Highly Efficient Self-Assembly of Heterometallic [2]Catenanes and Cyclic Bis[2]catenanes via Orthogonal Metal-Coordination Interactions.

Although catenated cages have been widely constructed due to their unique and elegant topological structures, cyclic catenanes formed by the connection of multiple catenane units have been rarely reported. Herein, based on the orthogonal metal-coordination-driven self-assembly, we prepare a series of heterometallic [2]catenanes and cyclic bis[2]catenanes, whose structures are clearly evidenced by single-crystal X-ray analysis. Owing to the multiple positively charged nature, as well as the potential synergistic effect of the Cu(I) and Pt(II) metal ions, the cyclic bis[2]catenanes display broad-spectrum antibacterial activity. This work not only provides an efficient strategy for the construction of heterometallic [2]catenanes and cyclic bis[2]catenanes but also explores their applications as superior antibacterial agents, which will promote the construction of advanced supramolecular structures for biomedical applications.

Multicomponent, Multicavity Metallacages That Contain Different Binding Sites for Allosteric Recognition.

The encapsulation of different guest molecules by their different recognition domains of proteins leads to selective binding, catalysis, and transportation. Synthetic hosts capable of selectively binding different guests in their different cavities to mimic the function of proteins are highly desirable but challenging. Here, we report three ladder-shaped, triple-cavity metallacages prepared by multicomponent coordination-driven self-assembly. Interestingly, the porphyrin-based metallacage is capable of heteroleptic encapsulation of fullerenes (C60 or C70) and coronene using its different cavities, allowing distinct allosteric recognition of coronene upon the addition of C60 or C70. Owing to the different binding affinities of the cavities, the metallacage hosts one C60 molecule in the central cavity and two coronene units in the side cavities, while encapsulating two C70 molecules in the side cavities and one coronene molecule in the central cavity. The rational design of multicavity assemblies that enable heteroleptic encapsulation and allosteric recognition will guide the further design of advanced supramolecular constructs with tunable recognition properties.

Statistical-physical method for simulating the transport of microplastic-antibiotic compound pollutants in typical bay area.

Microplastics and antibiotics are emerging pollutants in the environment and have received widespread attention globally. In coastal areas, microplastic and antibiotic pollution is ubiquitous and often overlapping. Microplastic-antibiotic compound pollutants that are formed through adsorption have thus become a major concern. However, modeling knowledge of microplastic transport in coastal areas is still limited, and research on the impact of compound pollutants caused by Polythene (PE)-antibiotics in such settings is in early stages. In this study, using a lattice Boltzmann method (LBM) and temporal Markov method (TMM) under a statistical-physical framework, we simulated pollutant transport and PE-antibiotic compound pollutants in coastal areas. First, a series of models are proposed, including an LBM wave-current coupling model, an LBM antibiotic transport model, an LBM particle-tracking model, a TMM microplastic transport model and the final LBM-TMM hybrid compound pollutant model. Then, the suitability and applicability of the models was validated using experimental data and numerical simulations. Finally, the models were applied to a study area, Laizhou Bay (China). The simulation results demonstrate that adsorption will reduce the concentration of antibiotics in the water environment. Within 44 days, the adsorbed antibiotic carried by PE particles migrate further, and the width of the pollution zone escalates from 234.2 m to 689.0 m.

Fibroblast growth factor 21 predicts arteriovenous fistula functional patency loss and mortality in patients undergoing maintenance hemodialysis.

BACKGROUND: Arteriovenous fistula (AVF) dysfunction is a common complication in patients undergoing maintenance hemodialysis (MHD). Elevated serum levels of fibroblast growth factor 21 (FGF21) are associated with atherosclerosis and cardiovascular mortality. However, its association with vascular access outcomes remains elusive. The present study evaluated the relationship of serum FGF21 levels with AVF dysfunction and all-cause mortality in patients undergoing MHD. METHODS: We included patients undergoing MHD using AVF from January 2018 to December 2019. FGF21 concentration was detected using enzyme-linked immunosorbent assay. Patients were followed up to record two clinical outcomes, AVF functional patency loss and all-cause mortality. The follow-up period ended on April 30, 2022. RESULTS: Among 147 patients, the mean age was 58.49 ± 14.41 years, and the median serum level of FGF21 was 150.15 (70.57-318.01) pg/mL. During the median follow-up period of 40.83 months, the serum level of FGF21 was an independent risk factor for AVF functional patency loss (per 1 pg/mL increase, HR 1.002 [95% CI: 1.001-1.003, p = 0.003]). Patients with higher serum levels of FGF21 were more likely to suffer from all-cause mortality (per 1 pg/mL increase, HR 1.002 [95% CI: 1.000-1.003, p = 0.014]). The optimal cutoffs for FGF21 to predict AVF functional patency loss and all-cause mortality in patients undergoing MHD were 149.98 pg/mL and 146.43 pg/mL, with AUCs of 0.701 (95% CI: 0.606-0.796, p < 0.001) and 0.677 (95% CI: 0.595-0.752, p = 0.002), respectively. CONCLUSIONS: Serum FGF21 levels were an independent risk factor and predictor for AVF functional patency loss and all-cause mortality in patients undergoing MHD.

Accuracy of the Cage Placement in Oblique Lumbar Interbody Fusion and its Effects on the Radiological Outcome in Lumbar Degenerative Disease.

STUDY DESIGN: A retrospective study. OBJECTIVES: This study aimed to check how accurately cages were inserted and how they affected the radiological results in oblique lumbar interbody fusion (OLIF) at L2-L5. METHODS: A total of 137 patients diagnosed with lumbar degenerative disease, 184 intervertebral discs were included. We used a new cage deviation classification system on magnetic resonance imaging (MRI) to determine cage insertion accuracy. Cage deviation angles (CDA) were classified into four groups based on the angle formed by the long axis of the cage and the horizontal axis of the vertebral body. Other radiological parameters on plain radiographs and MRI were compared based on this classification. RESULTS: Among 183 cages, 19 were in zone Ⅰ-Ⅱ (10.32%), 163 were in zone II-III (88.59%), and two were in zone III-IV (1.09%). The median cage deviation was 4.97°. No significant differences (H = 2.479, P = .290 > .05) of CDA were found among different segments. Posterior cage deviation accounted 94.57%. The minimal, mild, moderate, and severe cage deviation was 89 (48.4%), 51 (27.7%), 30 (16.3%), and 14 (7.6%) respectively. No differences in radiological parameter changes were noted among different cage obliquity categories. CONCLUSIONS: Approximately 98.91% of cages were placed in zones I-II and II-III. Most cages deviated posteriorly with CDA ranging minimal to moderate. Minimal to moderate cage deviation did not impact radiological outcomes significantly in OLIF at L2-L5. However, avoiding severe cage deviation is crucial to prevent contralateral traversing nerve root injuries.

Unraveling the rate-limiting step in microorganisms' mediation of denitrification and phosphorus absorption/transport processes in a highly regulated river-lake system.

River-lake ecosystems are indispensable hubs for water transfers and flow regulation engineering, which have frequent and complex artificial hydrological regulation processes, and the water quality is often unstable. Microorganisms usually affect these systems by driving the nutrient cycling process. Thus, understanding the key biochemical rate-limiting steps under highly regulated conditions was critical for the water quality stability of river-lake ecosystems. This study investigated how the key microorganisms and genes involving nitrogen and phosphorus cycling contributed to the stability of water by combining 16S rRNA and metagenomic sequencing using the Dongping river-lake system as the case study. The results showed that nitrogen and phosphorus concentrations were significantly lower in lake zones than in river inflow and outflow zones (p < 0.05). Pseudomonas, Acinetobacter, and Microbacterium were the key microorganisms associated with nitrate and phosphate removal. These microorganisms contributed to key genes that promote denitrification (nirB/narG/narH/nasA) and phosphorus absorption and transport (pstA/pstB/pstC/pstS). Partial least squares path modeling (PLS-PM) revealed that environmental factors (especially flow velocity and COD concentration) have a significant negative effect on the key microbial abundance (p < 0.001). Our study provides theoretical support for the effective management and protection of water transfer and the regulation function of the river-lake system.

Coexistence of Subcutaneous Panniculitis-Like T-Cell Lymphoma and Dermatomyositis in a 12-Year-Old Boy.

Subcutaneous panniculitis-like T-cell lymphoma (SPTL) is an extremely rare, indolent skin malignancy that can be difficult to distinguish from autoimmune disease-associated panniculitides. Here, we describe a 12-year-old boy who was diagnosed at age 7 years with dermatomyositis with classical manifestations, including poikiloderma, Gottron's sign, and symmetric muscle weakness. Recently, the boy presented multiple subcutaneous nodules and fever. Histopathological examination and immunohistochemical staining revealed coexistence of SPTL. To our knowledge, this is the first case of dermatomyositis accompanied with SPTL. This case alert clinical physicians of the possibility of SPTL should be considered when a patient with dermatomyositis has new lesions presenting as nodules and unknown fever.

Isoreticular Preparation of Tetraphenylethylene-based Multicomponent Metallacages towards Light-Driven Hydrogen Production.

Multicomponent metallacages can integrate the functions of their different building blocks to achieve synergetic effects for advanced applications. Herein, based on metal-coordination-driven self-assembly, we report the preparation of a series of isoreticular tetraphenylethylene-based metallacages, which are well characterized by multinuclear NMR, ESI-TOF-MS and single-crystal X-ray diffraction techniques. The suitable integration of photosensitizing tetraphenylethylene units as faces and Re catalytic complexes as the pillars into a single metallacage offers a high photocatalytic hydrogen production rate of 1707 µmol g-1 h-1 , which is one of the highest values among reported metallacages. Femtosecond transient absorption and DFT calculations reveal that the metallacage can serve as a platform for the precise and organized arrangement of the two building blocks, enabling efficient and directional electron transfer for highly efficient photocatalytic performance. This study provides a general strategy to integrate multifunctional ligands into a certain metallacage to improve the efficiency of photocatalytic hydrogen production, which will guide the future design of metallacages towards photocatalysis.

Hexaphenyltriphenylene-Based Multicomponent Metallacages: Host-Guest Complexation for White-Light Emission.

A hexaphenyltriphenylene-based hexatopic pyridyl ligand is designed and used to prepare three hexagonal prismatic metallacages via metal-coordination-driven self-assembly. Owing to the planar conjugated structures of the hexaphenyltriphenylene skeleton, such metallacages show good host-guest complexation with a series of emissive dyes, which have been further used to tune their emission in solution. Interestingly, based on their complementary emission colors, white light emission is achieved in a mixture of the host metallacages and the guests.

Successful treatment with secukinumab of psoriasis-like dermatitis in a patient with holocarboxylase synthetase deficiency.

Holocarboxylase synthetase deficiency (HSD) is a rare autosomal recessive disorder of biotin metabolism. Typical manifestations include irreversible metabolic disorders and erythroderma-like dermatitis. Most patients respond well to biotin supplementation. Psoriasis-like phenotype associated with this disease has been rarely reported in the literature and experiences with the use of biologics in patients with HSD are still lacking. We reported a rare case of recurrent psoriasis-like skin lesions in a 6-year-old child with HSD. The patient did not respond to initial therapy with high-dose oral biotin. Immunofluorescence staining showed an increased number of interleukin (IL)-17A+ cells in his skin lesions. Based on this finding, the patient was successfully treated with human anti-IL-17A monoclonal antibody (secukinumab). He did not report any side effects and remained healthy during the 2-year follow-up. We provide a comprehensive review of the reported cases of HSD with psoriasis-like dermatitis to date. The psoriasis-like phenotype of HSD is controversial in treatment and IL-17A inhibitor is an alternative therapeutic option.

Viscoelastic Behavior and Constitutive Relation of Heavy Crude Oils.

Heavy crude oil exhibits very complex viscoelastic behaviors due to its complex composition of resins, asphaltenes, saturates, and aromatics. It has a great influence on oil production and transportation. In this work, the viscoelastic behaviors of three different heavy crude oils were measured using a rotational rheometer. In conclusion, all of these heavy crude oils display linear viscoelastic behaviors in the experimental range. The loss modulus (E″) of the three crude oils decreased as the experimental temperature increased, and the variation trends of the three crude oils were basically the same. However, the experimental temperature has almost no effect on the storage modulus (E'), which always retained a constant value of 0.4 Pa. Furthermore, the storage modulus (E') and loss modulus (E″) increase as the angular frequency increases. To describe the physical deformation characteristics of viscoelastic materials, the generalized Maxwell model and the fractional derivative Maxwell model are used to establish the constitutive relation of heavy crude oil. In conclusion, the generalized Maxwell model and the fractional derivative Maxwell model can predict the experimental results very well. All of the square of the correlation coefficient (R 2) values are greater than 0.95. However, the number of fitting parameters for the fractional derivative Maxwell model is less than that for the fourth-order generalized Maxwell model which can save the calculating time. Therefore, the fractional derivative Maxwell model is suggested to describe the viscoelastic behavior of heavy crude oil in industrial applications.

Porphyrin-Based Multicomponent Metallacage: Host-Guest Complexation toward Photooxidation-Triggered Reversible Encapsulation and Release.

The development of supramolecular hosts with effective host-guest properties is crucial for their applications. Herein, we report the preparation of a porphyrin-based metallacage, which serves as a host for a series of polycyclic aromatic hydrocarbons (PAHs). The association constant between the metallacage and coronene reaches 2.37 × 107 M-1 in acetonitrile/chloroform (ν/ν = 9/1), which is among the highest values in metallacage-based host-guest complexes. Moreover, the metallacage exhibits good singlet oxygen generation capacity, which can be further used to oxidize encapsulated anthracene derivatives into anthracene endoperoxides, leading to the release of guests. By employing 10-phenyl-9-(2-phenylethynyl)anthracene whose endoperoxide can be converted back by heating as the guest, a reversible controlled release system is constructed. This study not only gives a type of porphyrin-based metallacage that shows desired host-guest interactions with PAHs but also offers a photooxidation-responsive host-guest recognition motif, which will guide future design and applications of metallacages for stimuli-responsive materials.

Hexaphenylbenzene-Based Deep Blue-Emissive Metallacages as Donors for Light-Harvesting Systems.

We herein report the preparation of a series of hexaphenylbenzene (HPB)-based deep blue-emissive metallacages via multicomponent coordination-driven self-assembly. These metallacages feature prismatic structures with HPB derivatives as the faces and tetracarboxylic ligands as the pillars, as evidenced by NMR, mass spectrometry and X-ray diffraction analysis. Light-harvesting systems were further constructed by employing the metallacages as the donor and a naphthalimide derivative (NAP) as the acceptor, owing to their good spectral overlap. The judiciously chosen metallacage serves as the antenna, providing the suitable energy to excite the non-emissive NAP, and thus resulting in bright emission for NAP in the solid state. This study provides a type of HPB-based multicomponent emissive metallacage and explores their applications as energy donors to light up non-emissive fluorophores in the solid state, which will advance the development of emissive metallacages as useful luminescent materials.

Tetraphenylethylene-Based Multicomponent Emissive Metallacages as Solid-State Fluorescent Materials.

The construction of solid-state fluorescent materials with high quantum yield and good processability is of vital importance in the preparation of organic light-emitting devices. Herein, a series of tetraphenylethylene (TPE)-based multicomponent emissive metallacages are prepared by the coordination-driven self-assembly of tetra-(4-pyridylphenyl)ethylene, cis-Pt(PEt3 )2 (OTf)2 and tetracarboxylic ligands. These metallacages exhibit good emission both in solution and in the solid state because the coordination bonds and aggregation restrict the molecular motions of TPE synergistically, which suppresses the non-radiative decay of these metallacages. Impressively, one of the metallacages achieves very high fluorescence quantum yield (ΦF =88.46 %) in the solid state, which is further used as the coatings of a blue LED bulb to achieve white-light emission. The study not only provides a general method to the preparation of TPE-based metallacages but also explores their applications as solid-state fluorescent materials, which will promote the future design and applications of metallacages as useful emissive devices.

Meta-analysis of the response of marine phytoplankton to nutrient addition and seawater warming.

As an indispensable part of the marine ecosystem, phytoplankton are important prey for zooplankton and various marine animals with important commercial value. The influence of seawater warming and eutrophication on phytoplankton communities is well known, but few studies have explained the effects of the interaction between temperature and nutrients on marine phytoplankton. Through meta-analysis and meta-regression, the phytoplankton responses to the effects of nutrient addition and seawater warming were evaluated in this study. Nitrogen (N) addition led to an increase in phytoplankton biomass, while phosphorus (P) had no significant effect on phytoplankton biomass. However, this result may be biased by the uneven distribution of the research area. N limitation is widespread in the areas where these collected studies were conducted, including many parts of North and South Atlantic and West Pacific Oceans. The key limiting nutrient in other areas lacking corresponding experiments, however, remain unclear. The effect of seawater warming was not significant, which indicates the uncertainty about the effect of temperature on phytoplankton. The results of ANOVA show that nutrient addition and seawater warming had similar effects in various marine habitats (coastal regions, estuaries and open seas), while salinity could have caused the difference in the N effects among the three habitats. Furthermore, our results showed that the impact of temperature depends on nutrient conditions, especially N status, which has rarely been considered before. This result demonstrated the importance of evaluating nutrient limitation patterns when studying climate warming. The impact of rising temperatures may need to be reevaluated because N limitation is common.

PBN protects NP cells from AAPH-induced degenerative changes by inhibiting the ERK1/2 pathway.

Aim: Intervertebral disc (IVD) degeneration (IDD) is one of the main causes for spinal degenerative diseases, such as disk herniation, spinal canal stenosis, and spinal deformities. Growing evidence has highlighted the contribution of oxidative stress in pathogenesis of IDD, and antioxidant treatment is thus considered to be a promising therapeutic strategy for IDD. The aim of this study was to investigate whether N-tert-butyl-α-phenylnitrone (PBN), a free radical scavenger, could attenuate the pathological changes of IDD by alleviating oxidative stress.Materials and Methods: Nucleus pulposus (NP) cells were isolated from rabbit lumbar disks. MTT assay, real-time PCR and western blotting were employed to evaluate the effects of PBN on oxidative damages induced by 2,2'-azobis (2-amidinopropane) dihydrochloride (AAPH) in NP cells.Results: AAPH induced oxidative stress and the subsequent degenerative changes in NP cells via the ERK/MAPK pathway. On the contrary, the oxidative stress induced by AAPH was significantly ameliorated by PBN. Moreover, PBN also attenuated AAPH-induced expression of matrix degradation proteases and apoptosis. PBN suppresses AAPH-induced activation of ERK/MAPK pathway, which may be the underlying mechanism for the protective effects of PBN.Conclusions: Our study for the first time identified a novel role and mechanism for PBN in protecting the IVD against oxidative stress, matrix catabolism and apoptosis, which may have implications for its further application in combating IVD degenerative diseases.Abbreviations: AAPH: 2,2'-azobis(2-methylpropanimidamidine) dihydrochloride; ADAMTS: a disintegrin and metalloproteinase with thrombospondin motifs; AF: annulus fibrosus; CEP: cartilage endplate; DCF: 2'7'-dichlorofluorescein; IDD: intervertebral disc degeneration; IVD: intervertebral disc; LPS: lipopolysaccharide; MMP: matrix metalloproteinase; MTT: methyl-thiazolyl-tetrazolium; NP: nucleus pulposus; PBN: N-tert-butyl-alfa-phenylnitrone; PGs: proteoglycans; ROS: reactive oxygen species; SDS: sodium dodecyl sulfate.

Effects of sulfasalazine combined with moxibustion methods on patients with cold-dampness obstruction type ankylosing spondylitis.

Twenty-four patients with cold, dampness, obstructive ankylosing spondylitis were treated with sulfasalazine and sulfasalazine in combination with moxibustion for 3 weeks. The results showed that the combined treatment of traditional Chinese and western medicine was significantly higher than those of western medicine treatment, meanwhile, the scoreofsymptoms quantification, C-reactive protein and erythrocyte sedimentation rate of the integrated Chinese and western medicine treatment were significantly lower than those of western medicine treatment, and the level of physical signs was significantly higher than that of western medicine treatment, and there were no significant differences in adverse reactions. Moxibustion combined with sulfasalazine in the treatment of cold and damp obstructive ankylosing spondylitis can effectively improve the characteristics of the body, relieve pain symptoms and improve the prognosis.

Numerical study of the antibiotic transport and distribution in the Laizhou Bay, China.

A large number of antibiotic residues are discharged into aquatic environments due to the widespread use of antibiotics in daily life. After a series of processes in the water, the residues will potentially have adverse impacts on water ecosystem and human health. Therefore, it is critical for mediating the pollution to know how the antibiotics transport and distribute in the water. This study utilizes a two-dimensional lattice Boltzmann model to find out the transport and distribution of antibiotics in a highly polluted area, the Laizhou Bay in China. Furthermore, the model was used to simulate two scenarios in the Laizhou Bay, the antibiotics from sewage treatment plants and the contamination of mariculture. The simulated results show that the model as an effective tool can provide a useful basis for the management of antibiotics-related environmental issues in the Laizhou Bay.

[Intervention with thumbtack needling on spinal low back pain in Air Force crew: a randomized controlled trial].

OBJECTIVE: To observe the clinical effect on spinal low back pain (SLBP) in Air Force crew treated with novel thumbtack needling therapy and to analyze the relevant factors of the therapeutic effect. METHODS: A total of 120 Air Force crew with SLBP were randomized into a thumbtack needling group (40 cases), an external treatment group (40 cases, 1 case dropped off ) and a combined treatment group (40 cases, 1 case dropped off ). In the thumbtack needling group, the thumbtack needling therapy was adopted. The novel thumbtack needles were inserted at the lower No.6 region of the wrist-ankle acupuncture, Yaotongdian (EX-UE 7), Yaoyangguan (GV 3), etc. Each point was pressed and kneaded for 1 min each time, 3 or 4 times a day. The treatment for 3 days was taken as one course. At the interval of 2 days, 3 courses were required totally. In the external treatment group, shangshi zhitong plaster was compressed on the center of the tender site in the lumbar region, once daily, consecutively for 6 days as one course. At an interval of 1 day, 2 courses were required totally. In the combined treatment group, the treatments in the thumbtack needling group and the external treatment group were used in combination. Before and after treatment, McGill score and the score of Oswestry dysfunction index (ODI) were compared in the patients among the three groups. The average EMG (AEMG) and the mean power frequency (MPF) were analyzed by using JE-TB0810 electromyography (EMG) acquisition system to evaluate the erector spinae tension in the patients before and after treatment. The clinical effect was observed in the patient of each group and the safety was evaluated. Logistic analysis was performed on the relevant factors of therapeutic effect in the patients. RESULTS: Compared with the values before treatment, McGill scores and ODI scores were reduced (P<0.05), and AEMG and MPF increased in the patients of each group after treatment (P<0.05). After treatment, McGill scores and ODI scores in the thumbtack needling group and the combined treatment group were lower than those in the external treatment group (P<0.05), and AEMG and MPF were higher than the external treatment group (P<0.05). The total effective rates were 87.5% (35/40) and 87.2% (34/39) in the thumbtack needling group and the combined treatment group respectively and were higher than 64.1% (25/39) in the external treatment group (P<0.05). The incidence of the adverse reaction in the combined treatment group was higher than the other two groups (P<0.05). The weekly exercise frequency was the independent factor of the therapeutic effect (OR =12.166, P<0.001). CONCLUSION: The thumbtack needling therapy is significantly effective on spinal low back pain in Air Force crew and is of the safety. Hence, this therapy is applicable to be promoted in the primary care army hospital.