Controllable Synthesis and Ultrahigh Proton Conduction of a Hydrogen-Bond Network.

The functionalization of polyoxometalates with organic ligands provides a new-style strategy to accurately incorporate polyoxometalates with advanced functional organic moieties on their surfaces, the development of which has attracted increasing research interest due to the potential applications. A germanium tungstate Na2(H3O)6[{RuIV(bpy)}2{WO2(C2O4)}2(GeW11O39)2]·27H2O (bpy = 2,2'-bipyridine) with two ligands covalently modified was triumphantly synthesized, using the conventional one-pot hydrothermal method. It was systematically characterized by thermogravimetric analysis (TGA), elemental analysis, infrared (IR) spectroscopy, single-crystal X-ray diffraction, X-ray photoelectron spectroscopy (XPS), powder diffraction (PXRD), scanning electronic microscopy (SEM), and ultraviolet-visible (UV-vis) spectroscopy. The two-dimensional (2D) layered structure was established through hydrogen bonding and Na+ bridges. Impedance measurements indicate that it displays outstanding proton conduction properties, with a splendid conductivity up to 1.24 × 10-2 S·cm-1 under 353 K and 90% relative humidity (RH), owing to the rich interlayer hydrogen-bond network formed by the organic ligands ({RuC10H8N2}4+ and {WC2O4}4+), hydrated protons (H3O+), and crystal waters.

Self-Assembled 8-Ti-Containing Polyoxomolybdate for the Photocatalytic Hydrogen Evolution.

An S-shaped 8-Ti-containing polyoxomolybdate (NH4)Cs2Na6H3[Ti8(GeMo9O34)2(GeMo5O23)2]·44H2O (1) has been prepared under the one-pot hydrothermal method and further characterized. According to single-crystal X-ray, compound 1 consists of two {GeMo9O34} and two {GeMo5O23} segments, which are linked with a {Ti8O34} cluster. Moreover, the {GeMo5O23} fragment is rare and the first discovery, which enriches the lacunary Keggin-type family and offers the possibility of obtaining new structures. Among all of the reported polyoxomolybdates, compound 1 has the highest nuclearity of Ti centers. From the photocatalytic hydrogen evolution studies, compound 1 can be used as the heterogeneous catalyst with an H2 evolution rate of 2392.6 µmol g-1 h-1 under minimally optimized conditions.

A Dawson-type {P4W24} modified using phenylphosphonic acid with excellent proton conductivity.

A case of organic-inorganic hybridized phosphotungstate modified using aromatic organophosphonic acid, K4Na4H11[KCo2(H2O)10P4W24O92{(PhPO)2}]·48H2O (1), was successfully synthesized in conventional aqueous solution. The prominent structural feature is that the total structure of [KP4W24O92{(PhPO)2}]23- resembles a V-shaped structure, which was stabilized by two [Co(H2O)5]2+ ions. Furthermore, it can be connected into a three-dimensional mesh structure using K+ ions. Surprisingly, 1 possesses a remarkably high proton conductivity of 1.59 × 10-2 S cm-1 at 95% RH and 318 K probably due to the fact that its structure contains large amounts of lattice water molecules, coordination water molecules and counter cations.

Restricted Growth of Vinylene-Linked Covalent Organic Frameworks along Two-Dimensional Plane Using Heterogeneous Catalysis.

The vinylene-linked covalent organic frameworks (viCOFs) have been generally synthesized in the presence of homogeneous catalysts such as KOH or trifluoroacetic acid. However, highly ordered viCOFs cannot always be obtained due to the uncommitted growth of viCOF layers in the homogeneous system with ubiquitous catalysts. Here, we propose a scalable protocol to restrict the growth of viCOFs along the two-dimensional (2D) plane by introducing a heterogeneous catalyst, polyoxometalates (POMs). With the unique Brønsted alkalinity and catalytic surface, POMs induce the growth of 2D viCOF layers along the surface of the catalytic substrate and restrain the generation of out-of-plane branches. Based on this protocol, six typical 2D viCOFs with high crystallinity and porosity were synthesized within a shorter reaction time as compared with the reported works using the common homogeneous catalysts for viCOF synthesis. On the basis of the density functional theory calculations and experimental results, a bottom intercalation growth pattern of viCOFs was revealed during the heterogeneous reaction. The unique growth pattern greatly promotes the orderly assembly of monomers, thus shortening the reaction time and improving the crystallinity of viCOFs. Furthermore, this heterogeneous catalysis strategy is suitable for the gram-scale preparation of 2D viCOFs. These results provide a novel avenue for the synthesis of high-quality viCOFs and may bring new insights into the synthetic methodology of COFs.

Time-Dependent Effects of Altered Prebedtime Light Exposure in Enclosed Spaces on Sleep Performance Associated with Human States.

Purpose: Exposure to artificial light influences human performance, which is essential for maintaining healthy work and sleep. However, existing research has not explored the intrinsic links between sleep performance and human states over time under prebedtime light exposure interventions (LEIs). Methods: To investigate the time-dependent effects of altered prebedtime light exposure, four LEI groupings (#L1 - #L4) and a Time factor (D8, D9, and D10) were chosen for sleep experiments in enclosed spaces. Forty-eight young adults recruited were available for data analysis. Subjective alertness (SA), negative affect (NA), subjective sleep, and objective sleep were measured via the Karolinska Sleepiness Scale, Positive and Negative Affect Schedule, Next-day Self-assessment Sleep Quality, and joint assessment of wrist actigraphy and sleep diaries, respectively. Statistical analysis was used for the effects of light exposure on the human states (corresponding to the SA and NA) and sleep performance, while the process model helped construct the associations between the two. Results: The statistical effects revealed that the Time had a significant main effect on subjective sleep and changes in prebedtime alertness; the LEI had a significant main effect only on sleep onset latency (SOL). After undergoing altered prebedtime light exposure, the mean SA increased at prebedtime of D9 (p = 0.022) and D10 (p = 0.044); No significant effect on the NA was observed; Mean subjective sleep had a significant increase from D8 to D10. Moreover, five actigraphy-estimated sleep parameters were interrelated. In light of this, a chained pathway relationship was identified. The SOL played a mediating predictor between prebedtime state and objective sleep, which was linked to the awakening state through subjective sleep. Conclusion: Our study suggests that time-dependent effects of altered prebedtime light exposure on sleep performance are associated with human states at prebedtime and awakening, with implications for its prediction of sleep health.

Factors Influencing the Visualization of Fallopian Tubes in Hysterosalpingo-Contrast Sonography (HyCoSy)-The Value of Multimodal HyCoSy in Visualizing the Fallopian Tubes.

BACKGROUND: Four-dimensional hysterosalpingo-contrast sonography (4D-HyCoSy) can non-invasively evaluate the patency of the fallopian tubes and is increasingly used in clinical practice. However, some factors may lead to false-positive diagnoses. This study aims to analyze the factors affecting clear imaging of the fallopian tubes in 4D-HyCoSy and explore methods to improve the quality of fallopian tube imaging. METHODS: A total of 118 patients were enrolled in this retrospective study. After injecting the SonoVue into the uterine cavity, three modes of HyCoSy were completed in sequence: 4D-HyCoSy, 2D-HyCoSy, and second harmonic imaging (SHI). Participants were divided into two groups: the easy visualization group (fallopian tubes could be visualized using only 4D-HyCoSy) and the difficult visualization group (a multimodal combination was required for visualization). The position of the uterus, the relationship between the ovaries and the uterus, endometrial thickness, time of catheterization in the uterine cavity, presence or absence of lesions in the uterine cavity, whether intestinal gas covers the fallopian tubes and the imaging effect of different modes on the fallopian tubes was analyzed, to determine the key factors affecting the clear imaging of the fallopian tubes. RESULTS: The positional relationship between the ovary and the uterus (OR = 4.711, 95% CI: 1.322-19.77, P = 0.023), the positioning of the uterus (OR = 3.843, 95% CI: 1.129-15.26, P = 0.04), endometrial thickness (OR = 3.985, 95% CI: 1.168-15.99, P = 0.036), and the duration of intrauterine catheter placement (OR = 3.547, 95% CI: 1.042-13.52, P = 0.05) were independent factors that affecting difficulty in visualizing the fallopian tubes. CONCLUSION: Uterine position, the positional relationship between the ovary and the uterus, endometrial thickness, and the time of catheter insertion are factors that affect visualizing the fallopian tubes during 4D-HyCoSy. The combination of multimodal imaging, especially the combination of 4D-HyCoSy with SHI mode, can help improve the quality of fallopian tube visualization.

Targeting anticancer immunity in melanoma tumour microenvironment: unleashing the potential of adjuvants, drugs, and phytochemicals.

Melanoma poses a challenge in oncology because of its aggressive nature and limited treatment modalities. The tumour microenvironment (TME) in melanoma contains unique properties such as an immunosuppressive and high-density environment, unusual vasculature, and a high number of stromal and immunosuppressive cells. In recent years, numerous experiments have focused on boosting the immune system to effectively remove malignant cells. Adjuvants, consisting of phytochemicals, toll-like receptor (TLR) agonists, and cytokines, have shown encouraging results in triggering antitumor immunity and augmenting the therapeutic effectiveness of anticancer therapy. These adjuvants can stimulate the maturation of dendritic cells (DCs) and infiltration of cytotoxic CD8+ T lymphocytes (CTLs). Furthermore, nanocarriers can help to deliver immunomodulators and antigens directly to the tumour stroma, thereby improving their efficacy against malignant cells. The remodelling of melanoma TME utilising phytochemicals, agonists, and other adjuvants can be combined with current modalities for improving therapy outcomes. This review article explores the potential of adjuvants, drugs, and their nanoformulations in enhancing the anticancer potency of macrophages, CTLs, and natural killer (NK) cells. Additionally, the capacity of these agents to repress the function of immunosuppressive components of melanoma TME, such as immunosuppressive subsets of macrophages, stromal and myeloid cells will be discussed.

Aptamer-based assembly systems for SARS-CoV-2 detection and therapeutics.

Nucleic acid aptamers are oligonucleotide chains with molecular recognition properties. Compared with antibodies, aptamers show advantages given that they are readily produced via chemical synthesis and elicit minimal immunogenicity in biomedicine applications. Notably, aptamer-encoded nucleic acid assemblies further improve the binding affinity of aptamers with the targets due to their multivalent synergistic interactions. Specially, aptamers can be engineered with special topological arrangements in nucleic acid assemblies, which demonstrate spatial and valence matching towards antigens on viruses, thus showing potential in the detection and therapeutic applications of viruses. This review presents the recent progress on the aptamers explored for SARS-CoV-2 detection and infection treatment, wherein applications of aptamer-based assembly systems are introduced in detail. Screening methods and chemical modification strategies for aptamers are comprehensively summarized, and the types of aptamers employed against different target domains of SARS-CoV-2 are illustrated. The evolution of aptamer-based assembly systems for the detection and neutralization of SARS-CoV-2, as well as the construction principle and characteristics of aptamer-based DNA assemblies are demonstrated. The typically representative works are presented to demonstrate how to assemble aptamers rationally and elaborately for specific applications in SARS-CoV-2 diagnosis and neutralization. Finally, we provide deep insights into the current challenges and future perspectives towards aptamer-based nucleic acid assemblies for virus detection and neutralization in nanomedicine.

Association between passing return-to-sport testing and re-injury risk in patients after anterior cruciate ligament reconstruction surgery: a systematic review and meta-analysis.

Background: Inconsistent results have been obtained regarding the association between return-to-sport (RTS) testing and the risk of subsequent re-injury following anterior cruciate ligament reconstruction (ACLR). We therefore conducted a systematic review and meta-analysis to assess the potential association between passing of RTS and the risk of re-injury for patients after ACLR. Methods: This meta-analysis was registered in INPLASY with the registration number INPLASY202360027. The electronic databases MedLine, EmBase, and the Cochrane library were systematically searched to identify eligible studies from their inception up to September 2023. The investigated outcomes included knee injury, secondary ACL, contralateral ACL injury, and graft rupture. The pooled odds ratios (ORs) and 95% confidence intervals (CIs) were calculated using the random-effects model. Results: A total number of nine studies involving 1410 individuals were selected for the final quantitative analysis. We noted that passing RTS test was not associated with the risk of subsequent knee injury (OR: 0.95; 95% CI: 0.28-3.21; P = 0.929), secondary ACL injury (OR: 0.98; 95% CI: 0.55-1.75; P = 0.945), and contralateral ACL injury (OR: 1.53; 95% CI: 0.63-3.71; P = 0.347). However, the risk of graft rupture was significantly reduced (OR: 0.49; 95% CI: 0.33-0.75; P = 0.001). Conclusions: This study found that passing RTS test was not associated with the risk of subsequent knee injury, secondary ACL injury, and contralateral ACL injury, while it was associated with a lower risk of graft rupture. Thus, it is recommended that patients after ACLR pass an RTS test in clinical settings.

A High Nucleus Cu-Incorporated Giant Phosphotungstate with Photocatalytic Oxidation C-H of Toluene.

Exploring a novel photocatalyst for catalytic oxidation of toluene is a sustainable strategy for energy conversion in times of an energy crisis. However, designing an effective photocatalyst for the conversion of toluene remains challenging. Herein, a novel organic monophosphonate-modified high nucleus Cu-incorporated polyoxotungstate, K8H33[{Cu0.5(H2O)4}{Cu2(O3PCH2COO)(1,4,9-α-P2W15O56)}]4·Cl·60H2O (1), has been intentionally synthesized by a self-assembly process utilizing conventional aqueous method. It reveals that 1 contains a polyanion of [{Cu0.5(H2O)}4{Cu2(O3PCH2COO)(1,4,9-α-P2W15O56)}]440- composed of four Dawson-type {1,4,9-α-P2W15} subunits, forming an oval-shaped structure and further connecting into a three-dimensional (3D) framework by lateral {Cu(H2O)4}2+. Interestingly, the trivacant {1,4,9-α-P2W15} subunits were observed in the organophosphonate acid-functionalized polyoxometalates for the first time. Notably, 1 exhibits a wonderful performance in catalytic oxidation of the recalcitrant C(sp3)-H bond of toluene to benzoic acid with a conversion as high as 97% under visible light utilizing O2 as an oxidant.

A Narrative Review of the Reciprocal Relationship Between Sleep Deprivation and Chronic Pain: The Role of Oxidative Stress.

Sleep is crucial for human health, insufficient sleep or poor sleep quality may negatively affect sleep function and lead to a state of sleep deprivation. Sleep deprivation can result in various health problems, including chronic pain. The intricate relationship between sleep and pain is complex and intertwined, with daytime pain affecting sleep quality and poor sleep increasing pain intensity. The article first describes the influence of sleep on the onset and development of pain, and then explores the impact of daytime pain intensity on nighttime sleep quality and subsequent pain thresholds. However, the primary emphasis is placed on the pivotal role of oxidative stress in this bidirectional relationship. Although the exact mechanisms underlying sleep and chronic pain are unclear, this review focuses on the role of oxidative stress. Numerous studies on sleep deprivation have demonstrated that it can lead to varying degrees of increased pain sensitivity, while chronic pain leads to sleep deprivation and further exacerbates pain. Further research on the role of oxidative stress in the mechanism of sleep deprivation-induced pain sensitization seems reasonable. This article comprehensively reviews the current research on the interrelationship between sleep deprivation, pain and the crucial role of oxidative stress.

Long-term hematopoietic transfer of the anti-cancer and lifespan-extending capabilities of a genetically engineered blood system by transplantation of bone marrow mononuclear cells.

A causal relationship exists among the aging process, organ decay and disfunction, and the occurrence of various diseases including cancer. A genetically engineered mouse model, termed Klf1K74R/K74R or Klf1(K74R), carrying mutation on the well-conserved sumoylation site of the hematopoietic transcription factor KLF1/EKLF has been generated that possesses extended lifespan and healthy characteristics, including cancer resistance. We show that the healthy longevity characteristics of the Klf1(K74R) mice, as exemplified by their higher anti-cancer capability, are likely gender-, age-, and genetic background-independent. Significantly, the anti-cancer capability, in particular that against melanoma as well as hepatocellular carcinoma, and lifespan-extending property of Klf1(K74R) mice, could be transferred to wild-type mice via transplantation of their bone marrow mononuclear cells at a young age of the latter. Furthermore, NK(K74R) cells carry higher in vitro cancer cell-killing ability than wild-type NK cells. Targeted/global gene expression profiling analysis has identified changes in the expression of specific proteins, including the immune checkpoint factors PDCD and CD274, and cellular pathways in the leukocytes of the Klf1(K74R) that are in the directions of anti-cancer and/or anti-aging. This study demonstrates the feasibility of developing a transferable hematopoietic/blood system for long-term anti-cancer and, potentially, for anti-aging.

Tuning A-Site Cation Deficiency in Pr0.5La0.5BaCo2O5+ δ Perovskite to Realize Large-Scale Hydrogen Evolution at 2000 mA cm-2.

Industrial-level hydrogen production from the water electrolysis requires reducing the overpotential (η) as much as possible at high current density, which is closely related to intrinsic activity of the electrocatalysts. Herein, A-site cation deficiency engineering is proposed to screen high-performance catalysts, demonstrating effective Pr0.5- xLa0.5BaCo2O5+ δ (P0.5- xLBC) perovskites toward alkaline hydrogen evolution reaction (HER). Among all perovskite compositions, Pr0.4La0.5BaCo2O5+ δ (P0.4LBC) exhibits superior HER performance along with unique operating stability at large current densities (J = 500-2000 mA cm-2 geo). The overpotential of ≈636 mV is achieved in P0.4LBC at 2000 mA cm-2 geo, which outperforms commercial Pt/C benchmark (≈974 mV). Furthermore, the Tafel slope of P0.4LBC (34.1 mV dec-1) is close to that of Pt/C (35.6 mV dec-1), reflecting fast HER kinetics on the P0.4LBC catalyst. Combined with experimental and theoretical results, such catalytic activity may benefit from enhanced electrical conductivity, enlarged Co-O covalency, and decreased desorption energy of H* species. This results highlight effective A-site cation-deficient strategy for promoting electrochemical properties of perovskites, highlighting potential water electrolysis at ampere-level current density.

Tetra-Ln3+-Implanted Tellurotungstates Covalently Modified by dl-Malic Acid: Proton Conduction and Photochromic Properties.

Three unique dl-malic acid covalently modified tetra-Ln3+-implanted tellurotungstates [H2(CH3)2]9NaH9[Ln4(H2O)14W6O13(OH)5(Mal)2(B-α-TeW9O33)4]·48H2O [Ln = La3+ (1), Ce3+ (2), Pr3+ (3); H3Mal = dl-malic acid] were fabricated by reacting Na2TeO3, Na2WO4·2H2O, Mal, and LnCl3·6H2O with dimethylamine hydrochloride in an aqueous solution. The most prominent architectural feature of these compounds is the covalent connection mode of an organic ligand and a polyoxometallate backbone, which is relatively rare in the realm of polyoxotungstates. The tetrameric polyanion can be deemed as four [TeW9O33]8- fragments fused together via an intriguing hexanuclearity [W6O13(OH)5(Mal)2Ln4(H2O)14]13+ cluster. Impedance measurements manifest that all three complexes display splendid proton conduction properties, with an exceptional conductivity for 2 up to 2.48 × 10-2 S·cm-1 under 85 °C and 95% relative humidity. Moreover, compounds 1 and 3 exhibited fast reversible photochromic properties with allochroic half-life periods t1/2 of 1.046 and 0.544 min, respectively.

Transient Acute Diplopia as a Rare Side Effect of Hydromorphone: A Case Report.

Diplopia, or double vision, has been listed as a rare adverse effect of intravenous hydromorphone, although there are no case studies or literature documenting this. We detail a case of acute transient diplopia correlated with the use of intraoperative hydromorphone and postoperative hydromorphone patient-controlled analgesia. Although the mechanism for this adverse effect is unknown, there may be risk factors that predispose patients to the potential toxic metabolic effects of hydromorphone. We share the first published case of diplopia as a clinically relevant adverse effect of hydromorphone and propose a potential reason behind this association.

Intensifying Photocatalytic Baeyer-Villiger Oxidation of Ketones with the Introduction of Ru Metalloligands and Bimetallic Units in POM@MOF.

The synthesis of visible light-responsive and efficient photocatalysts toward green Baeyer-Villiger oxidation organic synthesis is of extraordinary significance. In this work, we have synthesized two examples of visible light responsive crystalline polyoxometalate@metal-organic framework materials Ru-NiMo and Ru-CoMo by introducing Ru metalloligands and {CdM3O12} bimetallic units (M = Ni or Co). This is the first report of metalloligand-modified polyoxometalate@metal-organic framework materials with bimetallic nodes, and the materials form a three-dimensional framework directly through coordination bonds between {CdM3O12} bimetallic units and metalloligands. In particular, Ru-NiMo can achieve efficient photocatalytic conversion of cyclohexanone to ε-caprolactone in yields as high as 95.5% under visible light excitation in the range of λ > 400 nm, achieving a turnover number and turnover frequency of 955 and 440 h-1, respectively, which are the best known photocatalysts for Baeyer-Villiger oxidation, while apparent quantum yield measured at 485 nm is 4.4%. Moreover, Ru-NiMo exhibited excellent structural stability and recyclability, producing a 90.8% yield after five cycles of recycling.

James Watt, of Steam Engine Fame, Offered Inhaled Carbon Monoxide for Putative Therapeutic Action.

James Watt (1736-1819) is remembered as a steam engine innovator and industrial magnate. A polymath, he was also a hands-on contributor to the Medical Pneumatic Institution of Thomas Beddoes. Watt recruited Humphry Davy, who there discovered analgesic action of inhaled nitrous oxide in 1799. Watt also built pneumatic equipment, and he introduced a gas mixture, dubbed hydro-carbonate, as a medical tonic. The bioactive component was carbon monoxide, a readily-lethal inhibitor of the transport and utilization of respiratory oxygen. Despite appreciable toxicity, carbon monoxide is an endogenous product of heme catabolism, and low doses of the gas are under laboratory investigation for therapeutic purposes. However, Watt's hydro-carbonate constituted a setback in the development of pharmacologically useful gases.

Two binuclear Ni-inserted polyoxotantalates based on {NiTa10O32} units with catalytic activity.

Two Ni-inserted polyoxotantalates, K5.5Na2H0.5[Ni(H2O)2{NiTa10O30(OH)2}]·21H2O (1) and K6Na4[Ni(en){NiTa10O32}]·22H2O (2, en = ethanediamine), were synthesized in this work. Crystallographic data analyses reveal that 1 and 2 have similar configurations. A minor difference between these two structures is that the {Ni(H2O)2} unit in 1 is replaced by {Ni(en)} unit in 2. Notably, the other Ni in 1 and 2 is located as a heteroatom at the center of the {Ta10} unit, which is reported in POTas for the first time. Moreover, 2 exhibits excellent catalytic performance in transesterification reactions in a preliminary exploration of the catalytic ability of the synthesized POTas.

Synthesis and Characterization of 6-Ti-Substituted Polyoxomolybdate with High Catalytic Activity for Sulfide Oxidation.

A 6-Ti-substituted polyoxometalate, (NH4)5Cs7Na3H2[Cs@(Ti2GeMo10O39)3]·34H2O (1), was synthesized by reacting (NH4)6Mo7O24·4H2O, GeO2, and TiOSO4 through the conventional aqueous method. Polyanion 1a is composed of three {Ti2GeMo10} segments linked by Ti-O-Ti linkages and shows a trefoil-shaped structure. Furthermore, one Cs+ cation is encapsulated in the cavity of 1a. Notably, it possesses the highest number of Ti centers among the reported polyoxomolybdates. In addition, serving as a high-efficiency heterogeneous catalyst, 1 enables the conversion of methyl phenyl sulfide within 20 min, yielding 96.4% of the corresponding sulfoxide with good recyclability.

Photocatalytic Reduction of Nitrobenzene to Aniline by an Intriguing {Ru(C6H6)}-Based Heteropolytungstate.

In this paper, we have successfully synthesized a structurally novel heteropolytungstate via coordination of four {Ru(C6H6)} and trivacant {TeW9O33} clusters, formulated as Cs4Na2H2[Te2W20O72(H2O){(C6H6)Ru}4]·12H2O (1). Compound 1 inherited the strong absorption of [Ru(C6H6)Cl2]2 in the visible region and {TeW9O33} in the UV region, providing a good basis for photocatalysis. As expected, compound 1 showed good photocatalytic activity in the visible-light-driven reduction of nitrobenzene using N2H4·H2O as a reductant with a yield of 99.8%, a high turnover number (TON = 330), and a high turnover frequency (TOF = 24 h-1). The cyclic experiment of nitrobenzene reduction indicated that compound 1 was an effective and stable heterogeneous catalyst. Finally, the nitrobenzene reduction pathway was affirmed using condensation with azobenzene as a reaction intermediate based on control experiments.