Supramolecularly Connected Armor-like Nanostructure Enables Mechanically Robust Radiative Cooling Materials.

Passive daytime radiative cooling (PDRC) is a promising practice to realize sustainable thermal management with no energy and resources consumption. However, there remains a challenge of simultaneously integrating desired solar reflectivity, environmental durability, and mechanical robustness for polymeric composites with nanophotonic structures. Herein, inspired by a classical armor shell of a pangolin, we adopt a generic design strategy that harnesses supramolecular bonds between the TiO2-decorated mica microplates and cellulose nanofibers to collectively produce strong interfacial interactions for fabricating interlayer nanostructured PDRC materials. Owing to the strong light scattering excited by hierarchical nanophotonic structures, the bioinspired film demonstrates a desired reflectivity (92%) and emissivity (91%) and an excellent temperature drop of 10 °C under direct sunlight. Notably, the film guarantees high strength (41.7 MPa), toughness (10.4 MJ m-3), and excellent environmental durability. This strategy provides possibilities in designing polymeric PDRC materials, further establishing a blueprint for other functional applications like soft robots, wearable devices, etc.

Supramolecular metallic foams with ultrahigh specific strength and sustainable recyclability.

Porous materials with ultrahigh specific strength are highly desirable for aerospace, automotive and construction applications. However, because of the harsh processing of metal foams and intrinsic low strength of polymer foams, both are difficult to meet the demand for scalable development of structural foams. Herein, we present a supramolecular metallic foam (SMF) enabled by core-shell nanostructured liquid metals connected with high-density metal-ligand coordination and hydrogen bonding interactions, which maintain fluid to avoid stress concentration during foam processing at subzero temperatures. The resulted SMFs exhibit ultrahigh specific strength of 489.68 kN m kg-1 (about 5 times and 56 times higher than aluminum foams and polyurethane foams) and specific modulus of 281.23 kN m kg-1 to withstand the repeated loading of a car, overturning the previous understanding of the difficulty to achieve ultrahigh mechanical properties in traditional polymeric or organic foams. More importantly, end-of-life SMFs can be reprocessed into value-added products (e.g., fibers and films) by facile water reprocessing due to the high-density interfacial supramolecular bonding. We envisage this work will not only pave the way for porous structural materials design but also show the sustainable solution to plastic environmental risks.

Bioinspired H-Bonding Connected Gradient Nanostructure Actuators Based on Cellulose Nanofibrils and Graphene.

The construction of flexible actuators with ultra-fast actuation and robust mechanical properties is crucial for soft robotics and smart devices, but still remains a challenge. Inspired by the unique mechanism of pinecones dispersing seeds in nature, a hygroscopic actuator with interlayer network-bonding connected gradient structure is fabricated. Unlike most conventional bilayer actuator designs, the strategy leverages biobased polyphenols to construct strong interfacial H-bonding networks between 1D cellulose nanofibers and 2D graphene oxide, endowing the materials with high tensile strength (172 MPa) and excellent toughness (6.64 MJ m-3). Furthermore, the significant difference in hydrophilicity between GO and rGO, along with the dense interlayer H-bonding, enables ultra-fast water exchange during water absorption and desorption processes. The resulted actuator exhibits ultra-fast driving speed (154° s-1), excellent pressure-resistant and cyclic stability. Taking advantages of these benefits, the actuator can be fabricated into smart devices (such as smart grippers, humidity control switches) with significant potential for practical applications. The presented approach to constructing interlayer H-bonding in gradient structures is instructive for achieving high performance and functionalization of biomass nanomaterials and the complex of 1D/2D nanomaterials.

Anti-tumor necrosis factor-α therapy may not be safe during pregnancy in women with inflammatory bowel disease: an updated meta-analysis and systematic review.

BACKGROUND: Inflammatory Bowel Disease (IBD) affects reproductive-aged women. Active disease can lead to decreased fertility. Although the vast majority of international guidelines recommend for the continuation of anti-TNF-α during pregnancy, recent studies have raised concerns about the safety of anti-tumor necrosis factor-α (TNF-α) therapy during pregnancy, both for patients and for physicians. METHODS: Studies that evaluate the safety of anti-TNF-α therapy in pregnant women with IBD were identified using bibliographical searches. An updated meta-analysis was performed for pregnancy outcomes, such as live birth, abortion, still birth, preterm birth, low birth weight, congenital abnormalities, and neonatal infection. Odds ratio (OR) with 95% confidence interval (CI) are reported. Data on disease activity, timing of anti-TNF-α therapy were collected for further analysis. RESULTS: Overall, 11 studies were screened from on-line databases and international meeting abstracts. An increased risk of abortion (OR, 1.33; 95% CI, 1.02-1.74; P = 0.04) and preterm birth (OR, 1.16; 95% CI, 1.05-1.28; P = 0.004), and a decreased risk of live birth (OR, 0.83; 95% CI, 0.74-0.94; P = 0.002]) were found in the anti-TNF-α therapy group compared with the control group (no use of anti-TNF-α therapy). The subgroup analyses based on the disease activity showed there is no significant association between the use of anti-TNF-α therapy during pregnancy on adverse pregnancy outcomes of abortion, preterm birth, and live birth. The rates of still birth, low birth weight, and congenital abnormalities in the anti-TNF-α therapy group were not significantly different from those in the control group. CONCLUSIONS: Anti-TNF-α therapy does not increase the risks of still birth, low birth weight, and congenital abnormalities; however it may be assicated with increased risks of abortion and preterm birth, which are accompanied by a lower rate of live birth. Although these findings may be confounding by potential disease activity, they offer some opposite viewpoints with biologic agent use. Therefore, more studies are required to further confirm the safety of anti-TNF-α therapy in pregnancy with IBD.

Deciphering the Microdroplet Acceleration Factors of Aza-Michael Addition Reactions.

Microdroplet chemistry is emerging as a great tool for accelerating reactions by several orders of magnitude. Several unique properties such as extreme pHs, interfacial electric fields (IEFs), and partial solvation have been reported to be responsible for the acceleration; however, which factor plays the key role remains elusive. Here, we performed quantum chemical calculations to explore the underlying mechanisms of an aza-Michael addition reaction between methylamine and acrylamide. We showed that the acceleration in methanol microdroplets results from the cumulative effects of several factors. The acidic surface of the microdroplet plays a dominating role, leading to a decrease of ∼9 kcal/mol in the activation barrier. We speculated that the dissociation of both methanol and trace water contributes to the surface acidity. An IEF of 0.1 V/Šcan further decrease the barrier by ∼2 kcal/mol. Partial solvation has a negligible effect on lowering the activation barrier in microdroplets but can increase the collision frequency between reactants. With acidity revealed to be the major accelerating factor for methanol droplets, reactions on water microdroplets should have even higher rates because water is more acidic. Both theoretically and experimentally, we confirmed that water microdroplets significantly accelerate the aza-Michael reaction, achieving an acceleration factor that exceeds 107. This work elucidates the multifactorial influences on the microdroplet acceleration mechanism, and with such detailed mechanistic investigations, we anticipate that microdroplet chemistry will be an avenue rich in opportunities in the realm of green synthesis.

Designer "Quasi-Benzyne": The Spontaneous Reduction of Ortho-Diiodotetrafluorobenzene on Water Microdroplets.

It has been widely shown that water microdroplets have a plethora of unique properties that are highly distinct from those of bulk water, among which an especially intriguing one is the strong reducing power as a result of the electrons spontaneously generated at the air-water interface. In this study, we take advantage of the reducing power of water microdroplets to reduce ortho-diiodotetrafluorobenzene (o-C6F4I2) into a C6F4I2•- radical anion. Photoelectron spectroscopy and density functional theory computations reveal that the excess electron in C6F4I2•- occupies the I-C1-C2-I linkage, which elongates the C-I bonds but surprisingly shortens the C1-C2 bond, making the bond order higher than a double bond, similar to the benzyne molecule, so we named it "quasi-benzyne". The C6F4I2•- anion was further successfully utilized in a Diels-Alder reaction, a typical reaction for benzyne. This study provides a good example of strategically utilizing the spontaneous properties of water microdroplets and generating an especially exotic anion, and we anticipate that microdroplet chemistry can be an avenue rich in opportunities for new catalyst-free organic reactions.

Clinical characteristics of persistent or recurrent pneumonia combined with airway malacia in children.

OBJECTIVE: The aim of this study is to investigate the clinical characteristics and pathogens involved in persistent or recurrent pneumonia combined with airway malacia in children. METHODS: We retrospectively reviewed the information of children hospitalised with persistent or recurrent pneumonia, including clinical presentations, laboratory examination results and pathogens. RESULTS: A total of 554 patients were admitted, 285 (51.44%) of whom were found to have airway malacia. There were 78 (27.37%), 166 (58.25%) and 41 (14.39%) patients with mild, moderate and severe malacia, respectively. Patients with airway malacia were younger than those without malacia (6.0 vs. 12.0 months, p < 0.01) and were more likely to present with wheezing (75.07%), fever (34.39%), dyspnoea (28.77%), cyanosis (13.68%) and wheezing in the lungs (78.95%). The incidence of preterm delivery, oxygen therapy, paediatric intensive care unit (PICU) admission and mechanical ventilation was higher, and the hospital stay (11.0 vs. 10.0 days, p = 0.04) was longer in these patients than in those without malacia. Patients with severe airway malacia were more likely to undergo oxygen therapy, PICU admission, mechanical ventilation and have multiple malacia than were those with mild or moderate malacia. Mycoplasma pneumoniae (30.18%) was the most common pathogen. CONCLUSION: Severe airway malacia likely aggravates conditions combined with pneumonia. The proportion of multisite malacia was greater in severe airway malacia patients.

Proton-selective coating enables fast-kinetics high-mass-loading cathodes for sustainable zinc batteries.

The pressing demand for sustainable energy storage solutions has spurred the burgeoning development of aqueous zinc batteries. However, kinetics-sluggish Zn2+ as the dominant charge carriers in cathodes leads to suboptimal charge-storage capacity and durability of aqueous zinc batteries. Here, we discover that an ultrathin two-dimensional polyimine membrane, featured by dual ion-transport nanochannels and rich proton-conduction groups, facilitates rapid and selective proton passing. Subsequently, a distinctive electrochemistry transition shifting from sluggish Zn2+-dominated to fast-kinetics H+-dominated Faradic reactions is achieved for high-mass-loading cathodes by using the polyimine membrane as an interfacial coating. Notably, the NaV3O8·1.5H2O cathode (10 mg cm-2) with this interfacial coating exhibits an ultrahigh areal capacity of 4.5 mAh cm-2 and a state-of-the-art energy density of 33.8 Wh m-2, along with apparently enhanced cycling stability. Additionally, we showcase the applicability of the interfacial proton-selective coating to different cathodes and aqueous electrolytes, validating its universality for developing reliable aqueous batteries.

Intervention with ICOSL Antibodies Alleviates Inflammatory Infiltrations in Mice with Neutrophilic Asthma.

Background: Neutrophilic asthma is characterized by the predominant infiltration of neutrophils in airway inflammation. Objective: To explore the therapeutic potential of an antibody against the inducible T cell co-stimulator ligand (ICOSL) in a mouse model of neutrophilic asthma. Methods: Female BALB/c mice were randomly assigned to different groups. They were then injected with ovalbumin (OVA)/lipopolysaccharides (LPS) to induce neutrophilic asthma. The mice were then treated with either anti-ICOSL (the I group), control IgG (the G group), or no treatment (the N group). Additionally, a control group of mice received vehicle PBS and was labeled as the C group (n=6 per group). One day after the last allergen exposure, cytokine levels were measured in plasma and bronchoalveolar lavage fluid (BALF) using ELISA. After analyzing and categorizing BALF cells, the lung tissues were examined histologically and immunohistochemically. Results: Administering anti-ICOSL resulted in a significant decrease in the total number of inflammatory infiltrates and neutrophils found in BALF. Moreover, it led to a decrease in the levels of interleukin (IL)-6, IL-13, and IL-17 in both BALF and plasma. Additionally, there was an increase in IFN-γ levels in the BALF of asthmatic mice (p<0.05 for all). Treatment with anti-ICOSL also reduced lung interstitial inflammation, mucus secretion, and ICOSL expression in asthmatic mice. Conclusion: The treatment of anti-ICOSL effectively improved lung interstitial inflammation and mucus secretion in mice with neutrophilic asthma by restoring the balance of Th1/Th2/Th17 responses. These findings indicate that blocking the ICOS/ICOSL signaling could be an effective way to manage neutrophilic asthma.

Cellulose nanocrystal-based polymer hydrogel embedded with iron oxide nanorods for efficient arsenic removal.

A cellulose nanocrystal (CNC) polymer hydrogel containing magnetic iron oxide nanorods (Fe3O4NRs) was prepared for As(III) removal in water. Systematic studies on the performance of these prepared CNC-based composite hydrogels for the removal of As(III) have been undertaken. The maximum adsorption capacity of the CNC-g-PAA/qP4VP (CPqP) hydrogel was 241.3 mg/g. After introduction of Fe3O4NRs in the hydrogel, the maximum adsorption capacity of the resulting Fe3O4NRs@CNC-g-PAA/qP4VP (FN@CPqP) hydrogel was further improved to 263.0 mg/g. The high adsorption performance can be attributed to the facts that the 3D interconnected porous network of the hydrogel allows As species to easily enter into the hydrogel, the quaternized P4VP chains provides more adsorption sites, Fe3O4NRs uniformly distributed in the internal cavity of the hydrogel significantly reduces the nanoparticle aggregation. The adsorption kinetics indicated that the adsorption of arsenic by the hydrogel was mainly chemisorption. The isotherm analysis revealed that the adsorption of arsenic by the hydrogel was principally monolayer adsorption on a homogeneous surface. Moreover, the as-prepared CNC-based polymer hydrogels exhibited good stability and reusability with negligible performance loss after five adsorption-desorption cycles. The novel FN@CPqP hydrogel demonstrates great potential as a cost-effective adsorbent for the removal of arsenic contaminants from wastewater.

Identification of Binding Sites in Copper(II)-Peptide Complexes Using Infrared Spectroscopy.

Complex formation of the copper(II) ion (CuII) with histidine (H) and H-containing peptides plays a crucial role in various metallo-enzymatic reactions. To elucidate the nature of coordinate bonding in CuII complexes, Fourier-transform infrared spectroscopy and 2D IR spectroscopy were employed to investigate the coordination geometries of CuII with diglycine, l-histidylglycine (HG), glycyl-l-histidine (GH), and glycylglycyl-l-histidine. The coordination of CuII to different peptide groups, including the peptide N- and C-termini, the amide group, and the imidazole of the H side chain, exhibits distinct spectral features. The derived molecular structure of the CuII-HG complex based on these spectral features significantly differs from that of CuII-GH, suggesting a preference of the N-terminus and the steric hindrance of the H side chain in CuII chelation.

Dynamic Covalent Bonded Gradient Structured Actuators with Mechanical Robustness and Self-Healing Ability.

Flexible actuators with excellent adaptability and interaction safety have a wide range of application prospects in many fields. However, current flexible actuators have problems such as fragility and poor actuating ability. Here, inspired by the features of nacre structure, a gradient structured flexible actuator is proposed with mechanical robustness and self-healing ability. By introducing dynamic boronic ester bonds at the interface between MXene nanosheets and epoxy natural rubber matrix, the resulting nanocomposites with ordered micro-nano structures exhibit excellent tensile strength (25.03 MPa) and satisfactory repair efficiency (81.2%). In addition, the gradient distribution structure of MXene nanosheets endows the actuator with stable photothermal conversion capability, which can quickly respond to near-infrared light stimulation. The interlayer dynamic covalent bond crosslinking enables good response speed after multiple bending and is capable of functional self-healing after damage. This work introduces gradient structure and dynamic covalent bonding into flexible actuators, which provides a reference for the fabrication of self-healing soft robots, wearable, and other healable functional materials.

Construction of Mineralization Nanostructures in Polymers for Mechanical Enhancement and Functionalization.

Mineralization capable of growing inorganic nanostructures efficiently, orderly, and spontaneously shows great potential for application in the construction of high-performance organic-inorganic composites. As a thermodynamically spontaneous solid-phase crystallization reaction involving dual organic and inorganic components, mineralization allows for the self-assembly of sophisticated and exclusive nanostructures within a polymer matrix. It results in a diversity of functions such as enhanced strength, toughness, electrical conductivity, selective permeability, and biocompatibility. While there are previous reviews discussing the progress of mineralization reactions, many of them overlook the significant benefits of interfacial regulation and functionalization that come from the incorporation of mineralized structures into polymers. Focusing on different means of assembly of mineralized nanostructures in polymer, the work analyzes their design principles and implementation strategies. Then, their different advantages and disadvantages are analyzed by combining nanostructures with organic substrates as well as involving the basis of different functionalizations. It is anticipated to provide insights and guidance for the future development of mineralized polymer composites and their application designs.

Hepatocellular carcinoma­cavernous hemangioma collision tumor: A case report.

Collision tumors consisting of hepatocellular carcinoma (HCC) and cavernous hemangioma (CH) are rare and the clinicopathological characteristics or cause of the tumors remain unclear. The present study reports the case of a 71-year-old male patient who was admitted to Sunshine Union Hospital (Weifang, China) due to a liver mass found during a routine physical examination. computed tomography scans showed a main lesion of ~4.0×4.2×3.5 cm in segment IV of the patient's liver and a nodule of ~2.4×2.2×1.3 cm in the lower-left part of the lesion, which was clearly demarcated from the main lesion. The capsule of the lesion was found to be intact during the operation performed to remove the tumor. The final patient diagnosis was of a HCC-CH collision tumor based on pathology. The patient underwent follow-up for 6 months after surgery and no recurrence was observed.

Nanogap engineering of 3D nanoraspberries into 2D plasmonic nanoclusters toward improved SERS performance.

3D raspberry-like core/satellite nanostructures were prepared by controlled surface functionalization of silica spheres using crosslinked poly(4-vinylpyridine) (P4VP) chains with known binding affinity for gold nanoparticles (AuNPs). The 3D SiO2-g-P(4VP-co-DVB)/AuNP nanoraspberries can be further transformed into 2D plasmonic nanoclusters by etching the silica core with hydrofluoric acid (HF). After the transformation, the interparticle distance between the AuNPs dramatically reduced from a 10 nm scale to sub 2 nm. Owing to the strong electromagnetic field generated by the plasmonic coupling between AuNPs in very close proximity, the established P(4VP-co-DVB)/AuNP nanoclusters provided strong and undisturbed Raman signals as a SERS substrate. In addition, benefiting from the stabilizing effect of the crosslinked P(4VP-co-DVB) network, the prepared SERS substrate has the advantages of good uniformity, stability and reproducibility, as well as strong SERS enhancement, endowing it with great potential for rapid and efficient SERS detection.

Ln-HOF Nanofiber Organogels with Time-Resolved Luminescence for Programmable and Reliable Encryption.

Developing tunable luminescent materials for high throughput information storage is highly desired following the explosive growth of global data. Although considerable success has been achieved, achieving programmable information encryption remains challenging due to current signal crosstalk problems. Here, we developed long-lived room-temperature phosphorescent organogels enabled by lanthanum-coordinated hydrogen-bonded organic framework nanofibers for time-resolved information programming. Via modulating coassembled lanthanum concentration and Förster resonance energy transfer efficiency, the lifetimes are prolonged and facilely manipulated (20-644 ms), realizing encoding space enlargement and multichannel data outputs. The aggregated strong interfacial supramolecular bonding endows organogels with excellent mechanical toughness (36.16 MJ m-2) and self-healing properties (95.7%), synergistically achieving photostability (97.6% lifetime retention in 10000 fatigue cycles) via suppressing nonradiative decays. This work presents a lifetime-gated information programmable strategy via lanthanum-coordination regulation that promisingly breaks through limitations of current responsive luminescent materials, opening unprecedented avenues for high-level information encryption and protection.

Harnessing the High Interfacial Electric Fields on Water Microdroplets to Accelerate Menshutkin Reactions.

Even though it is still an emerging field, the application of a high external electric field (EEF) as a green and efficient catalyst in synthetic chemistry has recently received significant attention for the ability to deliver remarkable control of reaction selectivity and acceleration of reaction rates. Here, we extend the application of the EEF to Menshutkin reactions by taking advantage of the spontaneous high electric field at the air-water interfaces of sprayed water microdroplets. Experimentally, a series of Menshutkin reactions were accelerated by 7 orders of magnitude. Theoretically, both density functional theory calculations and ab initio molecular dynamics simulations predict that the reaction barrier decreases significantly in the presence of oriented external electric fields, thereby supporting the notion that the electric fields in the water droplets are responsible for the catalysis. In addition, the ordered solvent and reactant molecules oriented by the electric field alleviate the steric effect of solvents and increase the successful collision rates, thus facilitating faster nucleophilic attack. The success of Menshutkin reactions in this study showcases the great potential of microdroplet chemistry for green synthesis.

Toward real-time and accurate dense 3D mapping of crop fields for combine harvesters using a stereo camera.

Fast and accurate 3D scene perception is a crucial prerequisite for the autonomous navigation and harvesting of combine harvesters. However, crop field scenarios pose severe challenges for vision-based perception systems due to repetitive scenes, illumination changes and real-time constraints on embedded computing platforms. In this paper, we propose a feature-based, two-stage approach for real-time dense 3D mapping for combine harvesters. In the first stage, our approach constructs a sparse 3D map using reliable feature matching, which provides prior knowledge about the environment. In the second stage, our method formulates per-pixel disparity calculation as probabilistic inference. The key to our approach is the ability to compute dense 3D maps by combining Bayesian estimation with efficient and discriminative point cues from images, exhibiting tolerance against visual measurement uncertainties due to repetitive textures and uneven lighting in crop fields. We validate the performance of the proposed method using real crop field data, and the results demonstrate that our dense 3D maps provide detailed spatial metric information while maintaining a balance between accuracy and efficiency. This makes our approach highly valuable for online perception in combine harvesters operating with resource-limited systems.

Photoswitchable and Reversible Fluorescent Eutectogels for Conformal Information Encryption.

Smart fluorescent materials that can respond to environmental stimuli are of great importance in the fields of information encryption and anti-counterfeiting. However, traditional fluorescent materials usually face problems such as lack of tunable fluorescence and insufficient surface-adaptive adhesion, hindering their practical applications. Herein, inspired by the glowing sucker octopus, we present a novel strategy to fabricate a reversible fluorescent eutectogel with high transparency, adhesive and self-healing performance for conformal information encryption and anti-counterfeiting. Using anthracene as luminescent unit, the eutectogel exhibits photoswitchable fluorescence and can therefore be reversibly written/erased with patterns by non-contact stimulation. Additionally, different from mechanically irreversible adhesion via glue, the eutectogel can adhere to various irregular substrates over a wide temperature range (-20 to 65 °C) and conformally deform more than 1000 times without peeling off. Furthermore, by exploiting surface-adaptive adhesion, high transparency and good stretchability of the eutectogel, dual encryption can be achieved under UV and stretching conditions to further improve the security level. This study should provide a promising strategy for the future development of advanced intelligent anti-counterfeiting materials.

An intelligent decision support approach for quantified assessment of innovation ability via an improved BP neural network.

In today's competitive and changing social environment, innovation and entrepreneurial ability have become important factors for the successful development of college students. However, relying solely on traditional evaluation methods and indicators cannot comprehensively and accurately evaluate the innovation and entrepreneurial potential and ability of college students. Therefore, developing a comprehensive evaluation model is urgently needed. To address this issue, this article introduces machine learning methods to explore the learning ability of subjective evaluation processes and proposes an intelligent decision support method for quantitatively evaluating innovation capabilities using an improved BP (Back Propagation) neural network. This article first introduces the current research status of evaluating the innovation and entrepreneurship ability of college students, and based on previous research, it has been found that inconsistent evaluation standards are one of the important issues at present. Then, based on different BP models and combined with the actual situation of college student innovation and entrepreneurship evaluation, we selected an appropriate input layer setting for the BP neural network and improved the setting of the middle layer (hidden layer). The identification of output nodes was also optimized by combining the current situation. Subsequently, the conversion function, initial value and threshold were determined. Finally, evaluation indicators were determined and an improved BP model was established which was validated using examples. The research results indicate that the improved BP neural network model has a low error rate, strong generalization ability and ideal prediction effect which can be effectively used to analyze problems related to intelligent evaluation of innovation ability.