and breast implants are associated with chronic inflammation, leading to the formation of fibrous capsules. If the inflammation is left untreated, the fibrous capsules can become hard and brittle and lead to formation of capsular contracture. When capsular contracture occurs, implant failure and reoperation is unavoidable. Fibrous capsule formation to medical grade silicone rubber breast implants and polyisobutylene-based electrospun fiber mats attached to silicone rubber with and without an anti-inflammatory therapeutic were compared. A linear polyisobutylene (PIB)-based thermoplastic elastomer is currently applied as a polymer coating for drug release on coronary stents to reduce restenosis. Recent work has created a drug releasing electrospun fiber mat from PIB-based materials. Important to this study, poly(alloocimene-b-isobutylene-b-alloocimene) (AIBA) was electrospun with zafirlukast (ZAF). ZAF is an anti-inflammatory drug that is able to reduce capsule formation and complications to silicone breast implants. Fiber mats are advantageous for local drug delivery because of their high porosity and surface area for drug release. The chief hypothesis was that local release of ZAF from AIBA would lower inflammatory signaling and resulting capsular formation after 90 days in vivo. Electrospun AIBA mats locally released ZAF, lowering inflammation and fibrous capsule development compared to medical grade silicone rubber. Locally and orally released ZAF led to similar results, but the former had much lower concentration that highlights local delivery\'s therapeutic potential. Released ZAF from AIBA fiber mats mitigated inflammation and serves as an alternative to existing clinical approaches.
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  • 文章类型: Journal Article
    使用{(Me2Si(C13H8)2)Nd(μ-BH4)[(μ-BH4)Li(THF)]}2(1)金属配合物和用作链转移剂的各种有机镁化合物,包括正丁基-正辛基-镁(BOMAG),正丁基-均三甲苯基-镁(n-BuMgMes),正丁基氯化镁(n-BuMgCl),正戊基溴化镁(n-C5H11MgBr),戊二基-1,5-二(溴化镁)(PDMB)和异丁基-氯化镁(i-BuMgCl)。在控制(共)聚合方面的动力学和性能进行了比较讨论,特别是考虑到醚的存在和所用有机镁化合物的性质。利用腈和分子有机镁化合物之间众所周知的反应性,链的官能化进一步通过用苄腈或甲氧基苄腈化合物使聚合介质失活而进行,导致酮ω-官能化链。官能化的成功扩展到使用二腈试剂的偶联策略和高摩尔质量EBR的官能化。本文受版权保护。保留所有权利。
    Coordinative chain transfer polymerization (CCTP) of ethylene and its copolymerization with 1,3-butadiene is conducted in toluene at 80 °C using a combination of {(Me2Si(C13H8)2)Nd(μ-BH4)[(μ-BH4)Li(THF)]}2 (1) metal complex and various organomagnesium compounds used as chain transfer agents including n-butyl-n-octyl-magnesium (BOMAG), n-butyl-mesityl-magnesium (n-BuMgMes), n-butyl-magnesium chloride (n-BuMgCl), n-pentyl-magnesium bromide (n-C5H11MgBr), pentanediyl-1,5-di(magnesium bromide) (PDMB) and isobutyl-magnesium chloride (i-BuMgCl). Kinetics and performance in terms of control of the (co)polymerization are comparatively discussed particularly considering the presence of ether and the nature of the organomagnesium compounds employed. Taking advantage of the well-known reactivity between nitrile and molecular organomagnesium compounds, the functionalization of the chains is further carried out by deactivation of the polymerization medium with benzonitrile or methoxybenzonitrile compounds leading to ketone ω-functionalized chains. The success of the functionalizations is extended to coupling strategies using dinitrile reagents and to the functionalization of high molar mass ethylene butadiene rubber (EBR).
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