scholarly journals Unveiling the Enzymatic Degradation Process of Biobased Thiophene Polyesters

2021 ◽  
Vol 9 ◽  
Author(s):  
Federico A. Bertolini ◽  
Michelina Soccio ◽  
Simone Weinberger ◽  
Giulia Guidotti ◽  
Massimo Gazzano ◽  
...  

In the past 20 years, scientific research focused on the identification of valid alternatives to materials of fossil origin, in particular, related to biobased polymers. Recently, the efforts led to the synthesis of thiophene-based polymers (TBPs), a new class of polyesters based on 2,5-thiophenedicarboxylic acid (TPCA) that can be industrially produced using biomass-derived molecules. In this study, TBPs were synthesized using diols with different chain length (from C4 to C6) leading to poly(butylene 2,5-thiophenedicarboxylate) (PBTF), poly(pentamethylene 2,5-thiophenedicarboxylate) (PPeTF), and poly(hexamethylene 2,5-thiophenedicarboxylate) (PHTF), respectively, that were processed to thin films. To investigate enzymatic hydrolysis of these polymer films, cutinase 1 (Thc_cut1) and cutinase 2 (Thc_cut2) from Thermobifida cellulosilytica were recombinantly expressed in the host E. coli and purified. After 72 h of incubation at 65°C with 5 µM Thc_cut1, weight loss and HPLC analysis indicated 9, 100, and 80% degradation of PBTF, PPeTF, and PHTG with a concomitant release of 0.12, 2.70, and 0.67 mM of TPCA. The SEM analysis showed that tiny holes were formed on the surface of the films and after 72 h PPeTF was completely degraded. The LC-TOF/MS analysis indicated that Thc_cut2 in particular released various oligomers from the polymer during the reaction. In addition, the FTIR analysis showed the formation of novel acid and hydroxyl groups on the polymer surfaces. The results showed that the two used thermostable cutinases are promising biocatalysts for the environmentally friendly degradation of TPCA-based polyesters, in view of a possible sustainable recycling of plastic waste through resynthesis processes.

Author(s):  
E. Loren Buhle ◽  
Pamela Rew ◽  
Ueli Aebi

While DNA-dependent RNA polymerase represents one of the key enzymes involved in transcription and ultimately in gene expression in procaryotic and eucaryotic cells, little progress has been made towards elucidation of its 3-D structure at the molecular level over the past few years. This is mainly because to date no 3-D crystals suitable for X-ray diffraction analysis have been obtained with this rather large (MW ~500 kd) multi-subunit (α2ββ'ζ). As an alternative, we have been trying to form ordered arrays of RNA polymerase from E. coli suitable for structural analysis in the electron microscope combined with image processing. Here we report about helical polymers induced from holoenzyme (α2ββ'ζ) at low ionic strength with 5-7 mM MnCl2 (see Fig. 1a). The presence of the ζ-subunit (MW 86 kd) is required to form these polymers, since the core enzyme (α2ββ') does fail to assemble into such structures under these conditions.


2020 ◽  
Vol 25 (2) ◽  
pp. 111-122
Author(s):  
Aries Andrianto

Based on Bank Indonesia data, electronic money transactions have grown rapidly in the past 10 years. Throughout 2018, the volume of electronic money transactions was 2.92 billion transactions, growing 16,600 times compared to 2009.This study aims to analyze the factors that influence interest in using the LinkAja digital wallet using the UTAUT 2 method. The object of this study is the LinkAja digital wallet user who is domiciled in Jakarta. The independent variables examined in this study were Performance Expectancy, Effort Expectancy, Social Influence, Facilitating Conditions, Hedonic Motivation, and Habit on Behavior Intention using PLS-SEM analysis techniques. The results of this study indicate that Price Value has a positive effect on Behavior Intention.


2020 ◽  
Vol 17 (5) ◽  
pp. 716-724
Author(s):  
Yan A. Ivanenkov ◽  
Renat S. Yamidanov ◽  
Ilya A. Osterman ◽  
Petr V. Sergiev ◽  
Vladimir A. Aladinskiy ◽  
...  

Background: The key issue in the development of novel antimicrobials is a rapid expansion of new bacterial strains resistant to current antibiotics. Indeed, World Health Organization has reported that bacteria commonly causing infections in hospitals and in the community, e.g. E. Coli, K. pneumoniae and S. aureus, have high resistance vs the last generations of cephalosporins, carbapenems and fluoroquinolones. During the past decades, only few successful efforts to develop and launch new antibacterial medications have been performed. This study aims to identify new class of antibacterial agents using novel high-throughput screening technique. Methods: We have designed library containing 125K compounds not similar in structure (Tanimoto coeff.< 0.7) to that published previously as antibiotics. The HTS platform based on double reporter system pDualrep2 was used to distinguish between molecules able to block translational machinery or induce SOS-response in a model E. coli system. MICs for most active chemicals in LB and M9 medium were determined using broth microdilution assay. Results: In an attempt to discover novel classes of antibacterials, we performed HTS of a large-scale small molecule library using our unique screening platform. This approach permitted us to quickly and robustly evaluate a lot of compounds as well as to determine the mechanism of action in the case of compounds being either translational machinery inhibitors or DNA-damaging agents/replication blockers. HTS has resulted in several new structural classes of molecules exhibiting an attractive antibacterial activity. Herein, we report as promising antibacterials. Two most active compounds from this series showed MIC value of 1.2 (5) and 1.8 μg/mL (6) and good selectivity index. Compound 6 caused RFP induction and low SOS response. In vitro luciferase assay has revealed that it is able to slightly inhibit protein biosynthesis. Compound 5 was tested on several archival strains and exhibited slight activity against gram-negative bacteria and outstanding activity against S. aureus. The key structural requirements for antibacterial potency were also explored. We found, that the unsubstituted carboxylic group is crucial for antibacterial activity as well as the presence of bulky hydrophobic substituents at phenyl fragment. Conclusion: The obtained results provide a solid background for further characterization of the 5'- (carbonylamino)-2,3'-bithiophene-4'-carboxylate derivatives discussed herein as new class of antibacterials and their optimization campaign.


Polymers ◽  
2021 ◽  
Vol 13 (8) ◽  
pp. 1241
Author(s):  
Michael Ioelovich

In this study, physicochemical and chemical methods of cellulose modification were used to increase the hydrophobicity of this natural semicrystalline biopolymer. It has been shown that acid hydrolysis of the initial cellulose increases its crystallinity, which improves hydrophobicity, but only to a small extent. A more significant hydrophobization effect was observed after chemical modification by esterification, when polar hydroxyl groups of cellulose were replaced by non-polar substituents. The esterification process was accompanied by the disruption of the crystalline structure of cellulose and its transformation into the mesomorphous structure of cellulose esters. It was found that the replacement of cellulose hydroxyls with ester groups leads to a significant increase in the hydrophobicity of the resulting polymer. Moreover, the increase of the number of non-polar groups in the ester substituent contributes to rise in hydrophobicity of cellulose derivative. Depending on the type of ester group, the hydrophobicity increased in the following order: acetate < propionate < butyrate. Therefore, tributyrate cellulose (TBC) demonstrated the most hydrophobicity among all studied samples. In addition, the mixed ester, triacetobutyrate cellulose (TAB), also showed a sufficiently high hydrophobicity. The promising performance properties of hydrophobic cellulose esters, TBC and TAB, were also demonstrated.


Molecules ◽  
2021 ◽  
Vol 26 (10) ◽  
pp. 2852
Author(s):  
Paul A. Foster

Steroid sulphatase (STS), involved in the hydrolysis of steroid sulphates, plays an important role in the formation of both active oestrogens and androgens. Since these steroids significantly impact the proliferation of both oestrogen- and androgen-dependent cancers, many research groups over the past 30 years have designed and developed STS inhibitors. One of the main contributors to this field has been Prof. Barry Potter, previously at the University of Bath and now at the University of Oxford. Upon Prof. Potter’s imminent retirement, this review takes a look back at the work on STS inhibitors and their contribution to our understanding of sulphate biology and as potential therapeutic agents in hormone-dependent disease. A number of potent STS inhibitors have now been developed, one of which, Irosustat (STX64, 667Coumate, BN83495), remains the only one to have completed phase I/II clinical trials against numerous indications (breast, prostate, endometrial). These studies have provided new insights into the origins of androgens and oestrogens in women and men. In addition to the therapeutic role of STS inhibition in breast and prostate cancer, there is now good evidence to suggest they may also provide benefits in patients with colorectal and ovarian cancer, and in treating endometriosis. To explore the potential of STS inhibitors further, a number of second- and third-generation inhibitors have been developed, together with single molecules that possess aromatase–STS inhibitory properties. The further development of potent STS inhibitors will allow their potential therapeutic value to be explored in a variety of hormone-dependent cancers and possibly other non-oncological conditions.


1995 ◽  
Vol 50 (1-2) ◽  
pp. 123-126 ◽  
Author(s):  
Gottfried Raab ◽  
Jürgen Jacob

Abstract The uropygial gland waxes of the South American red-legged Seriema (Cariama cristata (L., 1766)) were found to be composed of unbranched alcohols and 2,2′-dialkyl-substituted acetic acids which so far have not been found in skin lipids. When used as a chemosystematic character, the occurrence of this lipid class separates the order Cariamiformes (Seriemas) from all other avian orders hitherto investigated, especially from the Gruiformes (cranes and rails) to which they have been tentatively attributed in the past. From the GC retention time data now available for a series of 2-alkyl-substituted fatty acid methyl esters relative retention time indices for other compounds may be predicted.


Author(s):  
I. B. Trindade ◽  
G. Hernandez ◽  
E. Lebègue ◽  
F. Barrière ◽  
T. Cordeiro ◽  
...  

AbstractIron is a fundamental element for virtually all forms of life. Despite its abundance, its bioavailability is limited, and thus, microbes developed siderophores, small molecules, which are synthesized inside the cell and then released outside for iron scavenging. Once inside the cell, iron removal does not occur spontaneously, instead this process is mediated by siderophore-interacting proteins (SIP) and/or by ferric-siderophore reductases (FSR). In the past two decades, representatives of the SIP subfamily have been structurally and biochemically characterized; however, the same was not achieved for the FSR subfamily. Here, we initiate the structural and functional characterization of FhuF, the first and only FSR ever isolated. FhuF is a globular monomeric protein mainly composed by α-helices sheltering internal cavities in a fold resembling the “palm” domain found in siderophore biosynthetic enzymes. Paramagnetic NMR spectroscopy revealed that the core of the cluster has electronic properties in line with those of previously characterized 2Fe–2S ferredoxins and differences appear to be confined to the coordination of Fe(III) in the reduced protein. In particular, the two cysteines coordinating this iron appear to have substantially different bond strengths. In similarity with the proteins from the SIP subfamily, FhuF binds both the iron-loaded and the apo forms of ferrichrome in the micromolar range and cyclic voltammetry reveals the presence of redox-Bohr effect, which broadens the range of ferric-siderophore substrates that can be thermodynamically accessible for reduction. This study suggests that despite the structural differences between FSR and SIP proteins, mechanistic similarities exist between the two classes of proteins. Graphic abstract


1995 ◽  
Vol 347 (1319) ◽  
pp. 21-25 ◽  

Over the past three or four years, great strides have been made in our understanding of the proteins involved in recombination and the mechanisms by which recombinant molecules are formed. This review summarizes our current understanding of the process by focusing on recent studies of proteins involved in the later steps of recombination in bacteria. In particular, biochemical investigation of the in vitro properties of the E. coli RuvA, RuvB and RuvC proteins have provided our first insight into the novel molecular mechanisms by which Holliday junctions are moved along DNA and then resolved by endonucleolytic cleavage.


2021 ◽  
Author(s):  
Eric Miller ◽  
Maciej Walczak

Stereoselective reactions at the anomeric carbon constitute the cornerstone of preparative carbohydrate chemistry. Here, we report the synthesis of axial C1 trifluoroborates and stereoselective C-arylation and etherification reactions under photoredox conditions. These reactions are characterized by high anomeric selectivities for 2-deoxysugars and broad substrate scope (24 examples), including disaccharides and trifluoroborates with free hydroxyl groups. Computational studies show that high axial selectivities for these reactions originate from a combination of kinetic anomeric effect of the intermediate C1 radical and stereoelectronic stabilization of Ni(III) through the metallo-anomeric effect. Taken together, this new class of carbohydrate reagents adds the palette of anomeric nucleophile reagents suitable for efficient installation C-C and Cheteroatom bonds.


2019 ◽  
Vol 69 (4) ◽  
pp. 313-321
Author(s):  
Xiaoxia Hu ◽  
Zhenghao Chen ◽  
Yang Cao ◽  
Zhangjing Chen ◽  
Shuangbao Zhang ◽  
...  

Abstract The focus of this study was to observe the properties of bamboo plastic composites modified with a self-made modifier, 18 acyl-dopamine (0, 0.25, 0.50, 0.75, 1.00, and 1.25 weight percent [wt%] based on the dry weight of bamboo powder). The effects of the modifier were demonstrated by measures of mechanical properties, water absorption, thermal stability, and scanning electron microscopy (SEM). The results revealed that 18 acyl-dopamine could be used as an effective modifier of bamboo powder/high-density polyethylene composites. When the modifier was increased, the toughness of the composite deteriorated, and the strength and rigidity improved. This indicated that when the dosage became higher, the compatibilization became stronger, and the toughening effect became worse. Based on the experimental data, a small dosage modifier acted as a toughening agent; as the dosage increased to 1.0 wt%, the compatibility began to appear. The modifier reacted with the hydroxyl groups on the surface of the bamboo powder, which caused the bamboo powder to absorb less water, so the thickness expansion rate was lowest at 1.25 wt%. The pyrolysis peak of bamboo powder and plastic showed a tendency to be close to each other, indicating that the interface was improving. Based on the equation of Flynn-Wall-Ozawa, as the dosage of the modifier increased from 0.50 to 1.25 wt%, the apparent activation energy also increased. The SEM analysis showed the binding between bamboo powder and the plastic matrix was strongest when the modifier dosage was 1.25 wt%.


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