Polypeptide organic radical batteries.

In only a few decades, lithium-ion batteries have revolutionized technologies, enabling the proliferation of portable devices and electric vehicles1, with substantial benefits for society. However, the rapid growth in technology has highlighted the ethical and environmental challenges of mining lithium, cobalt and other mineral ore resources, and the issues associated with the safe usage and non-hazardous disposal of batteries2. Only a small fraction of lithium-ion batteries are recycled, further exacerbating global material supply of strategic elements3-5. A potential alternative is to use organic-based redox-active materials6-8 to develop rechargeable batteries that originate from ethically sourced, sustainable materials and enable on-demand deconstruction and reconstruction. Making such batteries is challenging because the active materials must be stable during operation but degradable at end of life. Further, the degradation products should be either environmentally benign or recyclable for reconstruction into a new battery. Here we demonstrate a metal-free, polypeptide-based battery, in which viologens and nitroxide radicals are incorporated as redox-active groups along polypeptide backbones to function as anode and cathode materials, respectively. These redox-active polypeptides perform as active materials that are stable during battery operation and subsequently degrade on demand in acidic conditions to generate amino acids, other building blocks and degradation products. Such a polypeptide-based battery is a first step to addressing the need for alternative chemistries for green and sustainable batteries in a future circular economy.

Cell wall invertase 3 plays critical roles in providing sugars during pollination and fertilization in cucumber.

In plants, pollen-pistil interactions during pollination and fertilization mediate pollen hydration and germination, pollen tube growth, and seed set and development. Cell wall invertases (CWINs) help provide the carbohydrates for pollen development; however, their roles in pollination and fertilization have not been well established. In cucumber (Cucumis sativus), CsCWIN3 showed the highest expression in flowers, and we further examined CsCWIN3 for functions during pollination to seed set. Both CsCWIN3 transcript and CsCWIN3 protein exhibited similar expression patterns in the sepals, petals, stamen filaments, anther tapetum, and pollen of male flowers, as well as in the stigma, style, transmitting tract, and ovule funiculus of female flowers. Notably, repression of CsCWIN3 in cucumber did not affect the formation of parthenocarpic fruit but resulted in an arrested growth of stigma integuments in female flowers and a partially delayed dehiscence of anthers with decreased pollen viability in male flowers. Consequently, the pollen tube grew poorly in the gynoecia after pollination. In addition, CsCWIN3-RNA interference plants also showed affected seed development. Considering that sugar transporters could function in cucumber fecundity, we highlight the role of CsCWIN3 and a potential close collaboration between CWIN and sugar transporters in these processes. Overall, we used molecular and physiological analyses to determine the CsCWIN3-mediated metabolism during pollen formation, pollen tube growth, and plant fecundity. CsCWIN3 has essential roles from pollination and fertilization to seed set but not parthenocarpic fruit development in cucumber.

Interactive effects of dietary leucine and isoleucine affect amino acid profile and metabolism through AKT/TOR signaling pathways in blunt snout bream (Megalobrama amblycephala).

The purpose of this research is to explore the interaction between dietary leucine and isoleucine levels on whole-body composition, plasma and liver biochemical indexes, amino acids deposition in the liver, and amino acid metabolism of blunt snout bream (Megalobrama amblycephala). The test fish (average weight: 56.00 ± 0.55 g) were fed one of six diets at random containing two leucine levels (1.70% and 2.50%) and three isoleucine levels (1.00%, 1.20%, and 1.40%) for 8 weeks. The results showed that the final weight and weight gain rate were the highest in the fish fed low-level leucine and high-level isoleucine diets (P > 0.05). Furthermore, the crude lipid content was significantly adjusted by diets with diverse levels of leucine and isoleucine (P < 0.05). In addition, interactive effects of these two branched-chain amino acids (BCAAs) were found on plasma total protein, blood ammonia, and blood urea nitrogen of test fish (P < 0.05). Additionally, the liver amino acid profiles were significantly influenced by the interactive effects of the two BCAAs (P < 0.05). Moreover, interactive effects of dietary leucine and isoleucine were significantly observed in the expressions of amino acid metabolism-related genes (P < 0.05). These findings suggested that dietary leucine and isoleucine had interaction. Meanwhile, the interaction between them was more conducive to the growth and quality improvement of blunt snout bream when the dietary leucine level was 1.70% and isoleucine level was 1.40%.

Phloem loading in cucumber: combined symplastic and apoplastic strategies.

Phloem loading, as the first step of transporting photoassimilates from mesophyll cells to sieve element-companion cell complex, creates a driving force for long-distance nutrient transport. Three loading strategies have been proposed: passive symplastic loading, apoplastic loading and symplastic transfer followed by polymer-trapping of stachyose and raffinose. Although individual species are generally referred to as using a single phloem loading mechanism, it has been suggested that some plants may use more than one, i.e. 'mixed loading'. Here, by using a combination of electron microscopy, reverse genetics and 14 C labeling, loading strategies were studied in cucumber, a polymer-trapping loading species. The results indicate that intermediary cells (ICs), which mediate polymer-trapping, and ordinary companion cells, which mediate apoplastic loading, were mainly found in the fifth and third order veins, respectively. Accordingly, a cucumber galactinol synthase gene (CsGolS1) and a sucrose transporter gene (CsSUT2) were expressed mainly in the fifth/third and the third order veins, respectively. Immunolocalization analysis indicated that CsGolS1 was localized in companion cells (CCs) while CsSUT2 was in CCs and sieve elements (SEs). Suppressing CsGolS1 significantly decreased the stachyose level and increased sucrose content, while suppressing CsSUT2 decreased the sucrose level and increased the stachyose content in leaves. After 14 CO2 labeling, [14 C]sucrose export increased and [14 C]stachyose export reduced from petioles in CsGolS1i plants, but [14 C]sucrose export decreased and [14 C]stachyose export increased into petioles in CsSUT2i plants. Similar results were also observed after pre-treating the CsGolS1i leaves with PCMBS (transporter inhibitor). These results demonstrate that cucumber phloem loading depends on both polymer-trapping and apoplastic loading strategies.

Down-regulation of the Sucrose Transporter CsSUT1 Causes Male Sterility by Altering Carbohydrate Supply.

In plants, male sterility is an important agronomic trait, especially in hybrid crop production. Many factors are known to affect crop male sterility, but it remains unclear whether Suc transporters (SUTs) participate directly in this process. Here, we identified and functionally characterized the cucumber (Cucumis sativus) CsSUT1, a typical plasma membrane-localized energy-dependent high-affinity Suc-H+ symporter. CsSUT1 is expressed in male flowers and encodes a protein that is localized primarily in the tapetum, pollen, and companion cells of the phloem of sepals, petals, filaments, and pedicel. The male flowers of CsSUT1-RNA interference (RNAi) lines exhibited a decrease in Suc, hexose, and starch content, relative to those of the wild type, during the later stages of male flower development, a finding that was highly associated with male sterility. Transcriptomic analysis revealed that numerous genes associated with sugar metabolism, transport, and signaling, as well as with auxin signaling, were down-regulated, whereas most myeloblastosis (MYB) transcription factor genes were up-regulated in these CsSUT1-RNAi lines relative to wild type. Our findings demonstrate that male sterility can be induced by RNAi-mediated down-regulation of CsSUT1 expression, through the resultant perturbation in carbohydrate delivery and subsequent alteration in sugar and hormone signaling and up-regulation of specific MYB transcription factors. This knowledge provides a new approach for bioengineering male sterility in crop plants.

In Situ Production of Ag/Polymer Asymmetric Nanoparticles via a Powerful Light-Driven Technique.

As a rapid, controllable, and easily transferrable approach to the preparation of antimicrobial nanoparticle systems, a one-step, light-driven procedure was developed to produce asymmetric hybrid inorganic-organic nanoparticles (NPs) directly from a homogeneous Ag/polymer mixture. An amphiphilic triblock polymer was designed and synthesized to build biocompatible NPs, consisting of poly(ethylene oxide) (PEO), carboxylic acid-functionalized polyphosphoester (PPE), and poly(l-lactide) (PLLA). Unexpectedly, snowman-like asymmetric nanostructures were subsequently obtained by simply loading silver cations into the polymeric micelles together with purification via centrifugation. With an understanding of the chemistry of the asymmetric NP formation, a controllable preparation strategy was developed by applying UV irradiation. A morphology transition was observed by transmission electron microscopy over the UV irradiation time, from small silver NPs distributed inside the micelles into snowman-like asymmetric NPs, which hold promise for potential antimicrobial applications with their unique two-stage silver release profiles.

Down-Regulating Cucumber Sucrose Synthase 4 (CsSUS4) Suppresses the Growth and Development of Flowers and Fruits.

Sucrose synthase (SUS), which catalyzes the reversible conversion of sucrose and uridine diphosphate (UDP) into fructose and UDP-glucose, is a key enzyme in sucrose metabolism in higher plants. In this study, we used reverse genetic approaches and carbohydrate analysis to investigate the role of cucumber sucrose synthase gene 4 (CsSUS4) in the growth and development of sink organs. Transcript analyses showed that CsSUS4 was predominantly expressed in sink organs, particularly in flowers, fruits and roots, and that CsSUS4 protein was localized to companion cells and phloem parenchyma cells. Down-regulation of CsSUS4 expression resulted in a decrease in SUS activity in conjunction with lower hexose, starch and cellulose contents in fruits, and led to an overall reduction in the size and weight of flowers and fruits. Furthermore, CsSUS4 overexpression (OE) lines exhibited increased carbohydrate content, and larger and heavier flowers and fruits. The numbers of multi-petal flowers and multi-carpel fruits were greater in CsSUS4-OE plants compared with wild type and were regulated by MADS-box transcription factor. These results demonstrate that CsSUS4 plays important roles in the growth and development of cucumber flowers and fruits.

Transcriptional evidence for cross talk between JA and ET or SA during root-knot nematode invasion in tomato.

studies have demonstrated that jasmonic acid (JA) reduces root-knot nematode (RKN) infections in tomato plants. RKN invasion is sensed by roots, and root-derived JA signaling activates systemic defense responses, though this is poorly understood. Here, we investigate variations in the RKN-induced transcriptome in scion phloem between two tomato plant grafts: CM/CM ( Lycopersicum esculentum Mill. cv. Castlemart) and CM/ spr2 (a JA-deficient mutant). A total of 8,716 genes were differentially expressed in the scion phloem of the plants with JA-deficient rootstock via RNA sequencing. Among these genes, 535 upregulated and 153 downregulated genes with high copy numbers were identified as significantly differentially expressed. Among them, 34 predicted transcription factor genes were identified. Additionally, we used real-time quantitative PCR to analyze the expression patterns of 42 genes involved in the JA, ethylene, or salicylic acid pathway in phloem under RKN infection. The results suggested that in the absence of JA signaling, the ET signaling pathway is enhanced after RKN infection; however, alterations in the SA signaling pathway were not observed.

Chemical Design of Both a Glutathione-Sensitive Dimeric Drug Guest and a Glucose-Derived Nanocarrier Host to Achieve Enhanced Osteosarcoma Lung Metastatic Anticancer Selectivity.

Although nanomedicines have been pursued for nearly 20 years, fundamental chemical strategies that seek to optimize both the drug and drug carrier together in a concerted effort remain uncommon yet may be powerful. In this work, two block polymers and one dimeric prodrug molecule were designed to be coassembled into degradable, functional nanocarriers, where the chemistry of each component was defined to accomplish important tasks. The result is a poly(ethylene glycol) (PEG)-protected redox-responsive dimeric paclitaxel (diPTX)-loaded cationic poly(d-glucose carbonate) micelle (diPTX@CPGC). These nanostructures showed tunable sizes and surface charges and displayed controlled PTX drug release profiles in the presence of reducing agents, such as glutathione (GSH) and dithiothreitol (DTT), thereby resulting in significant selectivity for killing cancer cells over healthy cells. Compared to free PTX and diPTX, diPTX@CPGC exhibited improved tumor penetration and significant inhibition of tumor cell growth toward osteosarcoma (OS) lung metastases with minimal side effects both in vitro and in vivo, indicating the promise of diPTX@CPGC as optimized anticancer therapeutic agents for treatment of OS lung metastases.

Vacuum induced transparency in metamaterials.

For the cavity-based electromagnetically induced transparent (EIT), as the coherent driving field is enhanced by the optical cavity, the weak probe field can propagate through the atomic ensemble without absorption even if the driving field is weak. The extreme case of vacuum in the cavity is called "vacuum-induced transparency" (VIT) to distinguish it from the cavity EIT. Here we construct a new kind of cavity made of Metamaterials, i.e. ε-negative (EN) and µ-negative (MN) slabs, and study the VIT phenomena of the atomic ensemble doped within it. When the impedances of the MN and EN slabs are matched to each other and the dissipation of the material is small, it behaves as a surface plasmon cavity with a huge Q factor. And the VIT phenomenon in this cavity appears. By adjusting the position of atoms, the coupling strength between the atom and the structure could be changed. Two kinds of extremes of VIT, the coherent population trapping (CPT) and the Autler-Townes splitting (ATS), can be achieved in this system easily. Our proposal could be used in the realization of ultra-strong coupling and integrated devices on quantum memory or optical switch.

Controllable single-photon nonreciprocal propagation between two waveguides chirally coupled to a quantum emitter.

We investigate coherent controlling single-photon nonreciprocal propagation in a pair of waveguides chirally coupled to an atom by using a classical optical field. The results show that for a nonresonant photon, the perfect single-photon nonreciprocal propagation can be realized by adjusting the Rabi frequency and detuning. Furthermore, the nonreciprocal propagation is switchable by using the classic field. The calculated results also show that the system can be used as a frequency filter to filter out some special frequencies for single-photon nonreciprocal propagation. The influences of nonperfect chiral coupling and dissipations on the nonreciprocal propagation are also shown.

Multi-responsive polypeptide hydrogels derived from N-carboxyanhydride terpolymerizations for delivery of nonsteroidal anti-inflammatory drugs.

A polypeptide-based hydrogel system, when prepared from a diblock polymer with a ternary copolypeptide as one block, exhibited thermo-, mechano- and enzyme-responsive properties, which enabled the encapsulation of naproxen (Npx) during the sol-gel transition and its release in the gel state. Statistical terpolymerizations of l-alanine (Ala), glycine (Gly) and l-isoleucine (Ile) NCAs at a 1 : 1 : 1 feed ratio initiated by monomethoxy monoamino-terminated poly(ethylene glycol) afforded a series of methoxy poly(ethylene glycol)-block-poly(l-alanine-co-glycine-co-l-isoleucine) (mPEG-b-P(A-G-I)) block polymers. ß-Sheets were the dominant secondary structures within the polypeptide segments, which facilitated a heat-induced sol-to-gel transition, resulting from the supramolecular assembly of ß-sheets into nanofibrils. Deconstruction of the three-dimensional networks by mechanical force (sonication) triggered the reverse gel-to-sol transition. Certain enzymes could accelerate the breakdown of the hydrogel, as determined by in vitro gel weight loss profiles. The hydrogels were able to encapsulate and release Npx over 6 days, demonstrating the potential application of these polypeptide hydrogels as an injectable local delivery system for small molecule drugs.

Improving paclitaxel delivery: in vitro and in vivo characterization of PEGylated polyphosphoester-based nanocarriers.

Nanomaterials have great potential to offer effective treatment against devastating diseases by providing sustained release of high concentrations of therapeutic agents locally, especially when the route of administration allows for direct access to the diseased tissues. Biodegradable polyphosphoester-based polymeric micelles and shell cross-linked knedel-like nanoparticles (SCKs) have been designed from amphiphilic block-graft terpolymers, PEBP-b-PBYP-g-PEG, which effectively incorporate high concentrations of paclitaxel (PTX). Well-dispersed nanoparticles physically loaded with PTX were prepared, exhibiting desirable physiochemical characteristics. Encapsulation of 10 wt% PTX, into either micelles or SCKs, allowed for aqueous suspension of PTX at concentrations up to 4.8 mg/mL, as compared to <2.0 µg/mL for the aqueous solubility of the drug alone. Drug release studies indicated that PTX released from these nanostructures was defined through a structure-function relationship, whereby the half-life of sustained PTX release was doubled through cross-linking of the micellar structure to form SCKs. In vitro, physically loaded micellar and SCK nanotherapeutics demonstrated IC50 values against osteosarcoma cell lines, known to metastasize to the lungs (CCH-OS-O and SJSA), similar to the pharmaceutical Taxol formulation. Evaluation of these materials in vivo has provided an understanding of the effects of nanoparticle structure-function relationships on intratracheal delivery and related biodistribution and pharmacokinetics. Overall, we have demonstrated the potential of these novel nanotherapeutics toward future sustained release treatments via administration directly to the sites of lung metastases of osteosarcoma.

Identification of jasmonic acid-associated microRNAs and characterization of the regulatory roles of the miR319/TCP4 module under root-knot nematode stress in tomato.

MicroRNAs (miRNAs) are important transcriptional and post-transcriptional modulators of gene expression that play crucial roles in the responses to diverse stresses. To explore jasmonic acid (JA)-dependent miRNA-mediated regulatory networks that are responsive to root-knot nematode (RKN), two small RNA libraries were constructed from wild-type (WT) and JA mutant (spr2) plants. A total of 263 known miRNAs and 441 novel miRNAs were significantly regulated under RKN stress in the two libraries. The spatio-temporal expression of candidate miRNAs and their corresponding targets were analysed by qRT-PCR under RKN stress. A clear negative correlation was observed between miR319 and its target TEOSINTE BRANCHED1/CYCLOIDEA/PRO-LIFERATING CELL FACTOR 4 (TCP4) in leaf, stem, and root under RKN stress, implying that the miR319/TCP4 module is involved in the systemic defensive response. Reverse genetics demonstrated that the miR319/TCP4 module affected JA synthetic genes and the endogenous JA level in leaves, thereby mediating RKN resistance. These results suggested that the action of miR319 in serving as a systemic signal responder and regulator that modulated the RKN systemic defensive response was mediated via JA. The potential cross-talk between miR319/TCP4 and miR396/GRF (GROWTH RESPONDING FACTOR) in roots under RKN invasion is discussed, and a predictive model regarding miR319/TCP4-mediated RKN resistance is proposed.

Construction of Versatile and Functional Nanostructures Derived from CO2 -based Polycarbonates.

The construction of amphiphilic polycarbonates through epoxides/CO2 coupling is a challenging aim to provide more diverse CO2 -based functional materials. In this report, we demonstrate the facile preparation of diverse and functional nanoparticles derived from a CO2 -based triblock polycarbonate system. By the judicious use of water as chain-transfer reagent in the propylene oxide/CO2 polymerization, poly(propylene carbonate (PPC) diols are successfully produced and serve as macroinitiators in the subsequent allyl glycidyl ether/CO2 coupling reaction. The resulting ABA triblock polycarbonate can be further functionalized with various thiols by radical mediated thiol-ene click chemistry, followed by self-assembly in deionized water to construct a versatile and functional nanostructure system. This class of amphiphilic polycarbonates could embody a powerful platform for biomedical applications.

Supramolecularly knitted tethered oligopeptide/single-walled carbon nanotube organogels.

A facile polymerization of an allyl-functionalized N-carboxyanhydride (NCA) monomer is utilized to construct an A-B-A-type triblock structure containing ß-sheet-rich oligomeric peptide segments tethered by a poly(ethylene oxide) chain, which are capable of dispersing and gelating single-walled carbon nanotubes (SWCNTs) noncovalently in organic solvents, resulting in significant enhancement of the mechanical properties of polypeptide-based organogels.

Characteristics of nitrous oxide emissions and the affecting factors from vegetable fields on the North China Plain.

Nitrous oxide (N2O) is one of the most important greenhouse gases emitted from fertilized agricultural soils. Vegetable fields, mostly managed under intensive mode with higher rate nitrogen application, frequent irrigation, and multiple planting-harvest cycles, does contribute to national GHG inventory greatly due to the increasing planting area in China. N2O emissions from four different fields - a maize field (maize), a newly established open-ground vegetable field converted from a maize field four years earlier (OV4), an established open-ground vegetable field converted from a maize field more than 20 years ago (OV20), and an established sunlight heated greenhouse vegetable field converted from a maize field more than 20 years ago (GV20) with four different fertilization treatments for the OV4 field were measured using the closed chamber method between March 15th, 2012 and March 14th, 2013 in suburban area of Beijing, North China Plain. Results showed that the annual N2O emissions from vegetable fields were 3.1-4.6 times higher than the typical maize field. All the N2O emission peaks were occurred after fertilization and the fertilization associated emissions accounted for 81.1% (ranging from 77.0% to 87.2%) of the annual N2O emission with 22.2% time duration in the whole year for vegetable fields. Both the occurrence data and duration of N2O emission peaks were associated with N input type (chemical or manure) and the application rate. The N2O emission peaks appeared earlier (on the 3rd day after application) and lasted shorter when only chemical N was applied; while they appeared later (on the 7th to 10th day after application) and lasted longer when the combination of manure and chemical N were applied. The magnitudes of N2O emission peaks increased when the N application rate was higher. Dicyandiamide (DCD) decreased N2O emissions by 30.1% and 21.1% in the spring cucumber and autumn cabbage seasons respectively (averaged of 24.7% over the whole year). Calculations showed that it is critical to estimate the emission factor (EF) by N type in order to decrease the uncertainty of regional N2O emissions when using EF as calculation method. EFs were 0.20% and 0.42% for manure N in the cucumber and cabbage seasons respectively; and were 0.55-1.30% and 0.8-1.59% for chemical N in the cucumber and cabbage seasons respectively.

Responsive organogels formed by supramolecular self assembly of PEG-block-allyl-functionalized racemic polypeptides into ß-sheet-driven polymeric ribbons.

A chemically reactive hybrid diblock polypeptide gelator poly(ethylene glycol)-block-poly(dl-allylglycine) (PEG-b-PDLAG) is an exceptional material, due to the characteristics of thermo-reversible organogel formation driven by the combination of a hydrophilic polymer chain linked to a racemic oligomeric homopeptide segment in a range of organic solvents. One-dimensional stacking of the block copolymers is demonstrated by ATR-FTIR spectroscopy, wide-angle X-ray scattering to be driven by the supramolecular assembly of ß-sheets in peptide blocks to afford well-defined fiber-like structures, resulting in gelation. These supramolecular interactions are sufficiently strong to achieve ultra low critical gelation concentrations (ca. 0.1 wt%) in N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and methanol. The critical gel transition temperature was directly proportional to the polymer concentration, so that at low concentrations, thermoreversibility of gelation was observed. Dynamic mechanical analysis studies were employed to determine the organogel mechanical properties, having storage moduli of ca. 15.1 kPa at room temperature.

A two-stage intrusion detection method based on light gradient boosting machine and autoencoder.

Intrusion detection systems can detect potential attacks and raise alerts on time. However, dimensionality curses and zero-day attacks pose challenges to intrusion detection systems. From a data perspective, the dimensionality curse leads to the low efficiency of intrusion detection systems. From the attack perspective, the increasing number of zero-day attacks overwhelms the intrusion detection system. To address these problems, this paper proposes a novel detection framework based on light gradient boosting machine (LightGBM) and autoencoder. The recursive feature elimination (RFE) method is first used for dimensionality reduction in this framework. Then a focal loss (FL) function is introduced into the LightGBM classifier to boost the learning of difficult samples. Finally, a two-stage prediction step with LightGBM and autoencoder is performed. In the first stage, pre-decision is conducted with LightGBM. In the second stage, a residual is used to make a secondary decision for samples with a normal class. The experiments were performed on the NSL-KDD and UNSWNB15 datasets, and compared with the classical method. It was found that the proposed method is superior to other methods and reduces the time overhead. In addition, the existing advanced methods were also compared in this study, and the results show that the proposed method is above 90% for accuracy, recall, and F1 score on both datasets. It is further concluded that our method is valid when compared with other advanced techniques.