Simultaneous determination of trace marine lipophilic and hydrophilic phycotoxins in various environmental and biota matrices.

An efficient and sensitivity approach, which combines solid-phase extraction or ultrasonic extraction for pretreatment, followed by ultra-performance liquid chromatography-tandem mass spectrometry, has been established to simultaneously determine eight lipophilic phycotoxins and one hydrophilic phycotoxin in seawater, sediment and biota samples. The recoveries and matrix effects of target analytes were in the range of 61.6-117.3 %, 55.7-121.3 %, 57.5-139.9 % and 82.6 %-95.0 %, 85.8-106.8 %, 80.7 %-103.3 % in seawater, sediment, and biota samples, respectively. This established method revealed that seven, six and six phycotoxins were respectively detected in the Beibu Gulf, with concentrations ranging from 0.14 ng/L (okadaic acid, OA) to 26.83 ng/L (domoic acid, DA) in seawater, 0.04 ng/g (gymnodimine-A, GYM-A) to 2.75 ng/g (DA) in sediment and 0.01 ng/g (GYM-A) to 2.64 ng/g (domoic acid) in biota samples. These results suggest that the presented method is applicable for the simultaneous determination of trace marine lipophilic and hydrophilic phycotoxins in real samples.

Interfacial Engineering of MoS2@CoS2 Heterostructure Electrocatalysts for Effective pH-Universal Hydrogen Evolution Reaction.

The practical utilization of the hydrogen evolution reaction (HER) necessitates the creation of electrocatalysts that are both efficient and abundant in earth elements, capable of operating effectively within a wide pH range. However, this objective continues to present itself as an arduous obstacle. In this research, we propose the incorporation of sulfur vacancies in a novel heterojunction formed by MoS2@CoS2, designed to exhibit remarkable catalytic performances. This efficacy is attributed to the advantageous combination of the low work function and space charge zone at the interface between MoS2 and CoS2 in the heterojunction. The MoS2@CoS2 heterojunction manifests outstanding hydrogen evolution activity over an extensive pH range. Remarkably, achieving a current density of 10 mA cm-2 in aqueous solutions 1.0 M KOH, 0.5 M H2SO4, and 1.0 M phosphate-buffered saline (PBS), respectively, requires only an overpotential of 48, 62, and 164 mV. The Tafel slopes for each case are 43, 32, and 62 mV dec-1, respectively. In this study, the synergistic effect of MoS2 and CoS2 is conducive to electron transfer, making the MoS2@CoS2 heterojunction show excellent electrocatalytic performance. The synergistic effects arising from the heterojunction and sulfur vacancy not only contribute to the observed catalytic prowess but also provide a valuable model and reference for the exploration of other efficient electrocatalysts. This research marks a significant stride toward overcoming the challenges associated with developing electrocatalysts for practical hydrogen evolution applications.

The ratio of skeletal muscle mass to body mass index combined with inflammatory immune markers to stratify survival of pancreatic cancer after pancreatoduodenectomy.

BACKGROUND: We sought to combine skeletal muscle index and inflammatory immune markers to stratify long-term survival in patients with pancreatic cancer after pancreatoduodenectomy (PD). METHODS: A total of 581 patients with pancreatic cancer underwent PD were included, and divided into the training and validation cohort. Image analysis of computed tomography scans was used to calculate the ratio of skeletal muscle (SM) area to body mass index (BMI). Naples prognostic score (NPS) was calculated from blood-test inflammatory immune markers. Propensity score matching (PSM) analysis was performed to minimize biases of clinicopathological characteristics. To estimate the overall survival (OS), a nomogram was developed using the training cohort. The predictive accuracy of nomogram was estimated by concordance index (C-index), calibration curve, and receiver operating characteristics (ROC) curve. RESULTS: After PSM analysis, SM/BMI ratio, NPS, lymph node metastasis, TNM stage, surgical margin, tumor grade and adjuvant therapy were independent predictors of OS, which were all assembled into nomogram. The SM/BMI ratio was the best single-predictor for 3- and 5-year OS, with an AUC of 0.805 (95% CI: 0.755-0.855) and 0.812 (95% CI: 0.736-0.888), respectively. Harrell's c-index of the nomogram in the training cohort was 0.786 (95% CI: 0.770-0.802), and the area under ROC curve of 1-year, 3- and 5-year OS prediction were 0.869 (95%CI: 0.837-0.901), 0.846 (95%CI: 0.810-0.882) and 0.849 (95%CI: 0.801-0.896). CONCLUSIONS: The nomogram based on SM/BMI ratio and NPS had excellent predictive performance, which should be incorporated to conventional risk scores to stratify survival of patients with PDAC after PD.

Immunotherapy for patients with advanced non-small cell lung cancer harboring oncogenic driver alterations other than EGFR: a multicenter real-world analysis.

Background: The administration of immune checkpoint inhibitors (ICIs) in advanced non-small cell lung cancer (NSCLC) with oncogenic driver alterations other than epidermal growth factor receptor (EGFR) aroused a heated discussion. We thus aimed to evaluate ICI treatment in these patients in real-world routine clinical practice. Methods: A multicenter, retrospective study was conducted for NSCLC patients with at least one gene alteration (KRAS, HER2, BRAF, MET, RET, ALK, ROS1) receiving ICI monotherapy or combination treatment. The data regarding clinicopathologic characteristics, clinical efficacy, and safety were investigated. Results: A total of 216 patients were included, the median age was 60 years, 72.7% of patients were male, and 46.8% had a smoking history. The molecular alterations involved KRAS (n=95), HER2 (n=42), BRAF (n=22), MET (n=21), RET (n=14), ALK (n=14), and ROS1 (n=8); 56.5% of patients received immunotherapy in the first-line, and the rest 43.5% were treated as a second-line and above. For the entire cohort who received immunotherapy-based regimens in the first-line, the median progression-free survival (PFS) was 7.5 months and the median overall survival (OS) was 24.8 months. For the entire cohort who received immunotherapy-based regimens in the second-line and above, the median PFS was 4.7 months and median OS was 17.1 months. KRAS mutated NSCLC treated with immunotherapy-based regimens in the first-line setting had a median PFS and OS were 7.8 and 26.1 months, respectively. Moreover, the median PFS and OS of immunotherapy-based regimens for KRAS-mutant NSCLC that progressed after chemotherapy were 5.9 and 17.1 months. Programmed death ligand 1 (PD-L1) expression level was not consistently associated with response to immunotherapy across different gene alteration subsets. In the KRAS group, PD-L1 positivity [tumor proportion score (TPS) ≥1%] was associated with better PFS and OS according to the multivariate Cox analysis. No statistically significant association was found for smoking status, age, or gender with clinical efficacy in any gene group analyses. Conclusions: KRAS-mutant NSCLC could obtain clinical benefits from ICIs either for treatment-naive patients or those who have experienced progression after chemotherapy, and PD-L1 positive expression (TPS >1%) may be a potential positive predictor. For NSCLC with ALK, RET and ROS1 rearrangement, MET exon 14 skipping mutation, or BRAF V600E mutation, effectiveness of single or combined ICI therapy remains limited, therefore, targeted therapies should be considered prior to immunotherapy regimens. Future studies should address the investigation of better predictive biomarkers for immunotherapy response in oncogene-driven NSCLC.

Theoretical calculations and experimental verification of carbon dioxide reduction electrocatalyzed by metalloporphyrin.

Metal-functionalized porphyrin-like graphene structures are promising electrocatalysts for carbon dioxide reduction reaction (CO2RR) as their metal centers can modulate activity. Yet, the role of metal center of metalloporphyrins (MTPPs) in CO2 reaction activity is still lacking deep understanding. Here, CO2RR mechanism on MTPPs with five different metal centers (M = Fe, Co, Cu, Zn and Ni) are examined by first-principles calculations. The *COOH formation is the rate determined step on the five MTPP structures, and the CoTPP exhibits the best CO2RR activity while ZnTPP and NiTPP are the worst, which is also verified by our experiment. The CO2RR activity is controlled by adsorption states of intermediates (*CO, *COOH), i.e., chemisorption (e.g., on CoTPP) and physisorption (on ZnTPP and NiTPP) of intermediates will lead to good and poor activity, respectively. The deeper the d-band center of the porphyrin ring complexed metal atom, the weaker bonding of MTPP with CO and COOH. Theoretical calculations and experimental results indicate that MTPPs with Co and Fe centers lead to a reduction in the energy barriers for the two uphill reaction steps in the electrocatalytic CO2 reduction process, thereby enhancing CO2 reduction electrocatalytic activity. Faradaic efficiency of CO is correlated with the reaction energy barrier of the first proton-coupled electron reduction process, displaying a strong linear correlation. This work provides a fundamental understanding of MTPPs used as electrocatalysts for CO2RR.

3D Printed Room Temperature Phosphorescence Materials Enabled by Edible Natural Konjac Glucomannan.

Shaping room temperature phosphorescence (RTP) materials into 3D bodies is important for stereoscopic optoelectronic displays but remains challenging due to their poor processability and mechanical properties. Here, konjac glucomannan (KGM) is employed to anchor arylboronic acids with various π conjugations via a facile B─O covalent reaction to afford printable inks, using which full-color high-fidelity 3D RTP objects with high mechanical strength can be obtained via direct ink writing-based 3D printing and freeze-drying. The doubly rigid structure supplied by the synergy of hydrogen bonding and B─O covalent bonding can protect the triplet excitons; thus, the prepared 3D RTP object shows a striking lifetime of 2.14 s. The printed counterparts are successfully used for 3D anti-counterfeiting and can be recycled and reprinted nondestructively by dissolving in water. This success expands the scope of printable 3D luminescent materials, providing an eco-friendly platform for the additive manufacturing of sophisticated 3D RTP architectures.

Research progress on intestinal microbiota regulating cognitive function through the gut-brain axis.

The intestinal microbiota community is a fundamental component of the human body and plays a significant regulatory role in maintaining overall health and in the management disease states.The intestinal microbiota-gut-brain axis represents a vital connection in the cognitive regulation of the central nervous system by the intestinal microbiota.The impact of intestinal microbiota on cognitive function is hypothesized to manifest through both the nervous system and circulatory system. Imbalances in intestinal microbiota during the perioperative period could potentially contribute to perioperative neurocognitive dysfunction. This article concentrates on a review of existing literature to explore the potential influence of intestinal microbiota on brain and cognitive functions via the nervous and circulatory systems.Additionally, it summarizes recent findings on the impact of perioperative intestinal dysbacteriosis on perioperative neurocognitive dysfunction and suggests novel approaches for prevention and treatment of this condition.

Complementary Weaknesses: A Win-Win Approach for RGO/CdS to Improve the Energy Conversion Performance of Integrated Photorechargeable Li-S Batteries.

Integrating solar energy into rechargeable battery systems represents a significant advancement towards sustainable energy storage solutions. Herein, we propose a win-win solution to reduce the shuttle effect of polysulfide and improve the photocorrosion stability of CdS, thereby enhancing the energy conversion efficiency of rGO/CdS-based photorechargeable integrated lithium-sulfur batteries (PRLSBs). Experimental results show that CdS can effectively anchor polysulfide under sunlight irradiation for 20 minutes. Under a high current density (1 C), the discharge-specific capacity of the PRLSBs increased to 971.30 mAh g-1, which is 113.3 % enhancement compared to that of under dark condition (857.49 mAh g-1). Remarkably, without an electrical power supply, the PRLSBs can maintain a 21 hours discharge process following merely 1.5 hours of light irradiation, achieving a breakthrough solar-to-electrical energy conversion efficiency of up to 5.04 %. Ex situ X-ray photoelectron spectroscopy (XPS) and in situ Raman analysis corroborate the effectiveness of this complementary weakness approach in bolstering redox kinetics and curtailing polysulfide dissolution in PRLSBs. This work showcases a feasible strategy to develop PRLSBs with potential dual-functional metal sulfide photoelectrodes, which will be of great interest in future-oriented off-grid photocell systems.

Formation of Disordered High-Entropy-Alloy Nanoparticles for Highly Efficient Hydrogen Electrocatalysis.

Nanoparticles composed of high-entropy alloys (HEA NPs) exhibit remarkable performance in electrocatalytic processes such as hydrogen evolution and oxidations. In this study, two types of quinary HEA NPs of PtRhPdIrRu, are synthesized, featuring disordered and crystallized nanostructures, both with and without a boiling mixture. The disordered HEA NPs (d-HEA NPs) with a size of 3.5 nm is synthesized under intense boiling conditions, attributed to improved heat and mass transfer during reduction of precursors and particle growth. The disordered HEA NPs displayed an exceptionally high turnover frequency of 33.1 s-1 at an overpotential of 50 mV, surpassing commercial Pt NPs in acidic electrolytes by 5.4 times. Additionally, d-HEA NPs exhibited superior stability at a constant electrolyzing current of 50 mA cm-2 compared to commercial Pt NPs. When employed as the anodic catalyst in an H2-O2 fuel cell, d-HEA NPs demonstrated a remarkable high current power density of 15.3 kW per gram of noble metal. Consequently, these findings highlight the potential of d-HEA NPs in electrochemical applications involving hydrogen.

Hair-Derived Exposome Exploration of Cardiometabolic Health: Piloting a Bayesian Multitrait Variable Selection Approach.

Cardiometabolic health is complex and characterized by an ensemble of correlated and/or co-occurring conditions including obesity, dyslipidemia, hypertension, and diabetes mellitus. It is affected by social, lifestyle, and environmental factors, which in-turn exhibit complex correlation patterns. To account for the complexity of (i) exposure profiles and (ii) health outcomes, we propose to use a multitrait Bayesian variable selection approach and identify a sparse set of exposures jointly explanatory of the complex cardiometabolic health status. Using data from a subset (N = 941 participants) of the nutrition, environment, and cardiovascular health (NESCAV) study, we evaluated the link between measurements of the cumulative exposure to (N = 33) pollutants derived from hair and cardiometabolic health as proxied by up to nine measured traits. Our multitrait analysis showed increased statistical power, compared to single-trait analyses, to detect subtle contributions of exposures to a set of clinical phenotypes, while providing parsimonious results with improved interpretability. We identified six exposures that were jointly explanatory of cardiometabolic health as modeled by six complementary traits, of which, we identified strong associations between hexachlorobenzene and trifluralin exposure and adverse cardiometabolic health, including traits of obesity, dyslipidemia, and hypertension. This supports the use of this type of approach for the joint modeling, in an exposome context, of correlated exposures in relation to complex and multifaceted outcomes.

Glucocorticoid hormones in relation to environmental exposure to bisphenols and multiclass pesticides among middle aged-women: Results from hair analysis.

Bisphenols and pesticides have been shown to alter circulating glucocorticoids levels in animals, but there is limited human data. Moreover, measurements from biological fluids may not be able to reflect long-term status of non-persistent pollutants and glucocorticoids due to the high variability in their levels. Using hair analysis, we examined the associations between glucocorticoid hormones and environmental exposure to multi-class organic pollutants among a healthy female population aged 25-45 years old. Concentrations of four glucocorticoids, four polychlorinated biphenyl congeners (PCBs), seven polybrominated diphenyl ether congeners (PBDEs), two bisphenols and 140 pesticides and their metabolites were measured in hair samples collected from 196 Chinese women living in urban areas. Due to the low detection frequency of some pollutants, associations were explored only on 54 pollutants, i.e. PCB 180, bisphenol A, bisphenol S and 51 pesticides and their metabolites. Using stability-based Lasso regression, there were associations of cortisol, tetrahydrocortisol, cortisone, and tetrahydrocortisone with 14, 10, 13 and 17 biomarkers of exposure to pollutants, respectively, with bisphenol S, p,p'-dichlorodiphenyldichloroethylene, diethyl phosphate, 3,5,6-trichloro-2-pyridinol, thiamethoxam, imidacloprid, fipronil, tebuconazole, trifluralin, pyraclostrobin and 1-(3,4-dichlorophenyl)-3-methylurea being associated with at least three of the four hormones. There were also associations between cortisone/cortisol molar ratio and pollutants, namely dimethyl phosphate, 3-methyl-4-nitrophenol, carbofuran, λ-cyhalothrin, permethrin, fipronil, flusilazole, prometryn and fenuron. Some of these relationships were confirmed by single-pollutant linear regression analyses. Overall, our results suggest that background level of exposure to bisphenols and currently used pesticides may interfere with the glucocorticoid homeostasis in healthy women.

Efficacy and safety of 3D reconstruction and basket multi-electrode renal denervation (RDN) for refractory hypertensive patients with chronic kidney disease.

Renal Artery Sympathetic Denervation (RDN) can lower blood pressure. Different ablation catheters (single electrode, multi-electrode) have different scopes of ablation (renal artery main stem and branches). Few studies have compared the advantages and disadvantages of different ablation catheters and different procedures in terms of antihypertensive efficacy. To compare the efficacy and safety of 3D reconstruction radiofrequency ablation (3DRA) and basket multi-electrode radiofrequency ablation (BMRA) in Renal Artery Sympathetic Denervation. Fifty-three patients with Refractory hypertension (RHT) were divided into BMRA, (n = 28) and 3DRA(n = 25). BMRA group used a stereobasket multi-electrode ablation catheter with a controlled ablation temperature of 60°C and an ablation time of 120 s per site. 3DRA group used a NavStar pressure-monitored perfusion monopolar ablation catheter with a controlled ablation temperature of 40°C, an ablation time of 40 s per site, and an ablation energy of 12 W. Baseline and RDN parameters and complications were compared in both groups. Home and 24 h ambulatory blood pressure, type of anti-hypertensive medication taken, and serum creatinine were followed up at 1, 3, 6, 12, and 24 months after the RDN. There were no differences in baseline characteristics between the two groups. (23.14 ± 2.00)months of follow-up in the BMRA group resulted in a total of (25.86 ± 8.61) loci ablation. (19.28 ± 7.40)months of follow-up in the 3DRA group resulted in a total of (21.04 ± 6.47)loci ablation. Home SBP was significantly lower in both groups at 1 month after RDN treatment compared to baseline(H-SBP/mmHg: BMRA 149.9 ± 10.59 vs. baseline 168.36 ± 12.76; 3DRA 152.6 ± 14.91 vs. 164.89 ± 12.96, both p < .05). The proportion of people with 24 h ambulatory SBP attainment was significantly higher in both groups and was maintained for 24 months. At each follow-up time point, there were no differences in home and 24-h flow SBP, DBP, or Scr between the two groups. There were two cases of severe renal artery complications from implanted vascular stents and one case of femoral artery pseudoaneurysm in the 3DRA group. At follow-up, 1 (1.9%) patient in the 3DRA group died of unexplained death and 1 (1.9%) patient developed heart failure, and 1 (1.9%) patient in the BMRA group died of unexplained death. Basket multi-electrode radiofrequency ablation and 3D reconstruction radiofrequency ablation of the renal artery applied to RDN have comparable efficacy in reducing systolic blood pressure.

Dual Factor-Loaded Artificial Periosteum Accelerates Bone Regeneration.

In the clinic, inactivation of osteosarcoma using microwave ablation would damage the periosteum, resulting in frequent postoperative complications. Therefore, the development of an artificial periosteum is crucial for postoperative healing. In this study, we prepared an artificial periosteum using silk fibroin (SF) loaded with stromal cell-derived factor-1α (SDF-1α) and calcitonin gene-related peptide (CGRP) to accelerate bone remodeling after the microwave ablation of osteosarcoma. The prepared artificial periosteum showed a sustained release of SDF-1α and CGRP after 14 days of immersion. In vitro culture of rat periosteal stem cells (rPDSCs) demonstrated that the artificial periosteum is favorable for cell recruitment, the activity of alkaline phosphatase, and bone-related gene expression. Furthermore, the artificial periosteum improved the tube formation and angiogenesis-related gene expression of human umbilical vein endothelial cells (HUVECs). In an animal study, the periosteum in the femur of a rabbit was inactivated through microwave ablation and then removed. The damaged periosteum was replaced with the as-prepared artificial periosteum and favored bone regeneration. In all, the designed dual-factor-loaded artificial periosteum is a promising strategy to replace the damaged periosteum in the therapy of osteosarcoma for a better bone-rebuilding process.

Enhancing immune modulation and bone regeneration on titanium implants by alleviating the hypoxic microenvironment and releasing bioactive ions.

Bone implantation inevitably causes damage to surrounding vasculature, resulting in a hypoxic microenvironment that hinders bone regeneration. Although titanium (Ti)-based devices are widely used as bone implants, their inherent bioinert surface leads to poor osteointegration. Herein, a strontium peroxide (SrO2)-decorated Ti implant, Ti_P@SrO2, was constructed through coating with poly-L-lactic acid (PLLA) to alleviate the hypoxic microenvironment and transform the bioinert surface of the implant into a bioactive surface. PLLA degradation resulted in an acidic microenvironment and the release of SrO2 nanoparticles. The acidic microenvironment then accelerated the decomposition of SrO2, resulting in the release of O2 and Sr ions. O2 released from Ti_P@SrO2 can alleviate the hypoxic microenvironment, thus enhancing cell proliferation in an O2-insufficient microenvironment. Furthermore, under hypoxic and normal microenvironments, Ti_P@SrO2 enhanced alkaline phosphatase activity and bone-related gene expression in C3H10T1/2 cells with the continuous release of Sr ions. Meanwhile, Ti_P@SrO2 suppressed M1 polarization and promoted M2 polarization of bone marrow-derived monocytes under hypoxic and normal conditions. Furthermore, in a rat implantation model, the implant enhanced new bone formation and improved osteointegration after modification with SrO2. In summary, the newly designed O2- and Sr ion-releasing Ti implants are promising for applications in bone defects.

Oleanolic acid nanoparticles-stabilized W/O Pickering emulsions: Fabrication, characterization, and delivery application.

Water-in-oil (W/O) Pickering emulsions have wide applications in the food industries. However, the existing W/O Pickering particles have disadvantages such as lack of bioactivity and poor stability. In this study, naturally occurring bioactive oleanolic acid (OA) was used as a novel emulsifier for W/O emulsions. Results revealed that rod-like OA could formulate into spherical nanoparticles by self-assembly, and then be anchored onto the oil-water interface to stabilize the emulsions. Besides, both OA concentration and internal water fraction (φ) had significant effect on the properties of emulsions. Furthermore, the resulted emulsions exhibited potential application as carriers for epigallocatechin-3-gallate (EGCG), which significantly improved its UV and thermal stability. Meanwhile, it could effectively protect EGCG from gastric digestion, and controlled release in the intestine. This work demonstrated the successful application of OA as a stabilizer for W/O emulsions, and provided valuable insight into its potential as delivery system for hydrophilic instable compounds.

Catalyst Selection over an Electrochemical Reductive Coupling Reaction toward Direct Electrosynthesis of Oxime from NOx and Aldehyde.

Aqueous electrochemical coupling reactions, which enable the green synthesis of complex organic compounds, will be a crucial tool in synthetic chemistry. However, a lack of informed approaches for screening suitable catalysts is a major obstacle to its development. Here, we propose a pioneering electrochemical reductive coupling reaction toward direct electrosynthesis of oxime from NOx and aldehyde. Through integrating experimental and theoretical methods, we screen out the optimal catalyst, i.e., metal Fe catalyst, that facilitates the enrichment and C-N coupling of key reaction intermediates, all leading to high yields (e.g., ∼99% yield of benzaldoxime) for the direct electrosynthesis of oxime over Fe. With a divided flow reactor, we achieve a high benzaldoxime production of 22.8 g h-1 gcat-1 in ∼94% isolated yield. This work not only paves the way to the industrial mass production of oxime via electrosynthesis but also offers references for the catalyst selection of other electrochemical coupling reactions.

Improvement of an enzymatic cascade synthesis of nicotinamide mononucleotide via protein engineering and reaction-process reinforcement.

Enzymatic synthesis of ß-nicotinamide mononucleotide (NMN) from D-ribose has garnered widespread attention due to its cheap material, the use of mild reaction conditions, and the ability to produce highly pure products with the desired optical properties. However, the overall NMN yield of this method is impeded by the low activity of rate-limiting enzymes. The ribose-phosphate diphosphokinase (PRS) and nicotinamide phosphoribosyltransferase (NAMPT), that control the rate of the reaction, were engineered to improve the reaction efficacy. The actives of mutants PRS-H150Q and NAMPT-Y15S were 334% and 57% higher than that of their corresponding wild-type enzymes, respectively. Furthermore, by adding pyrophosphatase, the byproduct pyrophosphate which can inhibit the activity of NAMPT was degraded, leading to a 6.72% increase in NMN yield. Following with reaction-process reinforcement, a high yield of 8.10 g L-1 NMN was obtained after 3 h of reaction, which was 56.86-fold higher than that of the stepwise reaction synthesis (0.14 g L-1 ), indicating that the in vitro enzymatic synthesis of NMN from D-ribose and niacinamide is an economical and feasible route.

Universal insertion of molecules in ionic compounds under pressure.

Using first-principles calculations and crystal structure search methods, we found that many covalently bonded molecules such as H2, N2, CO2, NH3, H2O and CH4 may react with NaCl, a prototype ionic solid, and form stable compounds under pressure while retaining their molecular structure. These molecules, despite whether they are homonuclear or heteronuclear, polar or non-polar, small or large, do not show strong chemical interactions with surrounding Na and Cl ions. In contrast, the most stable molecule among all examples, N2, is found to transform into cyclo-N5- anions while reacting with NaCl under high pressures. It provides a new route to synthesize pentazolates, which are promising green energy materials with high energy density. Our work demonstrates a unique and universal hybridization propensity of covalently bonded molecules and solid compounds under pressure. This surprising miscibility suggests possible mixing regions between the molecular and rock layers in the interiors of large planets.

High stretchable and tough xylan-g-gelatin hydrogel via the synergy of chemical cross-linking and salting out for strain sensors.

Stretchable and tough hydrogels have been extensively used in tissue engineering scaffolds and flexible electronics. However, it is still a significant challenge to prepare hydrogels with both tensile strength and toughness by utilizing xylan, which is abundant in nature. Herein, we present a novel hydrogel of carboxymethyl xylan(CMX) graft gelatin (G) and doped with conductive hydroxyl carbon nanotubes (OCNT). CMX and G are combined through amide bonding as well as intermolecular hydrogen bonding to form a semi-interpenetrating hydrogel network. The hydrogel was further subjected to salting-out treatment, which induced the aggregation of the CMX-g-G molecular chain and the formation of chain bundles to toughen the hydrogel, the tensile strain, tensile stress, and toughness of CMX-g-G hydrogels were 1.547 MPa, 324 %, and 2.31 MJ m-3, respectively. In addition, OCNT was used as a conductive filler to impart electrical conductivity and further improve the mechanical properties of CMX-g-G/OCNT hydrogel, and a tensile strength of 1.62 MPa was obtained. Thus, the synthesized CMX-g-G/OCNT hydrogel can be used as a reliable and sensitive strain sensor for monitoring human activity. This study opens up new horizons for the preparation of xylan-based high-performance hydrogels.

Perforin-Mimicking Molecular Drillings Enable Macroporous Hollow Lignin Spheres for Performance-Configurable Materials.

Despite the first observations that the perforin can punch holes in target cells for live/dead cycles in the human immune system over 110 years ago, emulating this behavior in materials science remains challenging. Here, a perforin-mimicking molecular drilling strategy is employed to engineer macroporous hollow lignin spheres as performance-configurable catalysts, adhesives, and gels. Using a toolbox of over 20 molecular compounds, the local curvature of amphiphilic lignin is modulated to generate macroporous spheres with hole sizes ranging from 0 to 100 nm. Multiscale control is precisely achieved through noncovalent assembly directing catalysis, synthesis, and polymerization. Exceptional performance mutations correlate with the changes in hole size, including an increase in catalytic efficiency from 50% to 100%, transition from nonstick synthetics to ultrastrong adhesives (adhesion ≈18.3 MPa, exceeding that of classic epoxies), and transformation of viscous sols to tough nanogels. Thus, this study provides a robust and versatile noncovalent route for mimicking perforin-induced structural variations in cells, representing a significant stride toward the exquisite orchestration of assemblies over multiple length scales.