Role of Protecting Groups in Synthesis and Self-Assembly of Glycopolymers

Protection and deprotection are basic procedures in oligosaccharide synthesis. By taking advantage of the processes of attaching and removing the protecting groups, preparation of oligosaccharides with complex structures can be achieved with relatively high yields. However, the role of protecting groups in solution properties and self-assembly of synthetic glycopolymers has been overlooked in the literature. In this paper, we focused on such effects for well-designed copolymers in which different numbers of benzyl (<b>Bn</b>) groups are installed regioselectively in saccharide rings. Thus, three block copolymers <b>P1</b>, <b>P2</b>, and <b>P3</b> composed of a common block of PNIPAm and a glycopolymer block with trisaccharide triMan side chains differing in the respective number of <b>Bn</b> (0, 2, and 6) were prepared. The solutions of these block copolymers in water were investigated by dynamic and static light scatting and VT-¹H NMR. We found that all of the three copolymers <b>P1</b>, <b>P2</b>, and <b>P3</b> formed association at room temperature. Particularly, <b>P1</b> associated loosely due to carbohydrate-carbohydrate interaction (CCI) while <b>P3</b> formed tight aggregates due to hydrophobic interactions between <b>Bn</b>, and <b>P2</b> behaved between those of <b>P1</b> and <b>P3</b>. Moreover, upon heating, phase transition of PNIPAm block took place leading to micelle formation. Hydrodynamic radius of <b>P1</b> and <b>P2</b> increased significantly as expected, while <b>P3</b> did not follow this trend, because during heating, collapse and accumulation of the PNIPAm chains would occur within the tight aggregates mainly, so it leads to a little change of the size

Balsam-Pear-Skin-Like Porous Polyacrylonitrile Nanofibrous Membranes Grafted with Polyethyleneimine for Postcombustion CO₂ Capture

Amine-containing sorbents have been extensively studied for postcombustion carbon dioxide (CO₂) capture because of their ability to chemisorb CO₂ from the flue gas. However, most sorbents are in the form of powders currently, which is not the ideal configuration for the flue gas separation because of the fragile nature and poor mechanical properties, resulting in blocking of the flow pipes and difficult recycling. Herein, we present a novel approach for the facile fabrication of flexible, robust, and polyethyleneimine-grafted (PEI-grafted) hydrolyzed porous PAN nanofibrous membranes (HPPAN-PEI NFMs) through the combination of electrospinning, pore-forming process, hydrolysis reaction, and the subsequent grafting technique. Excitingly, we find that all the resultant porous PAN (PPAN) fibers exhibit a balsam-pear-skin-like porous structure due to the selective removal of poly­(vinylpyrrolidone) (PVP) from PAN/PVP fibers by water extraction. Significantly, the HPPAN-PEI NFMs retain their mesoporosity, as well as exhibit good thermal stability and prominent tensile strength (11.1 MPa) after grafting, guaranteeing their application in CO₂ trapping from the flue gas. When exposed to CO₂ at 40 °C, the HPPAN-PEI NFMs show an enhanced CO₂ adsorption capacity of 1.23 mmol g^–1 (based on the overall quantity of the sample) or 6.15 mmol g^–1 (based on the quantity of grafted PEI). Moreover, the developed HPPAN-PEI NFMs display significantly selective capture for CO₂ over N₂ and excellent recyclability. The CO₂ capacity retains 92% of the initial value after 20 adsorption–desorption cycle tests, indicating that the resultant HPPAN-PEI NFMs have good long-term stability. This work paves the way for fabricating NFM-based solid adsorption materials endowed with a porous structure applied to efficient postcombustion CO₂ capture

Fe₂O₃/SnSSe Hexagonal Nanoplates as Lithium-Ion Batteries Anode

Novel two-dimensional (2D) Fe₂O₃/SnSSe hexagonal nanoplates were prepared from hot-inject process in oil phase. The resulted hybrid manifests a typical 2D hexagonal nanoplate morphology covered with thin carbon layer. Serving as anode material of lithium-ion battery (LIB), the Fe₂O₃/SnSSe hybrid delivers an outstanding capacity of 919 mAh g^–1 at 100 mA g^–1 and a discharge capacity of 293 mAh g^–1 after 300 cycles at the current density of 5 A g^–1. Compared with pristine SnSSe nanoplates, the Fe₂O₃/SnSSe hybrid exhibits both higher capacity and better stability. The enhanced performance is mainly attributed to the 2D substrate together with the synergistic effects offered by the integration of SnSSe with Fe₂O₃. The 2D Fe₂O₃/SnSSe hybrid can afford highly accessible sites and short ion diffusion length, which facilitate the ion accessibility and improves the charge transport. The novel structure and high performance demonstrated here afford a new way for structural design and the synthesis of chalcogenides as LIB anodes

Glycocalyx-Mimicking Nanoparticles Improve Anti-PD-L1 Cancer Immunotherapy through Reversion of Tumor-Associated Macrophages

Immune checkpoint blockade by anti-PD-L1 monoclonal antibody (αPD-L1) has achieved unprecedented clinical benefits in certain cancers, whereas the therapeutic efficacy is often hindered by immunosuppressive tumor microenvironment mediated by tumor-associated macrophages (TAMs), which leads to innate resistance to this approach. To improve checkpoint blockade efficacy, the amphiphilic diblock copolymers poly­(mannopyranoside/galactopyranoside methacrylate)-<i>block</i>-polystyrene are prepared by RAFT polymerization, which are sequentially self-assembled into glycocalyx-mimicking nanoparticles (GNPs) to neutralize TAMs. It is shown that GNPs can be specifically internalized by TAMs via lectin receptors, which results in upregulation of immunostimulatory IL-12 and downregulation of immunosuppressive IL-10, arginase 1, and CCL22, indicating functional reversion of protumor TAMs toward antitumor phenotype. The reversion of TAMs is proved to be mainly controlled by suppressing STAT6 and activating NF-κB phosphorylation. In vivo therapeutic studies have demonstrated that GNPs significantly enhance the therapeutic efficacy of αPD-L1 cancer therapy by reduction of tumor burden. Moreover, combination therapies with GNPs and αPD-L1 greatly improve immunosuppressive tumor microenvironment by reciprocal modulation of tumor-infiltrating effector and regulatory T cells. Notably, for the first time, our results demonstrate the reversion of TAMs and improvement of αPD-L1 cancer therapy by synthetic carbohydrate-containing nanomaterials. This research highlights a promising strategy for optimizing immune checkpoint blockade in cancer immunotherapy

Image_1_Long-term treatment with Perampanel of Chinese patients with focal-onset seizures, especially in sleep-related epilepsy: a prospective real-world observational study.TIF

BackgroundThere is currently a lack of studies examining the long-term therapeutic effectiveness of the third-generation anti-sezure medication, perampanel (PER), for focal-onset seizures (FOS), particularly in Chinese patients with sleep-related epilepsy (SRE). Additionally, the appropriate dosage, plasma concentration, and the relationship between dose and plasma concentration of PER in Chinese patients are still uncertain.MethodsA prospective, single-center, 24-month observational study was conducted in patients diagnosed with FOS, with a focus on patients with SRE. Changes in seizure frequency from baseline, adverse events, and retention rates were analyzed at 12 and 24 months following the start of the treatment. Tolerability was evaluated based on adverse events and discontinuation profiles. PER plasma concentrations were used to assess dose-concentration-response relationships.ResultsA total of 175 patients were included (median age: 25 years; range: 4–72 years; 53. 1% males and 46.9% females), with the SRE population accounting for 49. 1% (n = 86). The patients diagnosed with SRE showed considerably higher response rates than those who did not have this diagnosis (p = 0.025, odds ratio = 3.8). Additionally, the SRE group adhered better to PER treatment (r = 0.0009). Patients with a shorter duration of epilepsy (median: 3 years; range:2–7 years) demonstrated a more favorable therapeutic response to PER (p = 0.032). Throughout the administration of maintenance doses, among the entire FOS population, the concentration of PER (C0) ranged between 101.5 and 917.4 ng/mL (median, 232.0 ng/mL), and the mean plasma concentration of PER in the responders was 292.8 ng/mL. We revealed a linear relationship between PER dose and plasma concentration, regardless of whether PER was used as monotherapy or add-on therapy. The retention rates were 77.7% and 65. 1% at 12 and 24 months, respectively. Drug-related adverse events occurred in 45.0% of the patients and were mostly manageable.ConclusionPER effectively reduced seizure frequency in Chinese patients with FOS, particularly in those with SRE, over a 24-month period. The treatment was well-tolerated and had a clear linear dose-plasma concentration relationship.</p

Metabolic Remodulation of Chassis and Corn Stover Bioprocessing to Unlock 3‑Hydroxypropionic Acid Biosynthesis from Agrowaste-Derived Substrates

Embracing the principles of sustainable development, the valorization of agrowastes into value-added chemicals has nowadays received significant attention worldwide. Herein, Escherichia coli was metabolically rewired to convert cellulosic hydrolysate of corn stover into a key platform chemical, namely, 3-hydroxypropionic acid (3-HP). First, the heterologous pathways were introduced into E. coli by coexpressing glycerol-3-P dehydrogenase and glycerol-3-P phosphatase in both single and fusion (gpdp12) forms, making the strain capable of synthesizing glycerol from glucose. Subsequently, a glycerol dehydratase (DhaB123-gdrAB) and an aldehyde dehydrogenase (GabD4) were overexpressed to convert glycerol into 3-HP. A fine-tuning between glycerol synthesis and its conversion into 3-HP was successfully established by 5′-untranslated region engineering of gpdp12 and dhaB123-gdrAB. The strain was further metabolically modulated to successfully prevent glycerol flux outside the cell and into the central metabolism. The finally remodulated chassis produced 32.91 g/L 3-HP from the cellulosic hydrolysate of stover during fed-batch fermentation

Formation of Nitrile Hydratase Cross-Linked Enzyme Aggregates in Mesoporous Onion-like Silica: Preparation and Catalytic Properties

Nitrile hydratase cross-linked enzyme aggregates (CLEAs) were formed in mesoporous onion-like silica (NHase-CLEAs@MOS) by using macromolecular dextran polyaldehyde as a cross-linker through the carrier-bound CLEAs method. The effect of preparation parameters on the recovery of enzyme activity was investigated. The properties such as pH, thermal and storage stability, and kinetic parameters of NHase-CLEAs@MOS were also studied. The maximum amount of NHase absorbed in MOS was 535 mg/g. Under optimized conditions, the maximum activity recovery of NHase-CLEAs@MOS was 48.2%. The stabilities of NHase-CLEAs@MOS were improved significantly compared to the NHase@MOS prepared by physical adsorption and free NHase. This work demonstrated that the mesoporous onion-like silica can be efficiently employed as host materials for NHase immobilization, and the carrier-bound CLEAs method can lead to enhanced activity and stability of the immobilized enzymes

Insights into Sexual Precocity of Female Oriental River Prawn <i>Macrobrachium nipponense</i> through Transcriptome Analysis

<div><p>Background</p><p>The oriental river prawn (<i>Macrobrachium nipponense</i>) is the most prevalent aquaculture species in China. The sexual precocity in this species has received considerable attention in recent years because more and more individuals matured at a small size, which devalues the commercial production. In this study, we developed deep-coverage transcriptomic sequencing data for the ovaries of sexually precocious and normal sexually mature <i>M</i>. <i>nipponense</i> using next-generation RNA sequencing technology and attempted to provide the first insight into the molecular regulatory mechanism of sexual precocity in this species.</p><p>Results</p><p>A total of 63,336 unigenes were produced from the ovarian cDNA libraries of sexually precocious and normal sexually mature <i>M</i>. <i>nipponense</i> using Illumina HiSeq 2500 platform. Through BLASTX searches against the NR, STRING, Pfam, Swissprot and KEGG databases, 15,134 unigenes were annotated, accounting for 23.89% of the total unigenes. 5,195 and 3,227 matched unigenes were categorized by GO and COG analysis respectively. 15,908 unigenes were consequently mapped into 332 KEGG pathways, and many reproduction-related pathways and genes were identified. Moreover, 26,008 SSRs were identified from 18,133 unigenes. 80,529 and 80,516 SNPs were yielded from ovarian libraries of sexually precocious and normal sexually mature prawn, respectively, and 29,851 potential SNPs between these two groups were also predicted. After comparing the ovarian libraries of sexually precocious and normal sexually mature prawn, 549 differentially expressed genes (DEGs) and 9 key DEGs that may be related to sexual precocity of <i>M</i>. <i>nipponense</i> were identified. 20 DEGs were selected for validation by quantitative real-time PCR (QPCR) and 19 DEGs show consistent expression between QPCR and RNAseq-based differential expression analysis datasets.</p><p>Conclusion</p><p>This is the first report on the large-scale RNA sequencing of ovaries of sexually precocious and normal sexually mature <i>M</i>. <i>nipponense</i>. The annotated transcriptome data will provide fundamental support for future research into the reproduction biology of <i>M</i>. <i>nipponense</i>. The large number of candidate SNPs and SSRs detected in this study could be used as genetic markers for population genetics and functional genomics in this species. More importantly, many DEGs, especially nine key DEGs between sexually precocious and normal sexually mature prawns were identified, which will dramatically improve understanding of molecular regulatory mechanism of sexual precocity of this species.</p></div

Image_2_Long-term treatment with Perampanel of Chinese patients with focal-onset seizures, especially in sleep-related epilepsy: a prospective real-world observational study.TIF

BackgroundThere is currently a lack of studies examining the long-term therapeutic effectiveness of the third-generation anti-sezure medication, perampanel (PER), for focal-onset seizures (FOS), particularly in Chinese patients with sleep-related epilepsy (SRE). Additionally, the appropriate dosage, plasma concentration, and the relationship between dose and plasma concentration of PER in Chinese patients are still uncertain.MethodsA prospective, single-center, 24-month observational study was conducted in patients diagnosed with FOS, with a focus on patients with SRE. Changes in seizure frequency from baseline, adverse events, and retention rates were analyzed at 12 and 24 months following the start of the treatment. Tolerability was evaluated based on adverse events and discontinuation profiles. PER plasma concentrations were used to assess dose-concentration-response relationships.ResultsA total of 175 patients were included (median age: 25 years; range: 4–72 years; 53. 1% males and 46.9% females), with the SRE population accounting for 49. 1% (n = 86). The patients diagnosed with SRE showed considerably higher response rates than those who did not have this diagnosis (p = 0.025, odds ratio = 3.8). Additionally, the SRE group adhered better to PER treatment (r = 0.0009). Patients with a shorter duration of epilepsy (median: 3 years; range:2–7 years) demonstrated a more favorable therapeutic response to PER (p = 0.032). Throughout the administration of maintenance doses, among the entire FOS population, the concentration of PER (C0) ranged between 101.5 and 917.4 ng/mL (median, 232.0 ng/mL), and the mean plasma concentration of PER in the responders was 292.8 ng/mL. We revealed a linear relationship between PER dose and plasma concentration, regardless of whether PER was used as monotherapy or add-on therapy. The retention rates were 77.7% and 65. 1% at 12 and 24 months, respectively. Drug-related adverse events occurred in 45.0% of the patients and were mostly manageable.ConclusionPER effectively reduced seizure frequency in Chinese patients with FOS, particularly in those with SRE, over a 24-month period. The treatment was well-tolerated and had a clear linear dose-plasma concentration relationship.</p

Statistics of SNP types and positions in the transcriptomes of MNOP when all sequences generated from the MNON transcriptome library were employed as reference sequences.

<p>Statistics of SNP types and positions in the transcriptomes of MNOP when all sequences generated from the MNON transcriptome library were employed as reference sequences.</p