The A9 Core Sequence from NRPS Adenylation Domain Is Relevant for Thioester Formation

The adenylation (A) domain in nonribosomal peptide synthetases catalyses a two-step reaction in which an amino acid is activated and then transferred to the neighbouring thiolation (T) domain. In this study, we investigated the role of the conserved A9 core sequence of the A-domain of tyrocidine synthetase 1, by analysis of single amino acid mutations in the A9 region. Mutation of an absolutely conserved proline (P490G) significantly reduced the conformational stability of the protein, as evidenced by increased susceptibility to proteolytic cleavage and denaturation. All mutant A-domains were capable of amino acid activation, but the activity in the overall reaction was reduced. Surprisingly, the S491R mutant (mutation at the first residue following the A9 motif) showed elevated overall activity compared to the wild-type protein. Our results suggest that the A9 core sequence plays a role in the second reaction step, in which it could serve as a "clip" for the proper positioning of residues important for the interaction with the T-domain, and/or stabilisation of the thioester-forming conformation.     

The comparative study of biocomposites based on hydrochar and chitosan-modified urea-formaldehyde resins

To provide new insight into the field of urea-formaldehyde (UF) adhesives science, in this work, for the first time, UF resin was modified with hydrochar of spent mushroom substrate (HCUF) and chitosan (CHUF) to investigate the effect of these bio-fillers on the hydrolytic and thermal stability of in situ prepared UF resins. The characterization of the modified UF biocomposites was performed using X-ray diffraction analysis (XRD), Fourier transforms infrared spectroscopy (FTIR), non-isothermal thermogravimetric analysis (TG), differential thermal gravimetry (DTG), and differential thermal analysis (DTA). Scanning electron micrographs (SEM) of the CHUF and HCUF biocomposites show a spherical structure that differs from each other because the surface of the CHUF biocomposite has pronounced pores that form a network structure. With its hydroxyl and amino groups, chitosan bonding to UF resin through hydrogen bonds, which is confirmed by FTIR analysis. The content of free FA in CHUF biocomposite is 0.06%, while that of HCUF is higher and amounts to 0.48%. The content of released FA in both modified UF biocomposites was similar (2.5% and 2.8% for CHUF and HCUF, respectively). The hydrolytic stability of CHUF is slightly higher compared to the HCUF biocomposite. Thermal analysis shows that the CHUF is thermally more stable because it starts to decompose at a slightly higher temperature than the HCUF biocomposite.     

Activation of Pozzolanic Reaction of Hydrated Portland Cement Fly Ash Pastes in Sulfate Solution

The activation of the pozzolanic reaction of fly ash in portland cement paste immersed in sulfate solution has been studied. Mixtures of two Spanish fly ashes (ASTM class F) with 0%, 15%, and 35% replacement of portland cement by fly ash were immersed in Na₂SO₄ solution, of 2880 ppm SO₄²⁻ concentration, for a period of 90 days. The resistance of the different mixtures to the sulfate attack was evaluated using the Koch-Steinegger test. The results showed that all of the mixtures were sulfate resistant, despite the high Al₂O₃ content of the fly ash. The diffusion of SO₄²⁻ and Na⁺ ions through the pore solution activated the pozzolanic reactivity of the fly ashes, causing microstructural changes, which were characterized by X-ray diffraction (XRD), mercury intrusion porosimetry (MIP), and scanning electron microscopy (SEM). As a result, the flexural strength of the mixtures increased, principally for the fly ash of a lower particle size and 35% of addition.     

Synthesis and characterization of phenolic and amino resins based on α, β-unsaturated aldehydes

Phenolic and amino resins on the basis of α,β-unsaturated aldehydes were synthesized in bulk or solution. Catalysts were HCl, H₃PO₄, or formic acid, and in some cases NaOH. The course of the reactions was followed by GPC and NMR while the structure of the reaction products was determined by one- and two-dimensional NMR. The course of the reactions is influenced by experimental conditions: the type of monomers, their molar ratio, the type and quantity of the catalyst, the reaction time and temperature, and the reaction medium. At the beginning of the reaction the addition of a nucleophile to an aldehyde takes place through parallel 1,2-addition to and 1,4-addition to group. Oligomers with ? OH, , and ? CHO functional groups are able to add new monomer units or to react mutually to form higher molecular weight addition and condensation products. The overall rate constants for the beginning of the reactions were between 10^?3 L/mol s for the high reactive mixtures and 10^?7 L/mol s for the less reactive mixtures. The resins were cured by heating at temperatures above 135°C with the addition of hexamethylenetetramine.     

Effects of dowels produced from various materials on withdrawal strength in MDF and Pb

Wood dowels are commonly used in the construction furniture, but little information is available about the additive effects of dowels on the ultimate withdrawal strength of single or multidowel joints. This study was carried out to determine the tensile strength of 10‐mm‐diameter dowels produced from medium‐density fiberboard (MDF), plywood, scotch pine (Pinus sylvestris L.), and beech (Fagus orientalis lipsky), bonded parallel and vertical to the surface of MDF and particleboard (Pb) with poly(vinyl acetate) (PVAc) and Desmodur‐VTKA (D‐VTKA). Tensile strength was applied to the dowels according to the procedure in the ASTM‐D 1037 standard. The effects of dowel species, direction of tensile, composite material, and type of adhesive on tensile strength were determined. The results showed that the highest tensile strength was obtained in beech dowels bonded vertically with PVAc adhesive to the surface of MDF at 7.91 N/mm². If the dowels used in furniture production are subjected to great tensile strength, beech dowels bonded with PVAc adhesive on MDF should be used. However, when dowels produced from MDF and plywood waste are used, they also can produce positive results. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 531–535, 2003     

An XRD,FTIR and TPD investigation of NO2 surface adsorption sites of δ, γ Al2O3 and barium supported δ, γ Al2O3

This work reviews the use of terpenes available from renewable resources in the fine chemicals industry. Different products and processes are discussed. Transformations of terpenes involving isomerization, hydration, condensation, hydroformylation, hydrogenation, cyclization, oxidation, rearrangement, and ring contraction/enlargement are routes to produce a variety of compounds of interest to the pharmaceutical, agrochemical, and flavors and fragrances industries.     

高含氮高浓度有机废水生物处理技术研究

分析了石家庄化纤公司己内酰胺生产废水的水质状况,指出该废水属高含氮、高浓度有机废水,虽然可生物降解性能较好,但因处理水在好氧硝化池(O1)中水力停留时间不够,难以达到硝化阶段,导致了原有生物处理工艺A／O／A／O系统无法正常运行。根据生物脱氮原理,提出了以SBR法作为处理工艺主体的ENSBR／BDAR／PCOR三段生物处理工艺。实验数据和生产运用表明,高含氮高浓度有机废水经该工艺处理后出水水质达到国家二级排放标准要求。     

Ring opening polymerization of 2,5-dihydro-2,5-dimethoxyfuran by electrochemical initiation

Summary 2,5-Dihydro-2,5-dimethoxyfuran (DHMF) was polymerized via constant current electrolysis (CCE), in CH₃CN-NaClO₄ solvent-electrolyte couple. Poly(DHMF) was obtained from the anolyte. The effect of current density, temperature, monomer and electrolyte concentrations on the polymer yield have been examined. The apparent activation energy for CCE of DHMF was found to be 37.2 kj/mol. The FTIR and ¹H-NMR analyses show that DHMF polymerizes by a ring opening. Molecular weight of poly(DHMF) was found by using cryoscopy.     

Ketonization of Proline Residues in the Peptide Chains of Actinomycins by a 4‐Oxoproline Synthase

X‐type actinomycins (Acms) contain 4‐hydroxyproline (Acm X₀) or 4‐oxoproline (Acm X₂) in their β‐pentapeptide lactone rings, whereas their α ring contains proline. We demonstrate that these Acms are formed through asymmetric condensation of Acm half molecules (Acm halves) containing proline with 4‐hydroxyproline‐ or 4‐oxoproline‐containing Acm halves. In turn, we show—using an artificial Acm half analogue (PPL 1) with proline in its peptide chain—their conversion into the 4‐hydroxyproline‐ and 4‐oxoproline‐containing Acm halves, PPL 0 and PPL 2, in mycelial suspensions of Streptomyces antibioticus. Two responsible genes of the Acm X biosynthetic gene cluster of S. antibioticus, saacmM and saacmN, encoding a cytochrome P450 monooxygenase (Cyp) and a ferredoxin were identified. After coexpression in Escherichia coli, their gene products converted PPL 1 into PPL 0 and PPL 2 in vivo as well as in situ in permeabilized cell of the transformed E. coli strain in conjunction with the host‐encoded ferredoxin reductase in a NADH (NADPH)‐dependent manner. saAcmM has high sequence similarity to the Cyp107Z (Ema) family of Cyps, which can convert avermectin B1 into its keto derivative, 4′′‐oxoavermectin B1. Determination of the structure of saAcmM reveals high similarity to the Ema structure but with significant differences in residues decorating their active sites, which defines saAcmM and its orthologues as a distinct new family of peptidylprolineketonizing Cyp.