Oxidised low-density lipoprotein and antibodies against oxidised low-density lipoprotein in patients with antiphospholipid syndrome.

OBJECTIVES: Recurrent thrombosis is one of the main clinical features of antiphospholipid syndrome (APS), and recent studies revealed that APS shares similar pathophysiological mechanisms with atherosclerosis. Oxidised low-density lipoprotein (OxLDL) and antibodies against OxLDL (anti-OxLDL) are involved in the development of atherosclerosis. This study aims to investigate the clinical significance of OxLDL and anti-OxLDL in APS patients. METHODS: One hundred and seventy APS patients and 39 healthy controls (HC) were enrolled. Clinical and laboratory data were collected from Clinical Data Center of Peking University People's Hospital. OxLDL and anti-OxLDL were detected using enzyme-linked immunosorbent assay. RESULTS: Among the 170 APS patients, 106 had isolated thrombotic APS. Compared with HC, APS patients exhibited higher titres of OxLDL [413.86 (220.11-853.67) ng/mL vs. 45.54 (0-105.98) ng/mL, p<0.001] and anti-OxLDL [107.62 (75.68-174.18) U/L vs. 44.13 (18.44-79.76) U/L, p<0.001]. Also, APS patients exhibited a higher positivity rate for OxLDL (88.2% vs. 5.1%, p<0.001) and anti-OxLDL (84.1% vs. 36.5%, p<0.001) compared to HC. APS patients with elevated levels of OxLDL had a higher rate of LAC positivity (68.0% vs. 45.0%, p=0.042). Furthermore, APS patients with positive anti-OxLDL demonstrated a higher occurrence of venous thrombosis (46.2% vs. 18.5%, p=0.008) and a lower rate of Coomb's test positivity (52.6% vs. 76.2%, p=0.049). Multivariate logistic regression revealed that anti-OxLDL positivity (OR 12.424, 95%CI 1.108-139.330, p=0.041) were risk factors for venous thrombotic APS. CONCLUSIONS: This study indicates that the presence of anti-OxLDL may serve as potential markers for venous thrombosis in APS patients. OxLDL and anti-OxLDL may function as valuable biomarkers for monitoring APS.

Plasma Apo-E mediated corticospinal tract abnormalities and suicidality in patients with major depressive disorder.

This study aims to explore the link between Apo-E, brain white matter, and suicide in patients with major depressive disorder (MDD) to investigate the potential neuroimmune mechanisms of Apo-E that may lead to suicide. Thirty-nine patients with MDD (22 patients with suicidality) and 57 age, gender, and education-matched healthy controls participated in this study, provided plasma Apo-E samples, and underwent diffusion tensor imaging scans. Plasma Apo-E levels and white matter microstructure were analyzed among the MDD with suicidality, MDD without suicidality, and HC groups using analysis of variance with post hoc Bonferroni correction and tract-based spatial statistics (TBSS) with threshold-free cluster enhancement correction. Mediation analysis investigated the relationship between Apo-E, brain white matter, and suicidality in MDD. The MDD with suicidality subgroup had higher depressive and suicide scores, longer disease course, and lower plasma Apo-E levels than MDD without suicidality. TBSS revealed that the MDD non-suicide subgroup showed significantly increased mean diffusivity in the left corticospinal tract and body of the left corpus callosum, as well as increased axial diffusivity in the left anterior corona radiata and the right posterior thalamic radiation compared to the suicidal MDD group. The main finding was that the increased MD of the left corticospinal tract contributed to the elevated suicide score, with Apo-E mediating the effect. Preliminary result that Apo-E's mediating role between the left corticospinal tract and the suicide factor suggests the neuroimmune mechanism of suicide in MDD. The study was registered on ClinicalTrials.gov (NCT03790085).

H2/D2 Separation Using UTSA-16@CAU-10-H@γ-AlOOH Composites as the Stationary Phase in Gas Chromatography via the Additive Effects of Kinetic Sieving and Chemical Affinity Quantum Sieving.

In this work, CAU-10-H@γ-AlOOH is prepared, and then UTSA-16 is loaded on CAU-10-H@γ-AlOOH to obtain UTSA-16@CAU-10-H@γ-AlOOH. Using the as-prepared composites as stationary materials by cryogenic gas chromatography at 77 K, while CAU-10-H@γ-AlOOH achieves the complete separation of ortho-H2 (o-H2) and D2 with a resolution R of 1.66 and a separation time t of 9.52 min, UTSA-16@CAU-10-H@γ-AlOOH achieves higher efficiency separation of hydrogen isotopes in a shorter separation time (4.56 min) with R = 1.7. Molecular simulation results show that CAU-10-H has both chemical affinity quantum sieving and kinetic sieving effects for H2/D2 at 77 K, and UTSA-16 can only exert the kinetic sieving effect. UTSA-16's load on CAU-10-H@γ-AlOOH weakens the adsorption of hydrogen isotopes, and the presence of Co2+ in UTSA-16 promotes the conversion of para-H2 to ortho-H2. In gas chromatography, H2 was preferentially desorbed from the system due to strong D2 adsorption caused by the chemical affinity quantum sieving effect and faster H2 diffusion caused by the kinetic sieving effect. These additive effects achieved efficient hydrogen isotope separation at 77 K.

Efficacy and safety of tocilizumab in Behçet's syndrome with refractory arterial lesions: a single-centre observational cohort study in China.

OBJECTIVE: The aim of this observational cohort study was to assess the effectiveness and safety of the IL-6-receptor inhibitor tocilizumab (TCZ) in Behçet's syndrome (BS) with refractory arterial involvement. METHODS: Ten patients admitted to the Rheumatology and Immunology Department of Peking University People's Hospital between January 2014 and December 2019 were enrolled. The enrolled patients met the BS international criteria and exhibited severe arterial impairments. Refractory arterio-BS was diagnosed based on objective vascular symptoms unexplainable by other known illnesses, and resistance to traditional immunosuppressants and glucocorticoids after 12 weeks. Patients received 8 mg/kg TCZ infusions every 4 weeks for ≥24 weeks, with simultaneous continuation of immunosuppressants and glucocorticoids. Clinical and imaging data were assessed before and after TCZ treatment. RESULTS: The enrolled patients were men aged 44.3 (10.5) years; the median disease duration was 186.5 (45.7) months, and the average age of arterial impairment onset was 38.7 (12.9) years. The following trends were observed: improvement and maintenance of symptoms after the 26.8 (7.2)-month follow-up, n = 9; complete remission, n = 6; partial response, n = 3; immunosuppressant dose reduction, n = 4; radiologic improvement of arterial lesions, n = 4; and TCZ discontinuation owing to enlarged abdominal aortic aneurysm relapse, n = 1. The average daily glucocorticoid dose reduced from 54.5 (20.6) to 8.3 (3.6) mg/d (P < 0.001), while the median ESR and CRP values reduced from 50 (2-82) mm/h and 32.9 (2.1-62.3) mg/dl to 4 (1-10) mm/h and 2.9 (0.2-12.1) mg/dl, respectively (P < 0.001). No TCZ-associated side effects were noted. CONCLUSION: TCZ proved to be safe and effective for refractory arterial lesions in BS, with a steroid- and immunosuppressant-sparing benefit.

Loading and Sustained Release of Pralidoxime Chloride from Swellable MIL-88B(Fe) and Its Therapeutic Performance on Mice Poisoned by Neurotoxic Agents.

Maintaining a long-term continuous and stable reactivator blood concentration to treat organophosphorus nerve agent poisoning using acetylcholinesterase (AChE) reactivator pralidoxime chloride (2-PAM) is very important yet difficult. Because the flexible framework of MIL-88B(Fe) nanoparticles (NPs) can swell in polar solvents, pralidoxime chloride (2-PAM) was loaded in MIL-88B(Fe) NPs (size: ca. 500 nm) by stirring and incubation in deionized water to obtain 2-PAM@MIL-88B(Fe), which had a maximum drug loading capacity of 12.6 wt %. The as-prepared composite was characterized by IR, powder X-ray diffraction (P-XRD), scanning electron microscopy (SEM), ζ-potential, Brunauer-Emmett-Teller (BET), and thermogravimetry/differential thermal analysis (TG/DTA). The results showed that under constant conditions, the maximum drug release rates of 2-PAM@MIL-88B(Fe) in absolute ethanol, phosphate-buffered saline (PBS) solution (pH = 7.4), and PBS solution (pH = 4) at 150 h were 51.7, 80.6, and 67.1%, respectively. This was because the composite showed different swelling behaviors in different solvents. In PBS solution with pH = 2, the 2-PAM@MIL-88B(Fe) framework collapsed after 53 h and released 100% of 2-PAM. For mice after intragastric poisoning with sarin (a neurotoxic agent), an atropine-assisted 2-PAM@MIL-88B(Fe) treatment experiment revealed that 2-PAM@MIL-88B(Fe) continuously released 2-PAM for more than 72 h so that poisoned AChE was continuously and steadily reactivated. The reactivation rate of AChE was 56.7% after 72 h. This composite is expected to provide a prolonged, stable therapeutic drug for the mid- and late-stage treatment of neurotoxic agent poisoning.

Efficacy and safety of low-dose IL-2 in the treatment of systemic lupus erythematosus: a randomised, double-blind, placebo-controlled trial.

OBJECTIVES: Open-labelled clinical trials suggested that low-dose IL-2 might be effective in treatment of systemic lupus erythematosus (SLE). A double-blind and placebo-controlled trial is required to formally evaluate the safety and efficacy of low-dose IL-2 therapy. METHODS: A randomised, double-blind and placebo-controlled clinical trial was designed to treat 60 patients with active SLE. These patients received either IL-2 (n=30) or placebo (n=30) with standard treatment for 12 weeks, and were followed up for additional 12 weeks. IL-2 at a dose of 1 million IU or placebo was administered subcutaneously every other day for 2 weeks and followed by a 2-week break as one treatment cycle. The primary endpoint was the SLE Responder Index-4 (SRI-4) at week 12. The secondary endpoints were other clinical responses, safety and dynamics of immune cell subsets. RESULTS: At week 12, the SRI-4 response rates were 55.17% and 30.00% for IL-2 and placebo, respectively (p=0.052). At week 24, the SRI-4 response rate of IL-2 group was 65.52%, compared with 36.67% of the placebo group (p=0.027). The primary endpoint was not met at week 12. Low-dose IL-2 treatment resulted in 53.85% (7/13) complete remission in patients with lupus nephritis, compared with 16.67% (2/12) in the placebo group (p=0.036). No serious infection was observed in the IL-2 group, but two in placebo group. Besides expansion of regulatory T cells, low-dose IL-2 may also sustain cellular immunity with enhanced natural killer cells. CONCLUSIONS: Low-dose IL-2 might be effective and tolerated in treatment of SLE. TRIAL REGISTRATION NUMBER: ClinicalTrials.gov Registries (NCT02465580 and NCT02932137).

Combining Two into One: A Dual-Function H5PV2Mo10O40@MOF-808 Composite as a Versatile Decontaminant for Sulfur Mustard and Soman.

Due to the unpredictable nature of a battlefield environment, in the simultaneous degradation of sulfur mustard and nerve agents it is preferable to use just one decontaminant. Herein, the new composite HPVMo@MOF-808 (HPVMo = H5PV2Mo10O40) was deliberately synthesized via a simple impregnation method and thoroughly characterized. The results showed that the decontamination rate of the composites (30-40 mg) with optimal HPVMo loadings for HD (4 µL) and GD (4 µL) under ambient conditions was 97.2% (within 120 min) and 90.8% (within 30 min), respectively. Due to the combinational/synergistic effect of MOF-808 and encapsulated homogeneously dispersed HPVMo, the composite can very efficiently oxidize HD to nontoxic products in a single system, while retaining the inherent excellence of MOF-808 in hydrolytically degrading GD. The decontamination process was found to follow first-order reaction kinetics, and the rate constant and half-life of the composite for HD and GD were 0.0231 min-1, 30.13 min and 0.0795 min-1, 8.72 min, respectively. In addition, experimental results in guinea pigs and Kunming mice used as animal models showed that the composite provided effective skin protection against HD and GD, showing great potential for application in skin decontamination and protection.

Tea Consumption Is Associated with Decreased Disease Activity of Rheumatoid Arthritis in a Real-World, Large-Scale Study.

INTRODUCTION: The role of tea consumption on rheumatoid arthritis (RA) has been studied in recent years, but no clear conclusion has been drawn as a result of small sample size of the studies or the fact that only in vitro studies have been performed. OBJECTIVES: The aim of this study was to explore the possible association of tea consumption with RA through a large-scale, real-world study. METHODS: A total of 733 RA patients were investigated from June to December, 2016. The disease activity of RA was assessed according to disease activity score 28-erythrocyte sedimentation rate. The amount and types of tea consumption were recorded by on-site self-administered questionnaires. Logistic regression models were applied to analyze the correlation between tea consumption and disease activity, adjusting for demographics, clinical and laboratory factors. RESULTS: There was an inverse association between tea consumption and disease activity in RA patients (OR 0.66, 95% CI 0.46-0.94). Compared with non-tea drinkers, a higher-intake of tea (>750 mL/day) was associated with lower disease activity of RA (OR 0.39, 95% CI 0.19-0.79), but not low-intake (≤750 mL/day; OR 0.83, 95% CI 0.42-1.63). A significant dose-response association was found between the amount of tea consumption and disease activity (p for trend <0.01). Further hierarchical regression analysis showed that such inverse associations were mainly present in female patients (p = 0.004), non-smokers (p = 0.01) or elders (≥60 years; p = 0.01). CONCLUSION: Tea consumption is associated with decreased disease activity of RA, suggesting the potential beneficial effect of tea in the disease.

From Simplicity to Complexity in Grafting Dawson-Type Polyoxometalates on Porphyrin, Leading to the Formation of New Organic-Inorganic Hybrids for the Investigation of Third-Order Optical Nonlinearities.

Four new organic-inorganic hybrids, [N(C4H9)4]5H[{HNC2O(CH2O)3P2V3W15O59}C44N4H29O3] (TPPOH-1POM), [N(C4H9)4]10H2[{HNC2O(CH2O)3P2V3W15O59}2C44N4H28O2] (TPPOH-2POM trans), [N(C4H9)4]10H2[{HNC2O(CH2O)3P2V3W15O59}2C44N4H28O2] (TPPOH-2POM cis), and [N(C4H9)4]15H3[{HNC2O(CH2O)3P2W15V3O59}3C44N4H27O] (TPPOH-3POM), have been synthesized by covalently grafting the Dawson-type polyoxometalate (POM) [N(C4H9)4]5[H4P2W15V3O62] onto new porphyrins N-[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]-4-[10,15,20-tris(4-hydroxyphenyl)porphyrin-5-yl]benzamide (TPPOH-1Tris), 4,4'-[5,15-bis(4-hydroxyphenyl)porphyrin-10,20-diyl]bis[ N-[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]benzamide] (TPPOH-2Tris trans), 4,4'-[10,15-bis(4-hydroxyphenyl)porphyrin-5,20-diyl]bis[ N-[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]benzamide] (TPPOH-2Tris cis). and 4,4',4″-[20-(4-hydroxyphenyl)porphyrin-5,10,15-triyl]tris[ N-[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]benzamide] (TPPOH-3Tris), respectively, in N, N-dimethylacetamide under nitrogen. The hybrid compounds were thoroughly characterized by elemental analysis, FT-IR, NMR (1H, 2D NOESY, 31P, and 51V), ESI-MS, MALDI-TOF-MS, UV-vis, and fluorescence spectroscopy. All porphyrins and their corresponding hybrids exhibited remarkable third-order nonlinear-optical responses under laser irradiation, with the intensity of light at focus E0 being 4.2 µJ at wavelength 532 nm, pulse duration τ = 6 ns, and repetition rate 10 Hz. The molecular second hyperpolarizability (γ) values of the hybrids (TPPOH-1POM, TPPOH-2POM trans, TPPOH-2POM cis, TPPOH-3POM) were calculated to be 8.48 × 10-28 esu, 8.94 × 10-28 esu, 10.16 × 10-28 esu, and 8.93 × 10-28 esu, while the molecular second hyperpolarizability (γ) of their corresponding porphyrin precursors (TPPOH-1Tris, TPPOH-2Tris trans, TPPOH-2Tris cis, and TPPOH-3Tris) were 7.19 × 10-28 esu, 8.09 × 10-28 esu, 9.07 × 10-28 esu, and 7.24 × 10-28 esu, respectively. The γ values of the cis forms were found to be superior to those of all other compounds, indicating the significant role of the greater dipole moment and low symmetry of the cis form compared to other compounds. It was also found that the fluorescence intensity was decreased by 81.52%, 90.37%, 93.93%, and 84.62% for the hybrids TPPOH-1POM, TPPOH-2POM trans, TPPOH-2POM cis, and TPPOH-3POM with respect to their corresponding precursors, respectively, which reveals the Dawson-type POM as a strong quencher. This quenching phenomenon not only indicates again unequivocally the formation of hybrid compounds but also may imply a photoinduced electron/energy-transfer process favored from a porphyrin moiety to a Dawson-type POM moiety.

Chiral Silver-Lanthanide Metal-Organic Frameworks Comprised of One-Dimensional Triple Right-Handed Helical Chains Based on [Ln7(µ3-OH)8]13+ Clusters.

Three new isostructural chiral silver-lanthanide heterometal-organic frameworks [Ag3Ln7(µ3-OH)8(bpdc)6(NO3)3(H2O)6](NO3)·2H2O [Ln = Eu (1), Tb (2, Sm (3); H2bpdc = 2,2'-bipyridine-3,3'-dicarboxylic acid] based on heptanuclear lanthanide clusters [Ln7(µ3-OH)8]13+ comprised of one-dimensional triple right-handed helical chains were hydrothermally synthesized. Various means such as UV-vis spectroscopy, IR spectroscopy, elemental analysis, powder X-ray diffraction, and thermogravimetric/differential thermal analysis were used to characterize the compounds, wherein compound 3 was crystallographically characterized. In the structure of compound 3, eight µ3-OH- groups link seven Sm3+ ions, forming a heptanuclear cluster, [Sm7(µ3-OH)8]13+, and the adjacent [Sm7(µ3-OH)8]13+ clusters are linked by the carboxylic groups of bpdc2- ligands, leading to the formation of a one-dimensional triple right-handed helical chain. The adjacent triple right-handed helical chains are further joined together by coordinating the pyridyl N atoms of the bpdc2- ligands with Ag+, resulting in a chiral three-dimensional silver(I)-lanthanide(III) heterometal-organic framework with one-dimensional channels wherein NO3- anions and crystal lattice H2O molecules are trapped. The compounds were studied systematically with respect to their photoluminescence properties and energy-transfer mechanism, and it was found that H2bpdc (the energy level for the triplet states of the ligand H2bpdc is 21505 cm-1) can sensitize Eu3+ luminescence more effectively than Tb3+ and Sm3+ luminescence because of effective energy transfer from bpdc2- to Eu3+ under excitation in compound 1.

Synthesis, Structure, and Photoluminescence of Color-Tunable and White-Light-Emitting Lanthanide Metal-Organic Open Frameworks Composed of AlMo6(OH)6O183- Polyanion and Nicotinate.

A series of isostructural compounds Na(HL)(CH3COO)Ln(Al(OH)6Mo6O18)(H2O)6·10H2O [L = nicotinate; Ln = Eu (1), Tb (2)] and Na(HL)(CH3COO)EumTbnLa1-m-n(AlMo6(OH)6O18)(H2O)6·10H2O (3-8, L = nicotinate), wherein Anderson-type polyanions AlMo6(OH)6O183- as basic inorganic building blocks are connected by Eu(CH3COO)(HL)(H2O)3]24+ and [Na2(H2O)8]2+ cations, resulting in formation of three-dimensional lanthanide metal-organic open frameworks, were synthesized successfully with AlCl3·6H2O, Na2MoO4·2H2O, nicotinic acid, and lanthanide nitrates as starting materials. The compounds were characterized by UV-vis, IR, elemental analysis, powder XRD, and TG-DTA measurements. The single-crystal structures of compounds 1 and 2 show that the two compounds display three-dimensional open frameworks with 1D channels along the b and c axes. Investigation of the energy transfer mechanism indicated that the organic nicotinate ligand can transfer energy efficiently to Tb3+ rather than Eu3+. The influence of the POM moiety on the fluorescence of the compounds is also studied. Compounds 1-8 exhibit tunable luminescence color, and emitting of white light was realized through adjusting the molar ratio of Eu:Tb:La within the compounds.

Covalent Synthesis of Two Hybrids Composed of Dawson-Type Polyoxometalate and Porphyrin with Remarkable Third-Order Optical Nonlinearities Reflecting the Effect of Polyoxometalates.

Two new porphyrin-polyoxometalate hybrids, namely, [(C4H9)4N]10H2[{COHNC(CH2O)3P2V3W15O59}2C44N4H28]·CH3CN 1, bearing two covalent-bonded Wells-Dawson-type polyoxometalates (POMs), and [(C4H9)4N)]5H[COHNC(CH2O)3P2V3W15O59{C44H29N4}]·CH3CN 2, bearing one covalent-bonded POM, have been synthesized and thoroughly characterized by means of elemental analysis, powder XRD, FT-IR, 1H (31P, 51V) NMR, MALDI-TOF-MS, UV-vis spectra, and cyclic voltammetry measurement. Experimental results demonstrate that while all the compounds show remarkable third-order optical nonlinearities, the hybrids 1 and 2 are superior to their corresponding porphyrin precursors (molecular second hyperpolarizability γ = 8.0 × 10-28 esu for 54-N-N'(1,3-tetrahydroxy-2-(dihydroxymethyl)propan-4-diyl)benz-diamide,10,15,20-triphenyl porphyrin that is the precursor for the hybrid 1, γ = 2.6 × 10-28 esu for 54-N-(1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl)benz-amide,10,15,20-triphenyl porphyrin that is the precursor for the hybrid 2), and the hybrid 1 (γ = 12.9 × 10-28 esu) is superior to the hybrid 2 (γ = 12.2 × 10-28 esu) reflecting more POM moieties covalently bonded to the porphyrin moiety exerting more significant influence on the third-order optical nonlinearities. Meanwhile, attachment of POMs on the porphyrin results in significant fluorescence quenching (fluorescence intensity is decreased 97% for the hybrid 1 and 80% for the hybrid 2 with respect to that of their corresponding porphyrin precursors) indicating strong electron transfer from porphyrin moiety to the polyoxometalate moiety. Lower transition energy, small energy difference between singlet and triplet excited states, and faster intersystem crossing (ISC) process of the hybrids are favorable to enhance the NLO responses of hybrids 1 and 2 resulting from the facile electron transfer from the porphyrin moiety to the Dawson POM moiety when the hybrids are subjected to laser irradiation, which is thought to be responsible to the superior of the hybrid 1 to hybrid 2 and the superior of the hybrids to their corresponding porphyrin precursors as well.

A series of mononuclear lanthanide complexes featuring 3-D supramolecular networks: synthesis, characterization and luminescent properties for sensing guest molecules.

A new series of four isostructural mononuclear lanthanide complexes Ln(HPDH)3(H2O)3·H2O (Ln = Sm(III) 1, Eu(III) 2, Tb(III) 3 and Dy(III) 4; H2PDH = 6,7-dihydropyrido(2,3-d)pyridazine-5,8-dione) has been prepared and characterized by IR, elemental analysis, XRD and TG-DTA methods. Single crystal X-ray diffraction analysis of both complexes 1 and 3 revealed that the mononuclear discrete complexes form 3-D supramolecular networks via hydrogen bonds and offset stacking (­H···π) interactions. The photoluminescence study of the title complexes revealed the photoluminescent potential of the antenna ligand (H2PDH) toward the concerned lanthanide cations. The luminescence based sensing ability of the partially dehydrated complex Tb(HPDH)3(H2O)33a towards small solvent molecules, along with its reusability, has been studied. Isopropyl alcohol was found to be an excellent sensitizer, while tetrahydrofuran was a highly quenching solvent with a first order behavior towards the photoluminescence intensity. The photoluminescence intensity was found to decrease with the increase of the dielectric constant and normalized Dimroth­Reichardt ET parameter values for protic solvents, while reverse behavior was observed for dipolar aprotic solvents.

3-D silver(I)-lanthanide(III) heterometallic-organic frameworks constructed from 2,2'-bipyridine-3,3'-dicarboxylic acid: synthesis, structure, photoluminescence, and their remarkable thermostability.

A new family of silver(I)-lanthanide(III) heterometallic-organic frameworks having the formula [AgLn(bpdc)2] (Ln = Eu (1), Tb (2), Sm (3), Dy (4), Y (5), Yb (6), Er (7), Ho (8); H2bpdc = 2,2'-bipyridine-3,3'-dicarboxylic acid), each of which crystallizes in the monoclinic space group C2/c with Z = 4, has been hydrothermally synthesized. The compounds were characterized by means of IR, elemental analysis, thermogravimetric-differential thermal analysis, and powder X-ray diffraction (XRD), wherein compounds 1, 2, and 4-8 were structurally characterized. The powder XRD and single-crystal structures of the title compounds indicate that all the compounds are isostructural and feature a three-dimensional (3-D) open framework. In the structures of the compounds, bpdc(2-) ligands link Ln(3+) through their carboxylic groups, resulting in the formation of a one-dimensional {Ln(bpdc)2}n infinite chain along the c direction. The adjacent chains are then connected to each other through the coordination interaction between Ag(+) and the pyridyl N atoms of bpdc(2-) ligands from the chains, resulting in a 3-D (2,4,6)-connected open framework with (4(11)·6(4))(4(3)·8(2)·10)(8)2 topology. The compounds show remarkable good thermally stability up to 370 °C because neither aquo ligands nor lattice water molecules exist in the composition of the compounds. The photoluminescent properties of compounds 1 and 2 were studied in detail. The energy level of the triplet states of the ligand H2bpdc 21,505 cm(-1) (465 nm) was determined based on the 77 K emission spectrum of the compound [Gd2(bpdc)3(phen)2(H2O)2]·6H2O 9. The (5)D0 and (5)D4 emission lifetimes (1.58 and 1.76 ms) and the overall quantum yields (21% and 22%) were determined for the compounds 1 and 2, respectively.

A new quaternary photoluminescence enhancement system of Eu-N-(o-vanillin)-1,8-diaminonaphthalene-1,10-phenanthroline-Zn and its application in determining trace amounts of europium and zinc.

A new sensitive quaternary photoluminescence enhancement system has been successfully developed to determine trace amounts of Eu(3+) and Zn(2+). The photoluminescence intensity of Eu - N-(o-vanilin)-1,8-diaminonaphthalene systems was greatly increased by the addition of specific concentrations of 1, 10-phenanthroline and Zn(2+). The excitation and emission wavelengths were 274 and 617 nm, respectively. Under optimal system conditions, the photoluminescence intensity showed a linear response toward Eu(3+) in the range of 5.0 × 10(-6) ~ 2.0 × 10(-5) M with a limit of detection (= 2.2 × 10(-9) M) and the photoluminescence intensity of the system decreased linearly by increasing the Zn(2+) concentration in the range of 5.0 × 10(-8) ~ 1.0 × 10(-6) M with a limit of detection (= 8.8 × 10(-11) M). This system was successfully applied for the determination of trace amounts of Eu(3+) in a high purity La2O3 matrix and in the synthetic rare earth oxide mixture, and of Zn(2+) in a high purity Mg(NO3)2 · 6H2O matrix and in synthetic coexisting ionic matrixes. The energy transfer mechanism, photoluminescence enhancement of the system and interference of other lanthanide ions and common coexisting ions were also studied in detail.

Mo polyoxometalate nanoparticles inhibit tumor growth and vascular endothelial growth factor induced angiogenesis.

Tumor growth depends on angiogenesis, which can furnish the oxygen and nutrients that proliferate tumor cells. Thus, blocking angiogenesis can be an effective strategy to inhibit tumor growth. In this work, three typical nanoparticles based on polyoxometalates (POMs) have been prepared; we investigated their capability as antitumor and anti-angiogenesis agents. We found that Mo POM nanoparticles, especially complex 3, inhibited the growth of human hepatocellular liver carcinoma cells (HepG2) through cellular reactive oxygen species levels' elevation and mitochondrial membrane potential damage. Complex 3 also suppressed the proliferation, migration, and tube formation of endothelial cells in vitro and chicken chorioallantoic membrane development ex vivo. Furthermore, western blot analysis of cell signaling molecules indicated that Mo POMs blocked the vascular endothelial growth factor receptor 2-mediated ERK1/2 and AKT signaling pathways in endothelial cells. Using transmission electron microscopy, we demonstrated their cellular uptake and localization within the cytoplasm of HepG2 cells. These results indicate that, owing to the extraordinary physical and chemical properties, Mo POM nanoparticles can significantly inhibit tumor growth and angiogenesis, which makes them potential drug candidates in anticancer and anti-angiogenesis therapies.

Construction of logic gate computation for the assay of the nerve agent sarin based on an AChE-based dual-channel sensing system.

Nerve agents have posed a huge threat to national and human security, and their sensitive detection is crucial. Herein, based on the oxidation of Ce4+ and the aggregation-induced emission (AIE) of glutathione-protected gold nanoclusters (GSH-Au NCs), a cascade reaction was designed to prepare oxidized 3,3',5,5'-tetramethylbenzidine (oxTMB) and GSH-Au NCs crosslinked by Ce3+ (Ce3+-GSH-Au NCs). oxTMB had a broad UV-visible absorption range (500-700 nm) and was capable of quenching the fluorescence of Ce3+-GSH-Au NCs at 590 nm through the internal filtration effect (IFE). Thiocholine (TCh), the hydrolysis product of acetylthiocholine chloride (ATCl) catalyzed by acetylcholinesterase (AChE), reduced oxTMB completely, resulting in a decrease in the absorption of oxTMB and the recovery of IFE-quenched fluorescence of Ce3+-GSH-Au NCs. Nerve agent sarin (GB) hindered the production of TCh and the reduction of oxTMB by inhibiting the AChE activity, leading to the fluorescence of Ce3+-GSH-Au NCs being quenched again. The dual-output sensing system (AChE + ATCl + oxTMB + Ce3+-GSH-Au NCs) exhibited a low limit of detection to GB (2.46 nM for colorimetry and 1.18 nM for fluorimetry) and excellent selectivity toward common interferences being unable to inhibit AChE. Moreover, the intelligent logic gate constructed based on the sensing system showed promising applications in the field of smart sensing of nerve agents.

Head to head comparison of 18F-FDG and Al18F-NOTA-FAPI-04 PET/CT imaging used in diagnosis of autoimmune rheumatic diseases.

OBJECTIVES: The aim of this study was to determine the performance of radionuclide-labeled fibroblast activation protein inhibitors (Al18F-NOTA-FAPI-04) PET/CT in patients with autoimmune rheumatic diseases (ARDs) and compare it with fluorine-18 (18F) labeled fluorodeoxyglucose (FDG) imaging. METHODS: Fifty-eight participants with ARDs were prospectively enrolled from April 2022 to February 2024 and underwent dual-tracer PET/CT imaging. For both 18F-FDG and Al18F-NOTA-FAPI-04 PET/CT, imaging findings were interpreted and compared. The clinical significance was compared between18F-FDG PET/CT and Al18F-NOTA-FAPI-04 PET/CT imaging. RESULTS: 18F-FDG imaging was positive in 53 out of 58 cases (91.4%) while Al18F-NOTA-FAPI-04 imaging was positive in 55 out of 58 cases (94.8%). Overall positive rate of Al18F-NOTA-FAPI-04 imaging was as high as 18F-FDG imaging (P = 0.625). 18F-FDG imaging detected more lesions in lymph node, spleen, and bone marrow. Al18F-NOTA-FAPI-04 imaging detected more lesions in the lung, muscle, and tendon/ligament. There was no statistical difference of composing ratio of grades of clinical significance between two imaging modalities (χ2 = 2.875, P = 0.238). The superior rate of Al18F-NOTA-FAPI-04 PET/CT imaging was higher than 18F-FDG imaging (P = 0.020). In subgroup of adult-onset Still's disease, 18F-FDG imaging showed better performance than Al18F-NOTA-FAPI-04 imaging. In most of the other subgroup of ARDs, Al18F-NOTA-FAPI-04 PET/CT imaging overperformed 18F-FDG imaging. CONCLUSION: Both 18F-FDG and Al18F-NOTA-FAPI-04 PET/CT imaging have excellent sensitivity in ARDs. The detection capabilities of two tracers varied according to the involving organs of ARDs. In most of ARDs except adult-onset Still's disease, Al18F-NOTA-FAPI-04 PET/CT imaging overperformed 18F-FDG imaging. Key Points • 18F-FDG and Al18F-NOTA-FAPI-04 PET/CT imaging have excellent sensitivity in diagnosing of ARDs. • 18F-FDG PET/CT imaging detected more lesions in lymph node, spleen, and bone marrow. • 18F-NOTA-FAPI-04 PET/CT imaging detected more lesions in the lung, muscle, and tendon/ligament. • 18F-NOTA-FAPI-04 PET/CT imaging overperformed18F-FDG in most subgroups of ARDs.

A predictive model for premature atherosclerosis in systemic lupus erythematosus based on clinical characteristics.

OBJECTIVE: Systemic lupus erythematosus (SLE) is associated with a significant risk of atherosclerotic cardiovascular disease, especially in the development of premature atherosclerosis. Specific prediction models for premature atherosclerosis in SLE patients are still limited. The objective of this study was to establish a predictive model for premature atherosclerosis in SLE. METHOD: The study collected clinical and laboratory data from 148 SLE patients under the age of 55, between January 2021 and June 2023. The least absolute shrinkage and selection operator logistic regression model was utilized to identify potentially relevant features. Subsequently, a nomogram was developed using multivariable logistic analysis. The performance of the nomogram was evaluated through a receiver-operating characteristic curve, calibration curve, and decision curve analysis (DCA). RESULTS: A total of 148 SLE patients who fulfilled the inclusion criteria were enrolled in the study, of whom 53 patients (35.81%) met the definition of premature atherosclerosis. Hypertension, antiphospholipid syndrome, azathioprine use, duration of glucocorticoid, and age of patients were included in the multivariable regression. The nomogram, based on the non-overfitting multivariable model, was internally validated and demonstrated sufficient clinical utility for assessing the risk of premature atherosclerosis (area under curve: 0.867). CONCLUSIONS: The comprehensive nomogram constructed in this study serves as a useful and convenient tool for evaluating the risk of premature atherosclerosis in SLE patients. It is helpful for clinicians to early identify SLE patients with premature atherosclerosis and facilitates the implementation of more effective preventive measures. Key Points • SLE patients are at a significantly higher risk of developing premature atherosclerosis compared to the general population, and this risk persists even in cases with low disease activity. Traditional models used to evaluate and predict premature atherosclerosis in SLE patients often underestimate the risk. • This study establishes a comprehensive and visually orientated predictive model of premature atherosclerosis in SLE patients, based on clinical characteristics. • The scoring system allows for convenient and effective prediction of individual incidence of premature atherosclerosis, and could provide valuable information for identification and making further intervention decision.

Interface-regulated S-type core-shell PCN-224@TiO2 heterojunction for visible-light-driven generation of singlet oxygen for selective photooxidation of 2-chloroethyl ethyl sulfide.

Selective oxidation of sulfur mustard gas (HD) to non-toxic sulfoxide by the visible-light-catalyzed generation of singlet oxygen (1O2) is a promising degradation strategy. Although PCN-224 can absorb visible light, it suffers from rapid electron-hole recombination and low redox capacity, which limits the performance of HD degradation. Titanium dioxide (TiO2) is an excellent photocatalyst but it lacks visible-light-activity in degrading HD. In this study, PCN-224@TiO2 heterojunction with S-type core-shell structure was synthesized by in-situ growth method to prolong the visible light absorption capacity of TiO2 and inhibit the rapid recombination of PCN-224. The interface formation and internal electric field were optimized by adjusting the Zr/Ti ratio to enhance the charge transfer, redox capacity, electron-hole separation, and visible light absorption. In this study, the formation of heterojunction composites based on Zr-O-Ti linkages is demonstrated by a series of characterization methods. It is demonstrated by experiments and theoretical calculations that PCN-224@TiO2 can generate nearly 100 % 1O2 under visible light conditions without a sacrificial agent, resulting in efficient and selective oxidation of 2-chloroethyl ethyl sulfide (CEES), a simulant of HD, to non-toxic sulfoxide form.