As fast and selective as enzymatic ligations: unpaired nucleobases increase the selectivity of DNA-controlled native chemical PNA ligation

DNA-controlled reactions offer interesting opportunities in biological, chemical, and nanosciences. In practical applications, such as in DNA sequence analysis, the sequence fidelity of the chemical-ligation reaction is of central importance. We present a ligation reaction that is as fast as and much more selective than enzymatic T4 ligase-mediated oligonucleotide ligations. The selectivity was higher than 3000-fold in discriminating matched from singly mismatched DNA templates. It is demonstrated that this enormous selectivity is the hallmark of the particular ligation architecture, which is distinct from previous ligation architectures designed as "nick ligations". Interestingly, the fidelity of the native chemical ligation of peptide nucleic acids was increased by more than one order of magnitude when performing the ligation in such a way that an abasic-site mimic was formed opposite an unpaired template base. It is shown that the high sequence fidelity of the abasic ligation could facilitate the MALDI-TOF mass-spectrometric analysis of early cancer onset by allowing the detection of as little as 0.2 % of single-base mutant DNA in the presence of 99.8 % wild-type DNA.     

A native chemical ligation approach for combinatorial assembly of affibody molecules

Affinity molecules labeled with different reporter groups, such as fluorophores or radionuclides, are valuable research tools used in a variety of applications. One class of engineered affinity proteins is Affibody molecules, which are small (6.5 kDa) proteins that can be produced by solid phase peptide synthesis (SPPS), thereby allowing site-specific incorporation of reporter groups during synthesis. The Affibody molecules are triple-helix proteins composed of a variable part, which gives the protein its binding specificity, and a constant part, which is identical for all Affibody molecules. In the present study, native chemical ligation (NCL) has been applied for combinatorial assembly of Affibody molecules from peptide fragments produced by Fmoc SPPS. The concept is demonstrated for the synthesis of three different Affibody molecules. The cysteine residue introduced at the site of ligation can be used for directed immobilization and does not interfere with the function of the investigated proteins. This strategy combines a high-yield production method with facilitated preparation of proteins with different C-terminal modifications.     

一种替代含铅助熔剂制备大尺寸氧化锌晶须方法的研究

以工业氧化锌(ZnO)粉为原料,助剂以四钛酸钾(K_2Ti_4O_9)为主,采用助熔剂法制备大尺寸针状ZnO晶须,并对其生长条件及影响因素进行了研究。主要采用X粉末衍射仪,能谱仪和超景深显微镜机等分析手段对ZnO晶须的结构和形貌进行了表征并进行了简单的探讨。结果表明,当物料配比为C∶ZnO(5%Na_2B_4O_9·10H_2O)∶K_2Ti_4-O_9=0.60g∶0.50g∶3.00g,其中K_2Ti_4O_9粒径为10目,反应温度为900℃,恒温时间120min,坩埚容量30mL时,便得到纯度高、颜色白、形貌均一、针体长度约20mm的ZnO晶须。     

一种替代含铅助熔剂制备大尺寸氧化锌晶须方法的研究

以工业氧化锌(ZnO)粉为原料,助剂以四钛酸钾(K_2Ti_4O_9)为主,采用助熔剂法制备大尺寸针状ZnO晶须,并对其生长条件及影响因素进行了研究。主要采用X粉末衍射仪,能谱仪和超景深显微镜机等分析手段对ZnO晶须的结构和形貌进行了表征并进行了简单的探讨。结果表明,当物料配比为C∶ZnO(5%Na_2B_4O_9·10H_2O)∶K_2Ti_4-O_9=0.60g∶0.50g∶3.00g,其中K_2Ti_4O_9粒径为10目,反应温度为900℃,恒温时间120min,坩埚容量30mL时,便得到纯度高、颜色白、形貌均一、针体长度约20mm的ZnO晶须。     

Nonenzymatic ligation of DNA with a reversible step and a final linkage that can be used in PCR

Nonenzymatic DNA ligation chemistries containing a reversible step allow thermodynamic control of product formation, but they are not necessarily compatible with polymerase enzymes. We report a ligation system that uses commercially available reagents, includes a reversible step, and results in a linkage that can function as a template for PCR amplification with accurate sequence transfer.     

Physical mixtures as simple and efficient alternative to alloy carriers in chemical looping processes

Chemical looping combustion is a clean combustion technology for fossil or renewable fuels. In a previous demonstration, chemical looping was applied to CO₂ activation via reduction to CO with concurrent production of synthesis gas (CO + H₂) from CH₄ via rationally designed Fe‐Ni alloys. Here, it is demonstrated that that a simple physical mixture can even outperform the equivalent alloy based on an intricate gas phase mediated coupling between the two metals: Ni cracks methane to carbon and H₂. The latter then reduces iron oxide carrier, forming steam, which gasifies the carbon deposits on Ni to produce a mixture of CO + H₂, thus regenerating the active Ni surface. It was suggested that the principle demonstrated here—the gas phase‐mediated coupling of two solid reactants with distinct functionalities—should be applicable broadly toward oxidation reactions and hence opens a new avenue for rational design of chemical looping processes. © 2016 American Institute of Chemical Engineers AIChE J, 63: 51–59, 2017     

A Helix‐Stabilized Cell‐Penetrating Peptide as an Intracellular Delivery Tool

Two types of cationic cyclic α,α‐disubstituted α‐amino acids: Api (which possesses a lysine mimic side chain) and Api^C2Gu (which possesses an arginine mimic side chain), were developed. These amino acids were incorporated into an arginine‐based peptide sequence [(l ‐Arg‐l ‐Arg‐dAA)₃: dAA=Api or Api^C2Gu], and the relationship between the secondary structures of the resulting peptides and their ability to pass through cell membranes was investigated. The peptide containing Api^C2Gu formed a stable α‐helical structure and was more effective at penetrating cells than the nonhelical Arg nonapeptide (R₉). Furthermore, the peptide was able to deliver plasmid DNA into various types of cells in a highly efficient manner.     

Characterization of ceramic sol-gel coatings as an alternative chemical conversion treatment on commercial carbon steel

Sol-gel yttria-stabilized zirconia (YSZ) thin films were prepared on commercial carbon steel sheets by dip-coating technique followed by a low temperature heat treatment (473, 573, and 673 K for 1 h) in order to improve both corrosion properties and adhesion. For comparison, zirconia (ZrO₂) coatings have been also analyzed. Electrochemical techniques, Fourier Transform Infrared (FT-IR), X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to characterize the anticorrosion behavior of the coatings in a 3.5 wt% NaCl solution. The adhesion with a polyester organic coating was evaluated by the pull-off technique. The typical thickness of the deposited layers ranged from 1 to 1.3 μm depending on process parameters. The obtained results indicated that sol-gel ZrO₂ and YSZ coatings without an organic coating can act as protective barriers against wet corrosion during the first hours, but they fail when the time exposure is longer than 1 day. However, when synthesized films were used as a pre-treatment and an organic coating was added (top-coated), the anticorrosive and adhesion properties were strongly affected by the temperature of the treatment, and an increase in both properties was observed at higher temperatures. The structural and morphological characteristics of the coating provide an explanation of the role of each film in the electrochemical behavior in this aggressive medium. Comparing both systems, YSZ displayed greater protective and adhesion values than exhibited for ZrO₂ which can be correlated with the stabilization of the cubic phase.     

Accelerated electrons as an alternative to natural fuel in aluminum production technologies

An approach to modernizing aluminum production technology based on an intense beam of accelerated electrons representing a principally new energy carrier for this production branch is proposed. Physicochemical principles for creating a new technology and reasons based on interest in modernization are discussed. Some peculiarities of the effect of accelerated electrons on the initiation of chemical reactions in liquid and solid materials used in aluminum production industry are considered. The energy balance of the classic thermal aluminum production technology is analyzed, and conclusions about engineering, economics, and the environmental advisability of developing an approach to modernizing aluminum production technology with a new energy carrier, an accelerated electron beam, is formulated based on theoretical and experimental data. The parameters of some electron accelerators that satisfy the conditions needed to develop the proposed technology even now are given.     

Benzodioxoles as alternative coinitiators for radical polymerization in a model‐dental adhesive resin

This study evaluated the effectiveness of benzodioxole derivatives as coinitiators of radical polymerization in a model‐dental adhesive resin. To compose the adhesive resin, a monomer mixture based on 50 wt % of Bis‐GMA, 25 wt % of TEGDMA, and 25 wt % of HEMA was used. Camphorquinone (CQ) 1 mol % was used as a photoinitiator to initiate polymerization. 1,3‐Benzodioxole (BDO) and piperonyl alcohol (PA) were used as coinitiators at 0.25, 0.5, 1, 2, 4, 8, and 16 mol % level. In addition, tertiary amine, ethyl 4‐dimethylamino benzoate (EDAB) was used as coinitiator in the control group. Some physical, chemical, and mechanical properties of the polymer formed in the experimental adhesives were evaluated using the kinetics of polymerization, sorption and solubility, flexural strength, and elastic modulus tests. The results indicated that BDO and PA were effective coinitiators in the photoinitiator system based on CQ. Comparisons between the benzodioxoles derivative coinitiators and EDAB showed similar performance in the kinetics of polymerization and flexural strength. For water sorption and solubility evaluation, BDO and PA demonstrated significantly more sorption of water and less solubility than the EDAB control group. The findings suggest that BDO and PA were feasible alternatives to conventional amine as coinitiator. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Nitrogen‐doped graphene as an alternative to ecotoxic zinc oxide in rubbers

Zinc oxide (ZnO) is an essential ingredient in industrial rubber production; it regulates the onset of vulcanization, accelerates the kinetics of vulcanization, and improves the mechanical properties of rubber. However, environmental pollution with ZnO is a concern because it is recognized to be significantly ecotoxic and might also have adverse effects on human health. One of the major sources of ZnO environmental pollution is rubber items, tires in particular. Nitrogen (N)‐doped graphene is a promising next‐generation catalyst. We show here that the replacement of 3 phr ZnO by just 0.1 phr N‐doped graphene in styrene–butadiene rubber reduced the vulcanization onset time by more than a factor of two while retaining the fast vulcanization kinetics and enhancing the tensile strength in comparison with rubber with just ZnO. A shorter vulcanization time implies energy savings, which, together with the nontoxicity of N‐graphene, should make the resulting rubbers substantially more environmentally friendly. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46116.     

Functionalized lactic acid macromonomers via polycondensation as an alternative to ring opening polymerization

Engineered polylactic acid (PLA) nanoparticles synthesized from oligo(lactic acid) macromonomers have been studied over the last decades for controlled drug delivery. These macromonomers are typically produced via ring-opening polymerization (ROP) of the cyclic dimer lactide, initiated by 2-hydroxyethyl methacrylate (HEMA). This reaction route, despite leading to well-defined macromonomers, relies on the production of lactide from lactic acid, which burdens the ROP overall cost for more than 30%. In this work, we report the synthesis of PLA-based macromonomers by direct polycondensation of lactic acid in the presence of HEMA as a valuable alternative to ROP. In particular, we compare the two processes side by side, focusing on the production of three HEMA-LA_n macromonomers, with n = 2, 4, and 6. Detailed kinetic models are developed for both reaction systems, and the corresponding parameters are estimated by fitting the experimental data. Through these models, the reaction kinetics as well as the time evolution of the entire chain length distributions of the products from polycondensation and ROP could be reliably predicted. This way, we demonstrated that polycondensation is a valuable alternative to ROP only for macromonomers with an average chain length of up to 4 and that ROP remains the main route to longer chains, when a strict control over the chain length distribution is required.     

Amide Neighbouring‐Group Effects in Peptides: Phenylalanine as Relay Amino Acid in Long‐Distance Electron Transfer

In nature, proteins serve as media for long‐distance electron transfer (ET) to carry out redox reactions in distant compartments. This ET occurs either by a single‐step superexchange or through a multi‐step charge hopping process, which uses side chains of amino acids as stepping stones. In this study we demonstrate that Phe can act as a relay amino acid for long‐distance electron hole transfer through peptides. The considerably increased susceptibility of the aromatic ring to oxidation is caused by the lone pairs of neighbouring amide carbonyl groups, which stabilise the Phe radical cation. This neighbouring‐amide‐group effect helps improve understanding of the mechanism of extracellular electron transfer through conductive protein filaments (pili) of anaerobic bacteria during mineral respiration.     

装饰性锡锌镍三元合金代镍工艺研究

研究了装饰性电镀锡锌镍三元合金代镍工艺。采用赫尔槽试验探讨了主盐、添加剂、溶液温度和pH对镀层镍含量、镀层外观及镀液稳定性的影响。结果表明:该工艺操作方便,镀液分散能力和覆盖能力好,所得锡锌镍合金镀层结晶细致,光亮,类似镍层,其耐蚀性明显优于锌镀层,适用于钢铁件高耐蚀装饰性电镀。