Unveiling the Dynamic Self-Assembly of a Recombinant Dragline-Silk-Mimicking Protein.

Despite the considerable interest in the recombinant production of synthetic spider silk fibers that possess mechanical properties similar to those of native spider silks, such as the cost-effectiveness, tunability, and scalability realization, is still lacking. To address this long-standing challenge, we have constructed an artificial spider silk gene using Golden Gate assembly for the recombinant bacterial production of dragline-mimicking silk, incorporating all the essential components: the N-terminal domain, a 33-residue-long major-ampullate-spidroin-inspired segment repeated 16 times, and the C-terminal domain (N16C). This designed silk-like protein was successfully expressed in Escherichia coli, purified, and cast into films from formic acid. We produced uniformly 13C-15N-labeled N16C films and employed solid-state magic-angle spinning nuclear magnetic resonance (NMR) for characterization. Thus, we could demonstrate that our bioengineered silk-like protein self-assembles into a film where, when hydrated, the solvent-exposed layer of the rigid, ß-nanocrystalline polyalanine core undergoes a transition to an α-helical structure, gaining mobility to the extent that it fully dissolves in water and transforms into a highly dynamic random coil. This hydration-induced behavior induces chain dynamics in the glycine-rich amorphous soft segments on the microsecond time scale, contributing to the elasticity of the solid material. Our findings not only reveal the presence of structurally and dynamically distinct segments within the film's superstructure but also highlight the complexity of the self-organization responsible for the exceptional mechanical properties observed in proteins that mimic dragline silk.

Zhang equivalency of inequation-to-inequation type for constraints of redundant manipulators.

In solving specific problems, physical laws and mathematical theorems directly express the connections between variables with equations/inequations. At times, it could be extremely hard or not viable to solve these equations/inequations directly. The PE (principle of equivalence) is a commonly applied pragmatic method across multiple fields. PE transforms the initial equations/inequations into simplified equivalent equations/inequations that are more manageable to solve, allowing researchers to achieve their objectives. The problem-solving process in many fields benefits from the use of PE. Recently, the ZE (Zhang equivalency) framework has surfaced as a promising approach for addressing time-dependent optimization problems. This ZEF (ZE framework) consolidates constraints at different tiers, demonstrating its capacity for the solving of time-dependent optimization problems. To broaden the application of ZEF in time-dependent optimization problems, specifically in the domain of motion planning for redundant manipulators, the authors systematically investigate the ZEF-I2I (ZEF of the inequation-to-inequation) type. The study concentrates on transforming constraints (i.e., joint constraints and obstacles avoidance depicted in different tiers) into consolidated constraints backed by rigorous mathematical derivations. The effectiveness and applicability of the ZEF-I2I are verified through two optimization motion planning schemes, which consolidate constraints in the velocity-tier and acceleration-tier. Schemes are required to accomplish the goal of repetitive motion planning within constraints. The firstly presented optimization motion planning schemes are then reformulated as two time-dependent quadratic programming problems. Simulative experiments conducted on the basis of a six-joint redundant manipulator confirm the outstanding effectiveness of the firstly presented ZEF-I2I in achieving the goal of motion planning within constraints.

Effects of pelvic floor myofascial manipulation intervention on primiparas and neonates during the second stage of vaginal delivery.

A prolonged second stage of vaginal delivery increases the risk of shoulder dystocia, unnecessary episiotomies and cesarean sections. However, no standardized method has been proposed to tackle this issue. The effects of pelvic floor myofascial manipulation intervention during the second stage of labor in primiparas and its prognostic value in neonatal postpartum outcomes remain unknown. In the present study, a total of 60 primiparas who were expecting a vaginal delivery in the Second Affiliated Hospital of Hainan Medical College (Haikou, China) between October 2021 and January 2022 were selected. These women were randomly assigned to a control group (standard intrapartum care) or an experimental group (pelvic floor myofascial manipulation for 15-20 min during the second stage of labor along with standard intrapartum care) using a random number table, with 28 patients in each group. There was no significant difference in age, gestational time or body mass index between the two groups before delivery, indicating that the baseline data were comparable. The second stage of labor duration, forced breath-holding time and postpartum hemorrhage volume in the experimental group were significantly lower than those in the control group. The pain visual analog scale scores, fatigue scores and neonatal Apgar scores in the experimental group were also significantly lower than those in the control group. The rate of episiotomy in the experimental group was lower than that in the control group, but the difference was not statistically significant. In conclusion, pelvic floor myofascial manipulation intervention during the second stage of labor for primiparas with vaginal delivery can reduce the duration of the second stage of labor, the amount of bleeding during labor and the pain during labor. Meanwhile, it has the potential to improve neonatal outcomes.

Azide Ionic Liquids for Safe, Green, and Highly-Efficient Azidation Reactions to Produce Azide Polymers.

Azide compounds are widely used and especially, polymers bearing pendant azide groups are highly desired in numerous fields. However, harsh reaction conditions are always mandatory to achieve full azidation, causing severe side reactions and degradation of the polymers. Herein, we report the design and preparation of two azide ionic liquids (AILs) with azide anion and triethylene glycol (E3 )-containing cation, [P444E3 ][N3 ] and [MIME3 ][N3 ]. Compared with the traditional sodium azide (NaN3 ) approach, both AILs showed much higher reaction rates and functional-group tolerance. More importantly, they could act as both reagents and solvents for the quantitative azidation of various polymeric precursors under mild conditions. Theoretical simulations suggested that the outstanding performance of AILs originated from the existence of ion pairs during the reaction, and the E3 moieties played a crucial role. Lastly, after the reaction, the AILs could be easily regenerated, presenting a safer, greener, and highly efficient synthesis route for azide polymers.

Correction: Highly photoluminescent nitrogen-rich carbon dots from melamine and citric acid for the selective detection of iron(iii) ion.

[This corrects the article DOI: 10.1039/C5RA26521E.].

Binuclear cobalt(II) and two-dimensional manganese(II) coordination compounds self-assembled by mixed bipyridine-tetracarboxylic ligands with single-ion magnet properties.

A cobalt(II) complex and manganese(II) coordination polymer, formulated as [Co2(H2btca)(mbpy)4][H2btca]·4H2O (1) and {Mn2(btca)(mbpy)2(H2O)2}n (2) (H4btca = 1,2,4,5-benzenetetracarboxylic acid; mbpy = 4,4'-dimethyl-2,2'-bipyridyl), constructed by mixed bipyridine-tetracarboxylic ligands were synthesized and characterized. Single-crystal structural analyses reveal that compound 1 is a discrete neutral binuclear molecule, while compound 2 is a two-dimensional (2D) coordination polymer. The metal ions in these compounds are well isolated, with an intramolecular Co2+⋯Co2+ distance of 9.170 Å for 1 and Mn2+⋯Mn2+ separation of 10.984 and 11.164 Å for 2 due to the bulk tetracarboxylic linker. This isolation gives rise to a single-ion magnetism origin of the compounds. Magnetic studies reveal a large zero-field splitting parameter D of 82.6 cm-1 for 1, while a very small D of 0.42 cm-1 was observed for 2. Interestingly, dynamic ac magnetic measurements exhibited slow magnetic relaxation under the external dc field of the two compounds, revealing the field-supported single-ion magnet (SIM) of 1 and 2. The detailed theoretical calculations were further applied to understand the electronic structures, magnetic anisotropy, and relaxation dynamics in 1 and 2. Combined with our recently reported compound (Eur. J. Inorg. Chem., 2022, e202200354), the foregoing results provide not only a rare binuclear cobalt(II) SIM and the first 2D manganese(II) SIM coordination polymer but also a bipyridine-tetracarboxylic ligand approach toward novel SIMs.

Hexatopic Vertex-Directed Approach to Vinylene-Linked Covalent Organic Frameworks with Heteroporous Topologies.

A D3h-symmetric hexatopic monomer was first prepared by attaching the three-fold ditopic moiety 2,6-dimethylpyridine to the meta-positions of a phenyl ring. It was further condensed at its six pyridylmethyl carbons with linear ditopic aromatic dialdehydes, resulting in two vinylene-linked COFs with heteroporous topologies, as revealed by powder X-ray diffraction (PXRD), nitrogen sorption, and pore-size distribution analyses, as well as transmission electron microscopy (TEM) image. The linear- and cross-conjugations, respectively, arising from the 2,6-linked pyridines and meta-linked phenylenes in the hexatopic nodes rendered the resultant COFs with well-patterned π-delocalization, allowing for efficiently catalyzing the bromination of aromatic derivatives with the pore-size-dependent conversion yields and regioselectivity under the irradiation of green light.

Construction of N-Ferrocene Substituted Benzodihydrooxazoles via a Catalyst-Free Aza-Michael Addition/C(sp3)-O Bond Formation Tandem Reaction.

A catalyst-free aza-Michael addition/C(sp3)-O bond formation tandem reaction of substituted amino ferrocenes with quinone esters was developed, which provided a green and efficient strategy for the construction of a C(sp3)-O bond from C(sp3)-H, and a series of N-ferrocene-substituted benzodihydrooxazoles were smoothly produced in moderate to excellent yields (up to >99% yield). The mechanism experiments showed that quinone esters performed as both substrate and oxidant. The salient features of this transformation include good functional group tolerance, broad substrate scope and mild conditions.

Brønsted Acid-Catalyzed Reaction of N-arylnaphthalen-2-amines with Quinone Esters for the Construction of Carbazole and C-N Axially Chiral Carbazole Derivatives.

We demonstrated here an efficient synthetic method of carbazole derivatives from readily available N-arylnaphthalen-2-amines and quinone esters catalyzed by Brønsted acid. With this strategy, a series of carbazole derivatives were obtained in good to excellent yields (76 to >99) under mild conditions. Large scale reaction illustrated the synthetic utility of this protocol. Meanwhile, a series of C-N axially chiral carbazole derivatives were also constructed in moderate to good yields (36-89% yield) with moderate to excellent atroposelectivities (44-94% ee) by using chiral phosphoric acid as a catalyst, which provides a novel strategy for the atroposelective construction of C-N axially chiral compounds and a new member of the C-N atropisomers.

All-Carbon Solution-Gated Transistor with Low Operating Voltages for Highly Selective and Stable Dopamine Sensing.

The diversity of carbon materials makes it possible to prepare all-carbon electronic devices requiring components with different properties and functions. In this work, we fabricate an all-carbon solution-gated transistor (AC-SGT) based dopamine (DA) sensor with Nafion coated nitrogen and oxygen co-doped carbon yarn (Nafion/NOCY) as the gate electrode and graphene as the channel. The carbon materials in AC-SGT render the usage of a variety of strategies to improve its electrochemical sensing capability including the modification of the gate electrode and the modulation of the operating voltage. With a low gate-source voltage of 0.02 V as well as a low drain-source voltage of 0.05 V, AC-SGT manifests the outstanding DA sensing performances in terms of sensitivity, selectivity, limit of detection (3 nM, S/N > 3), linear range (3 nM to 300 µM), long-term stability (over 30 days), and preconditioning time (60 s). Furthermore, a smartphone controlled portable sensing system integrated with AC-SGT is fabricated herein, which shows the excellent in vitro sensing capability of DA in urine, proving the potential of all-carbon transistors in smart wearable biosensors.

Interplay Between Liver Type 1 Innate Lymphoid Cells and NK Cells Drives the Development of Alcoholic Steatohepatitis.

BACKGROUND & AIMS: Liver contains high frequency of group 1 innate lymphoid cells (ILC), which are composed of comparable number of type 1 ILC (ILC1) and natural killer (NK) cells in steady state. Little is known about whether and how the interaction between ILC1 and NK cells affects the development of alcoholic liver disease. METHODS: A mouse model of chronic alcohol abuse plus single-binge (Gao-Binge model) was established. The levels of alanine aminotransferase/aspartate aminotransferase, hepatic lipid, and inflammatory cytokines or neutrophils were measured to evaluate the degree of liver injury, steatosis, and inflammation. Flow cytometric analysis, cell depletion, or adoptive transfer were used to interrogate the interaction between ILC1 and NK cells. RESULTS: Upon chronic alcohol consumption, NK cells, but not ILC1, underwent apoptosis, resulting in ILC1 dominance among group 1 ILC. Interleukin (IL) 17A expression was up-regulated, and increased IL17A was mainly derived from liver ILC1 after chronic alcohol feeding. Either depletion of ILC1 or neutralization of IL17A could significantly attenuate liver steatosis, inflammation, and injury in alcohol-fed mice. In contrast, normalization of the ILC1/NK cells ratio through NK cells transfer or expanding NK cells had a significant hepatoprotection against alcohol-induced steatohepatitis. Furthermore, NK cell-derived interferon gamma exerted a protective function via inhibiting IL17A production by liver ILC1 during alcoholic steatohepatitis. CONCLUSIONS: This is the first study showing that the interplay between liver ILC1 and NK cells occurs and drives the development of alcoholic steatohepatitis. Our findings support further exploration of liver ILC1 or NK cells as a therapeutic target for the treatment of alcohol-associated liver disease.

2,4,6-Trimethylpyridine-Derived Vinylene-Linked Covalent Organic Frameworks for Confined Catalytic Esterification.

Knoevenagel condensation is a powerful tool for the construction of vinylene-linked covalent organic frameworks. Herein, we established a concise approach to vinylene-linked COFs by Knoevenagel condensation at the multi-methyl groups of a pyridine ring through in situ formation of an N-acyl pyridinium cation in the presence of various acylating reagents. Following this strategy, two vinylene-linked COFs were constructed using 2,4,6-trimethylpyridine and multi-aldehyde-substituted aromatic derivatives as monomers. The resultant COFs are highly crystalline and assembled into hexagonal lattices with specific surface areas as large as 1915 m2 g-1 (vs. 1972 m2 g-1 of the theoretical value). The stable and abundant pyridine-decorated regular nanochannels within the COFs allow for catalyzing the esterification of several pharmaceutical intermediates with distinct spatially confined selectivity and recyclability, representing an environmentally friendly catalytic organic transformation.

Divergent Synthesis of Double Heterohelicenes as Strong Chiral Double Hydrogen-Bonding Donors.

We developed a very efficient and expandable divergent approach initiated by a direct electrophilic borylation at phenyl rings to synthesize a series of double heterohelicenes. Their π-extended structures with pristine zigzag nitrogen (N)-boron (B)-nitrogen (N) edges offer them substantial physical properties and strong double hydrogen-bond donating capability. The isolated (P,P) and (M,M) enantiomers exhibit circularly polarized luminescence in response to hydrogen-bonding interactions.

A book-like organic based electrode with high areal capacity for high performance flexible lithium/sodium-ion batteries.

By directly bonding the monolayer organic based electrodes together to assemble the book-like multilayer electrode, increased areal capacity and high flexibility can be achieved. The electrodes represent 5.88 mA h cm-2 at 0.7C and 5.24 mA h cm-2 at 0.2C areal capacity in lithium-ion and sodium-ion batteries, respectively.

Field-induced slow magnetic relaxation behaviours in binuclear cobalt(II) metallocycles and exchange-coupled clusters.

Precise control of the structures and magnetic properties of a molecular material constitutes an important challenge to realize tailor-made magnetic function. Herein, we report that the ligand-directed coordination self-assembly of a dianionic cobalt(II) mononuclear complex and selective organic linkers has led to two distinct dicobalt(II) complexes, [Co2(pdms)2(bpym)3]·2MeCN (1) and [Co(pdms)(bipm)]2·3DMF (2) (H2pdms = 1,2-bis(methanesulfonamide)benzene; bpym = 2,2'-bipyrimidine; bimp = 1,4-bis[(1H-imidazol-1-yl)methyl]benzene). Structural analyses revealed that complexes 1 and 2 are discrete binuclear molecules containing two neutral {Co(pdms)} species bridged by bpym and bimp ligands, respectively, forming an exchange-coupled CoII2 dimer and a rare CoII2 metallocycle. Magnetic studies found that 1 exhibits considerable antiferromagnetic interactions transferred by the bpym bridge while negligible magnetic interactions in 2 due to the long bimp ligands. Interestingly, both the complexes show significant magnetic anisotropy and thus exhibit slow magnetic relaxation under an external dc field originating from spin-lattice relaxation. Detailed theoretical calculations were further applied to understand the magnetic interactions and magnetic anisotropy in 1 and 2. The foregoing results highlight that coordination solids with programmed structures and magnetic properties can be designed and prepared through a judicious selection of molecular complex building blocks and organic linkers.

[Field greenhouse gas emission characteristics and carbon footprint of ratoon rice]. / 再生稻田温室气体排放特征及碳足迹.

It is of great significance to understand the effects of different rice cultivation methods in southeast China on greenhouse gas emission characteristics and carbon footprint of paddy fields during rice cultivation for rice sustainable production. In this study, the popular conventional rice 'Jiafuzhan' and hybrid rice 'Yongyou 2640' were used as materials to establish four rice cultivation patterns suitable for different ecological types in Fujian Province: 1) double-cropping system, early rice and late rice with Jiafuzhan (D-J); 2) early maturing ratooning system, first season rice and ratooning season rice with Jiafuzhan (R-J); 3) middle-maturing ratooning system, first season rice and ratooning season with Yongyou 2640 (R-Y); and 4) single cropping system with Yongyou 2640 (S-Y), which should be synchronized in heading time with the counterpart (the ratooning season rice). Greenhouse gas emissions from paddy soil were measured by the closed static black box observation method and the gas chromatography method, respectively. The total direct and indirect greenhouse gas emissions (carbon footprints) from different rice farming patterns were evaluated by using the life cycle analysis. The results showed that greenhouse gas emissions in different rice cropping systems were lower in the early growth stage, then decreased after reaching the peak at the booting stage, demonstrating a double peak curve in the whole growth stage, in which the first peak was higher in early season or first season than the second peak in the late season or ratooning season in the cropping patterns. Moreover, the total greenhouse gas emissions were significantly different among cropping systems. The global warming potential (GWP) of different cropping patterns was in order of R-Y>D-J>S-Y>R-J, while the annual greenhouse gas emission intensity (GHGI) was D-J>S-Y>R-Y>R-J. GWP and GHGI of the ratooning system decreased by 26.1% and 14.1%, respectively, compared with those of the double-cropping system. The same pattern was observed in the ratooning rice of Yongyou 2640, which were decreased by 74.3% and 56.7%, respectively, compared with the counterpart, Yongyou 2640 in a single-cropping system synchronized heading. Carbon footprint of rice per unit yield ranged from 0.38-1.08 kg CO2-eq.·kg-1 under the different cropping systems, of which the carbon footprint of rice per unit yield was the highest under the double cropping system compared with that under other cropping systems. The reverse was true in the case of carbon footprint of rice per unit yield under the ratooning system with Yongyou 2640. Additionally, the main source of carbon footprint of different rice cropping patterns was CH4, contributing 44.2%-71.5%, suggesting that rice ratooning system could significantly reduce global warming potential and carbon emission intensity of rice in comparison with other cropping patterns. Therefore, it is key to select rice varieties with high yield and low carbon emission and to establish the supporting scientific cultivation techniques for effective reduction of CH4 emission and carbon footprint of paddy fields and promotion of ratooning rice production.

Calcium Based All-Organic Dual-Ion Batteries with Stable Low Temperature Operability.

In response to the application requirements of secondary batteries at low temperature, an all-organic dual-ion battery with calcium perchlorate contained acetonitrile as the electrolyte (CAN-ODIB) is fabricated in this work. The electrochemical energy is stored in CAN-ODIB via the association and disassociation of calcium and perchlorate ions in perylene diimide-ethylene diamine/carbon black composite based anode and polytriphenylamine based cathode with highly reversible redox states. Benefiting from the energy storage mechanism, CAN-ODIB exhibits excellent electrochemical performances in tests with the temperature ranging from 25 to -50 °C. Especially, CAN-ODIB at -50 °C reserves ≈61% of the capacity at 25 °C (83.4 mA h g-1 ) with the current density of 0.2 A g-1 . CAN-ODIB also shows excellent cycling stability at low temperature by retaining 90.3% of the initial capacity at 1.0 A g-1 after 450 charge-discharge cycles at -30 °C. The impedance analysis of CAN-ODIB at different temperatures indicates that the low temperature performance of CAN-ODIB depends more on the electrode materials than the electrolyte, which provides the important guidance for the further design of secondary batteries operable at low temperatures.

Two types of C-terminal regions of RNA-binding proteins play distinct roles in stress tolerance of Synechocystis sp. PCC 6803.

In the phylogenetic tree of RRM-type Rbps (RNA-binding proteins) in cyanobacteria, Rbp1 of Synechocystis 6803, with a single RRM (RNA recognition motif) region and a C-terminal glycine-rich region, and Rbp2, without the C-terminal region, both belong to the cluster I, whereas Rbp3 with a different type of C-terminal region is in the cluster II. Rbp1 is required for the cold adaptability of the cyanobacterium, and Rbp3 is for salt tolerance. Here, we report that the C-terminal region of Rbp1 is not required for the cold adaptability function but the C-terminal region of Rbp3 can direct the RRM of Rbp1 to the salt tolerance function. Bioinformatic and experimental analyses indicate that Rbps in cyanobacteria should be classified as two types. It is the first report for the distinct roles of C-terminal regions of Rbps in stress tolerance of cyanobacteria.

Synthesis of Vinylene-Linked Covalent Organic Frameworks by Monomer Self-Catalyzed Activation of Knoevenagel Condensation.

Reticular chemistry based on thermodynamically controlled linking modes and numerous organic building blocks has constituted versatile crystalline frameworks in molecular-level precision. However, vinylene-linked covalent organic frameworks (COFs) are still quite far from flexible tailoring in either their structures or topologies, due to the lack of monomers with sufficient activities. Herein, we establish a strategy to synthesize vinylene-linked COFs via Knoevenagel condensation between a tetratopic monomer 2,2',6,6'-tetramethyl-4,4'-bipyridine (TMBP) and linear aromatic dialdehydes in a mixed solvent of benzoic anhydride and benzoic acid. Mechanistic investigation suggests that the condensation was promoted by a pyridine self-catalyzed benzoylation upon the cleavage of benzoic anhydride solvent molecules. The layered structures of the resultant COFs are highly crystallized into orthorhombic lattices with vertically aligned AA stacking modes, delivering high surface areas up to 1560 m2 g-1. The π-extended conjugated skeletons comprising para-bipyridyl units and vinylene linkages endow these COFs with substantial semiconducting properties, releasing visible-light-stimulated catalytic activity in water-splitting hydrogen evolution with a rate as high as 3230 µmol g-1 h-1.

Chromosomal-level genome and multi-omics dataset of Pueraria lobata var. thomsonii provide new insights into legume family and the isoflavone and puerarin biosynthesis pathways.

Pueraria lobata var. thomsonii (hereinafter abbreviated as Podalirius thomsonii), a member of legumes, is one of the important traditional Chinese herbal medicines, and its puerarin extraction is widely used in health and pharmaceutical industry. Here, we assembled a high-quality genome of P. thomsonii using long-read single-molecule sequencing and Hi-C technologies. The genome assembly is approximately 1.37 Gb in size and consists of 5145 contigs with a contig N50 of 593.70 Kb, further clustered into 11 pseudochromosomes. The genome structural annotation resulted in about 869.33 Mb (about 62.70% of the genome) repeat regions and 45 270 protein-coding genes. Genome evolution analysis revealed that P. thomsonii is most closely related to soybean and underwent two ancient whole-genome duplication events, one was in the common ancestor shared by legume species, the other occurred independently at around 7.2 million years ago after its specification. A total of 2373 gene families were found unique in P. thomsonii comparing to five other legume species. Genes and metabolites related to puerarin content in tuberous tissues were characterized. A total of 572 genes upregulated in the puerarin biosynthesis pathway were identified, and 235 candidate genes were further enriched by omics data. Furthermore, we identified 6 8-C-glucosyltransferase (8-C-GT) candidate genes significantly involved in puerarin metabolism. Our study filled in a key genomic gap in legume family, and provided valuable multi-omic resources for the genetic improvement of P. thomsonii.