Cellular Synthesis and X-ray Crystal Structure of a Designed Protein Heterocatenane

Herein, we report the biosynthesis of protein heterocatenanes using a programmed sequence of multiple post-translational processing events including intramolecular chain entanglement, in situ backbone cleavage, and spontaneous cyclization. The approach is general, autonomous, and can obviate the need for any additional enzymes. The catenane topology was convincingly proven using a combination of SDS-PAGE, LC-MS, size exclusion chromatography, controlled proteolytic digestion, and protein crystallography. The X-ray crystal structure clearly shows two mechanically interlocked protein rings with intact folded domains. It opens new avenues in the nascent field of protein-topology engineering.     

Cross-Linked Polyphosphazene Hollow Nanosphere-Derived N/P-Doped Porous Carbon with Single Nonprecious Metal Atoms for the Oxygen Reduction Reaction

Heteroatom-doped polymers or carbon nanospheres have attracted broad research interest. However, rational synthesis of these nanospheres with controllable properties is still a great challenge. Herein, we develop a template-free approach to construct cross-linked polyphosphazene nanospheres with tunable hollow structures. As comonomers, hexachlorocyclotriphosphazene provides N and P atoms, tannic acid can coordinate with metal ions, and the replaceable third comonomer can endow the materials with various properties. After carbonization, N/P-doped mesoporous carbon nanospheres were obtained with small particle size (≈50 nm) and high surface area (411.60 m² g⁻¹). Structural characterization confirmed uniform dispersion of the single atom transition metal sites (i.e., Co-N₂P₂) with N and P dual coordination. Electrochemical measurements and theoretical simulations revealed the oxygen reduction reaction performance. This work provides a solution for fabricating diverse heteroatom-containing polymer nanospheres and their derived single metal atom doped carbon catalysts.     

ZIF-Induced d-Band Modification in a Bimetallic Nanocatalyst: Achieving Over 44 % Efficiency in the Ambient Nitrogen Reduction Reaction

The electrochemical nitrogen reduction reaction (NRR) offers a sustainable solution towards ammonia production but suffers poor reaction performance owing to preferential catalyst–H formation and the consequential hydrogen evolution reaction (HER). Now, the Pt/Au electrocatalyst d-band structure is electronically modified using zeolitic imidazole framework (ZIF) to achieve a Faradaic efficiency (FE) of >44 % with high ammonia yield rate of >161 μg mg_cat⁻¹ h⁻¹ under ambient conditions. The strategy lowers electrocatalyst d-band position to weaken H adsorption and concurrently creates electron-deficient sites to kinetically drive NRR by promoting catalyst–N₂ interaction. The ZIF coating on the electrocatalyst doubles as a hydrophobic layer to suppress HER, further improving FE by >44-fold compared to without ZIF (ca. 1 %). The Pt/Au-N_ZIF interaction is key to enable strong N₂ adsorption over H atom.     

A Fully Non-fused Ring Acceptor with Planar Backbone and Near-IR Absorption for High Performance Polymer Solar Cells

Fused-ring electron acceptors have made significant progress in recent years, while the development of fully non-fused ring acceptors has been unsatisfactory. Here, two fully non-fused ring acceptors, o-4TBC-2F and m-4TBC-2F, were designed and synthesized. By regulating the location of the hexyloxy chains, o-4TBC-2F formed planar backbones, while m-4TBC-2F displayed a twisted backbone. Additionally, the o-4TBC-2F film showed a markedly red-shifted absorption after thermal annealing, which indicated the formation of J-aggregates. For fabrication of organic solar cells (OSCs), PBDB-T was used as a donor and blended with the two acceptors. The o-4TBC-2F-based blend films displayed higher charge mobilities, lower energy loss and a higher power conversion efficiency (PCE). The optimized devices based on o-4TBC-2F gave a PCE of 10.26 %, which was much higher than those based on m-4TBC-2F at 2.63 %, and it is one of the highest reported PCE values for fully non-fused ring electron acceptors.     

Iron-Catalyzed Radical Relay Enabling the Modular Synthesis of Fused Pyridines from Alkyne-Tethered Oximes and Alkenes

We have rationally designed a new class of alkyne-tethered oximes and applied them in an unprecedented iron-catalyzed radical relay protocol for the rapid assembly of a wide array of structurally new and interesting fused pyridines. This method shows broad substrate scope and good functional-group tolerance and enabled the synthesis of several biologically active molecules. Furthermore, the fused pyridines could be diversely functionalized through various simple transformations, such as cyclization, C−H alkylation, and a click reaction. DFT calculation studies indicate that the reactions involve cascade 1,5-hydrogen atom transfer, 5-exo-dig radical addition, and cyclization processes. Moreover, preliminary biological investigations suggest that some of the fused pyridines exhibit good anti-inflammatory activity by restoring the imbalance of inflammatory homeostasis of macrophages in a lipopolysaccharide-induced model.     

Research on gamma-ray irradiation-assisted synthesis of cross-linked polystyrene via bulk polymerization

Journal of Radioanalytical and Nuclear Chemistry - Controlling heat accumulation is one of the major challenges for block materials synthesizing via bulk polymerization. In the paper, cross-linked...     

Quick stabilization of capillary for rapid determination of potassium ions in the blood of epilepsy patients by capillary electrophoresis without sample pretreatment

Mutations in the potassium channel genes may be linked to the development of epilepsy and affect the blood potassium levels. Therefore, accurate determination of potassium in the blood will be critical to diagnose the cause of epilepsy. CE is a competent technique for the fast detection of multiple ions, but complicated matrices of a blood sample may cause significant variation of migration times and the peak shape. In this work, a procedure for rapid stabilization of the capillary inner surface through preflushing of a blood sample was employed. The process takes only 40 min for a capillary and then it can be used for more than 2 weeks. No pretreatment of the blood sample or other surface modification of the capillary is needed for the analysis. The RSDs of the migration time and peak area were reduced to 1.5 and 5.1% from 12.6 and 14.5%, respectively. The proposed method has been successfully applied to the determination of the potassium contents in the blood sample of patients with epilepsy at different stages. The recoveries of potassium ions in these blood samples are in a range from 86.5 to 104.5%.     

Characterization of sequence variation at 30 autosomal STRs in Chinese Han and Tibetan populations

Massively parallel sequencing (MPS) technologies have the ability to reveal sequence variations within STR alleles as well as their nominal allele lengths, which have traditionally been detected by CE instruments. Recently, Thermo Fisher Scientific has updated the MPS-STR panel, named the Precision ID GlobalFiler next-generation sequencing (NGS) STR Panel version 2, with primers redesigned to add two pentanucleotide tandem repeat loci and profile interpretation supported by the Converge software. Using the Ion Chef System, the Ion S5XL System, and the Converge software, genetic variations were characterized within STR repeat and flanking regions of 30 autosomal STR markers in 115 unrelated individuals from two Chinese population groups (58 Tibetans and 57 Hans). Nineteen STRs demonstrated a relative increase in diversity with the variant sequence alleles compared with those of traditional nominal length alleles. In total, 390 alleles were identified by their sequences compared with 258 alleles that were identified by length. Of these 92 sequence variants found within the STR repeat regions, 40 variants were located in STR flanking regions. Additionally, the agreement of the results with CE data was evaluated, as was the ability of this new MPS panel to analyze case-type (11 samples) and artificially degraded samples (seven samples in triplicate). The results generated from this study illustrate that extensive sequence variation exists in commonly used STR markers in the selected population samples and indicate that this NGS STR panel has the potential to be used as an effective tool for human forensics.     

两亲性嵌段共聚物PMnEOS-b-PAA的可控合成及与PS-b-PAA共组装体的形貌

在苯乙烯单体的对位引入具有亲水性链段的乙二醇单元, 利用可逆加成断裂链转移聚合方法(RAFT), 可控合成了几种新的两亲性嵌段共聚物聚(4-乙烯基苄基乙二醇单甲醚)-b-聚丙烯酸(PMnEOS-b-PAA, n=1~3), 对其温敏和pH敏性质进行了初步研究. 同时, 研究了PMnEOS-b-PAA分别在亲水性环境下(四氢呋喃/水)和亲脂性环境下(四氢呋喃/甲苯)自组装体的形貌. 将聚对二乙二醇单甲醚苯乙烯-b-聚丙烯酸与聚苯乙烯-b-聚丙烯酸按质量比1:1[m(PMDEOS-b-PAA)/m(PS-b-PAA)=1:1]共混进行共组装, 在四氢呋喃/甲苯体积比为2∶1的混合溶剂中, 发现了一类新型具有均匀分布内部孔道且表面光滑的球形组装体. 进一步研究了该组装体的可重复性和组装机理, 为其后期应用于工业上的负载催化、 小分子识别与释放提供了一种新的策略.     

La0.7Sr0.3CoO3-δ钙钛矿催化剂表征及其催化氧化碳黑性能研究

为了研究La_(0.7)Sr_(0.3)CoO_(3-δ)钙钛矿催化剂对碳黑的催化氧化过程,本研究通过研究催化剂和碳黑的两种不同接触方式,即紧密接触与松散接触,讨论了其对碳黑催化氧化过程的影响。结果表明,与松散接触和无催化剂接触条件相比,紧密接触条件下碳黑的tig(起燃温度)分别下降了89.5和157.4℃,同时随着催化剂/碳黑的比例增加,碳黑氧化的tig、tm(最大转化温度)、tf(燃净温度)均向低温区域移动,表明该催化剂对碳黑有着良好的催化氧化性能。