Atomically dispersed cobalt activator with nitrogen and sulfur co-coordination for high-efficiency Fenton-like catalysis: Insights into density-dependent activity and mechanisms.

Atomically dispersed metal activators (ADMAs) have demonstrated unique advantages in environmental remediation, but how to controllably regulate the active site density and electronic structure of ADMAs to further enhance activation efficiency remains challenging. Here, we introduce a sulfur-atom-doping approach that allows the fine-tuning of atomic Co site content and electronic structure, enabling exploration of density-dependent activation performance of ADMAs for peroxymonosulfate (PMS)-based Fenton-like catalysis. Our investigation reveals a direct correlation between activation capacity and single-Co-site density. The optimal SNC@CoSA-0.05 activator with densely populated Co-N3S1 sites (10.1 wt%) displays exceptional efficacy in eliminating Rhodamine B, with specific activity of 31.0 min-1 g-1 L, outperforming most previously published activators. Moreover, SNC@CoSA-0.05 showed a remarkedly reduced metal leaching (47.4 µg L-1) than its nanocluster counterpart (194 µg L-1) at pH 3.2. Experimental and theoretical analyses unveiled that coordinated sulfur actively modulates the electronic structure of the central Co atom, enhancing the adsorption and activation of PMS, thereby improving decontamination efficiency. Mechanistic studies further elucidate the predominant electron-transfer regime involved in oxidizing micropollutants by SNC@CoSA-0.05/PMS, with Co(IV)=O, •OH, and SO4•- being the auxiliary oxidizing species. This study not only offers a method for concurrent adjustment of active site density and electronic structure in ADMAs but also sheds light on the activation mechanisms of atomic metal sites.

Collaborative rp-hplc method development for modafinil and scopolamine hydrobromide in sublingual tablets: involving key industry players

Objective: This research aims to develop and validate a collaborative RP-HPLC method, with input from key industry players, for the simultaneous determination of modafinil and scopolamine hydrobromide in compound sublingual tablets. The focus is on ensuring the safety and efficacy of these substances for enhancing the physical and cognitive fitness of athletes and players. Method: Utilizing a C18 chromatographic column (200mm×4.6mm, 5μm), the method employs a mobile phase of acetonitrile-water (25:75) with 0.02mol/L ammonium acetate and 0.02% triethylamine, pH adjusted to 6.0. The flow rate was set at 1 mL/min, detection at 225 nm wavelength, and an injection volume of 20 μL.Results: Scopolamine hydrobromide showed a linear range of 1-50 μg/mL, with a standard curve equation of A=0.2187C+0.0708 (R²=0.9993), and modafinil exhibited a range of 10-500 μg/mL, with A=0.6702C-1.6855 (R²=0.9993). Both substances demonstrated average recoveries of over 99%, within acceptable variance limits, signifying reliable quantification for fitness-related applications. Conclusion: The developed method is sensitive, precise, accurate, and reproducible, conforming to the standards of the Chinese Pharmacopoeia (2020 edition). It is particularly valuable for monitoring the quality of substances used by athletes and players to ensure their safe application in enhancing fitness and performance. The method benefits significantly from the collaboration with industry experts, addressing the specific needs of fitness and sports professionals (AU)

Gold nanoparticle-directed autophagy intervention for antitumor immunotherapy via inhibiting tumor-associated macrophage M2 polarization.

Tumor-associated macrophages (TAMs), one of the dominating constituents of tumor microenvironment, are important contributors to cancer progression and treatment resistance. Therefore, regulation of TAMs polarization from M2 phenotype towards M1 phenotype has emerged as a new strategy for tumor immunotherapy. Herein, we successfully initiated antitumor immunotherapy by inhibiting TAMs M2 polarization via autophagy intervention with polyethylene glycol-conjugated gold nanoparticles (PEG-AuNPs). PEG-AuNPs suppressed TAMs M2 polarization in both in vitro and in vivo models, elicited antitumor immunotherapy and inhibited subcutaneous tumor growth in mice. As demonstrated by the mRFP-GFP-LC3 assay and analyzing the autophagy-related proteins (LC3, beclin1 and P62), PEG-AuNPs induced autophagic flux inhibition in TAMs, which is attributed to the PEG-AuNPs induced lysosome alkalization and membrane permeabilization. Besides, TAMs were prone to polarize towards M2 phenotype following autophagy activation, whereas inhibition of autophagic flux could reduce the M2 polarization of TAMs. Our results revealed a mechanism underlying PEG-AuNPs induced antitumor immunotherapy, where PEG-AuNPs reduce TAMs M2 polarization via induction of lysosome dysfunction and autophagic flux inhibition. This study elucidated the biological effects of nanomaterials on TAMs polarization and provided insight into harnessing the intrinsic immunomodulation capacity of nanomaterials for effective cancer treatment.

Generation of the induced pluripotent stem cell line (ZSPHARi001-A) from a patient with recessive dystrophic epidermolysis bullosa carrying compound heterozygous mutation in the COL7A1 gene.

The COL7A1 gene mutation causes type VII collagen dysfunction, which subsequently leads to recessive dystrophic epidermolysis bullosa (RDEB). Patients who suffer from RDEB experience severe blisters and chronic trauma, which can eventually result in serious infection and the development of fatal squamous cell carcinoma. In our study, peripheral blood mononuclear cells (PBMCs) from an RDEB patient with the COL7A1 compound heterozygous mutation were collected and then reprogrammed into induced pluripotent stem cells (iPSC). The RDEB iPSC line can provide a cellular resource for the study of pathogenesis and drug screening.

Tumor RNA-loaded nanoliposomes increases the anti-tumor immune response in colorectal cancer.

PURPOSE: Tumor RNA vaccines can activate dendritic cells to generate systemic anti-tumor immune response. However, due to easily degraded of RNA, direct RNA vaccine is less effective. In this study, we optimized the method for preparing PEGylated liposom-polycationic DNA complex (LPD) nanoliposomes, increased encapsulate amount of total RNA derived from CT-26 colorectal cancer cells. Tumor RNA LPD nanoliposomes vaccines improved anti-tumor immune response ability of tumor RNA and can effectively promote anti-tumor therapeutic effect of oxaliplatin. METHODS: Total tumor-derived RNA was extracted from colorectal cancer cells (CT-26 cells), and loaded to our optimized the LPD complex, resulting in the LPD nanoliposomes. We evaluated the characteristics (size, zeta potential, and stability), cytotoxicity, transfection ability, and tumor-growth inhibitory efficacy of LPD nanoliposomes. RESULTS: The improved LPD nanoliposomes exhibited a spherical shape, RNA loading efficiency of 9.07%, the average size of 120.37 ± 2.949 nm and zeta potential was 3.34 ± 0.056 mV. Also, the improved LPD nanoliposomes showed high stability at 4 °C, with a low toxicity and high cell transfection efficacy toward CT-26 colorectal cancer cells. Notably, the improved LPD nanoliposomes showed tumor growth inhibition by activating anti-tumor immune response in CT-26 colorectal cancer bearing mice, with mini side effects toward the normal organs of mice. Furthermore, the effect of the improved LPD nanoliposomes in combination with oxaliplatin can be better than that of oxaliplatin alone. CONCLUSION: The improved LPD nanoliposomes may serve as an effective vaccine to induce antitumor immunity, presenting a new treatment option for colorectal cancer.

Dual-triggered biomimetic vehicles enable treatment of glioblastoma through a cancer stem cell therapeutic strategy.

Glioma stem cells (GSCs) and their complex microenvironment play a crucial role in the high invasion of cancer and therapeutic resistance and are considered to be the most likely cause of cancer relapse. We constructed a biomimetic vehicle (LDL-SAL-Ang) based on a low density lipoprotein triggered by Angiopep-2 peptide and ApoB protein, to improve the transport of an anti-GSC therapeutic agent into the brain. The LDL-SAL-Ang showed significant inhabitation for GSC microsphere formation and induced the highest apoptotic rate in two types of GSCs. LDL-SAL-Ang reduced the number of GSC-derived endothelial tubules at a lower drug concentration and inhibited endothelial cell migration and angiogenesis. The pharmacokinetic analysis showed that the brain tissue uptake rate (% ID g-1) for LDL-SAL-Ang was significantly enhanced at 0.45. For anti-glioblastoma activity in vivo, the median survival time of LDL-SAL-Ang plus temozolomide group was 47 days, which were significantly increased compared with the control or temozolomide only groups. The endogenous biomimetic nanomedicine that we designed provides a potential approach to improve treatments for intracranial tumors and reduced neurotoxicity of nanomedicine.

Pure Red Iridium(III) Complexes Possessing Good Electron Mobility with 1,5-Naphthyridin-4-ol Derivatives for High-Performance OLEDs with an EQE over 31.

Three iridium(III) complexes (Ir(4tfmpq)2mND, Ir(4tfmpq)2mmND, and Ir(4tfmpq)2mpND) with the 4-(4-(trifluoromethyl)phenyl)quinazoline (4tfmpq) main ligand and 1,5-naphthyridin-4-ol derivatives (mND: 8-methyl-1,5-naphthyridin-4-ol, mmND: 2,8-dimethyl-1,5-naphthyridin-4-ol, mpND: 8-methyl-2-phenyl-1,5-naphthyridin-4-ol) as ancillary ligands were studied. The complexes (Ir(4tfmpq)2mND, Ir(4tfmpq)2mmND, and Ir(4tfmpq)2mpND) emit pure red emissions of 626-630 nm with high photoluminescence quantum yields of 85.2-93.4% in CH2Cl2 and better electron mobilities than that of tri(8-hydroxyquinoline)aluminum. By employing three pure red emitters, all the phosphorescent organic light-emitting diodes exhibited superior performances with a maximum external quantum efficiency of 31.48% and the efficiency roll-off is very mild, which are among the best results ever reported for pure red organic light-emitting diodes using Ir(III) complexes. In addition, CIE( x, y) coordinates of (0.670, 0.327) are also close to the standard red emission required by the National Television System Committee.

Rapid room temperature synthesis of red iridium(iii) complexes containing a four-membered Ir-S-C-S chelating ring for highly efficient OLEDs with EQE over 30.

Three red cyclometalated iridium(iii) complexes (4tfmpq)2Ir(dipdtc), (4tfmpq)2Ir(dpdtc) and (4tfmpq)2Ir(Czdtc) (4tfmpq = 4-(4-(trifluoromethyl)phenyl)quinazoline, dipdtc = N,N-diisopropyl dithiocarbamate, dpdtc = N,N-diphenyl dithiocarbamate, and Czdtc = N-carbazolyl dithiocarbamate) containing the unique four-membered Ir-S-C-S backbone ring were synthesized in five minutes at room temperature with good yields, and the Gibbs free energy calculation results indicate that all reactions are exothermic and thermodynamically favorable processes. The emission colors (λ peak = 641-611 nm), photoluminescence quantum efficiencies (Φ P = 58.3-93.0%) and bipolar properties can be effectively regulated by introducing different electron-donating substituents into the dithiocarbamate ancillary ligands. Employing these emitters, organic light emitting diodes (OLEDs) with double emissive layers exhibit excellent performances with a maximum brightness over 60 000 cd m-2, a maximum current efficiency of 40.68 cd A-1, a maximum external quantum efficiency (EQEmax) of 30.54%, and an EQE of 26.79% at the practical luminance of 1000 cd m-2. These results demonstrate that Ir(iii) complexes with sulfur-containing ligands can be rapidly synthesized at room temperature, which is key to the production of metal luminescent materials for large-scale application in highly efficient OLEDs.

Two platinum(ii) complexes with a 4-phenyl-4H-1,2,4-triazole derivative as an ancillary ligand for efficient green OLEDs.

Two new cyclometalated platinum(ii) complexes ((TN3T)Pt(dptp), (4tfmppy)Pt(dptp)) with 2',6'-bis(trifluoromethyl)-2,3'-bipyridine (TN3T) and 4-trifluoromethylphenylpyridine (4tfmppy) as the cyclometalated ligands and the nitrogen heterocycle 2-(4,5-diphenyl-4H-1,2,4-triazol-3-yl)phenol (dptp) as the ancillary ligand were developed. Both complexes are green phosphors with high photoluminescence quantum efficiency yields (λmax = 532 nm, Φp = 65% for (TN3T)Pt(dptp) and λmax = 502 nm, Φp = 71% for (4tfmppy)Pt(dptp)) in CH2Cl2 solutions at room temperature, respectively. Organic light-emitting diodes (OLEDs) with single-emitting layer and double-emitting layer structures were fabricated with good performances. Particularly, the double-emitting layer device D2 based on the complex (4tfmppy)Pt(dptp) with 6 wt% doped concentration shows superior performances with a maximum EQE of 26.90% with mild efficiency roll-off. This study demonstrates that the ancillary ligand attached with a 4-phenyl-4H-1,2,4-triazole group could facilitate charge trapping across the bulk of the device for efficient OLEDs.

Correction: Rapid room temperature synthesis of red iridium(iii) complexes containing a four-membered Ir-S-C-S chelating ring for highly efficient OLEDs with EQE over 30.

[This corrects the article DOI: 10.1039/C8SC05605F.].

NIR-Responsive Copolymer Upconversion Nanocomposites for Triggered Drug Release in Vitro and in Vivo.

Light has several advantages as the stimulus for a triggered drug release. Currently, the applications of phototriggered drug-release devices (PDDs) are largely limited by two factors: the limited tissue penetration and detrimental effects caused by excitation light (ultraviolet or visible light). To address this disadvantage, this study developed nanocomposites based on upconversion nanoparticles (UC), which could convert near-infrared light to ultraviolet-visible light and trigger drug release. By loading UC and doxorubicin (DOX) into photoresponsive copolymer PEG-NMAB-PLA (PNP), near-infrared responsive copolymer upconversion nanocomposites (PNP-DOX-UC) were constructed. We proved that PNP-DOX-UC showed the fast release and strong cytotoxicity under near-infrared irradiation in vitro. The therapeutic efficacy study indicated that PNP-DOX-UC+hv had the enhanced antitumor efficiency. In the study, UC becoming an internal ultraviolet-visible light source for near-infrared excitation develops an applicable and efficient approach to meet the requirements for UV/vis excitation, which is a major disadvantage in photosensitive materials developed for pharmaceutical and biomedical applications.

Efficient orange-red electroluminescence of iridium complexes with 1-(2,6-bis(trifluoromethyl)pyridin-4-yl)isoquinoline and 4-(2,6-bis(trifluoromethyl)pyridin-4-yl)quinazoline ligands.

Two novel iridium(iii) complexes, Ir(tfmpiq)2(acac) (tfmpiq = 1-(2,6-bis(trifluoromethyl)pyridin-4-yl)isoquinoline, acac = acetylacetone) and Ir(tfmpqz)2(acac) (tfmpqz = 4-(2,6-bis(trifluoromethyl)pyridin-4-yl)quinazoline), were synthesized and thoroughly investigated. Both complexes emit orange-red photoluminescence with high quantum yields (Ir(tfmpiq)2(acac): λmax: 587 nm, ηPL: 42%; Ir(tfmpqz)2(acac): λmax: 588 nm, ηPL: 91%). Furthermore, the complex containing quinazoline shows higher electron mobility than that with isoquinoline. The organic light-emitting diodes (OLEDs) with single- or double-emitting layers (EML) were fabricated using two new emitters. The double-EML device using Ir(tfmpqz)2(acac) with the structure of ITO (indium-tin-oxide)/MoO3 (molybdenum oxide, 3 nm)/TAPC (di-[4-(N,N-ditolyl-amino)-phenyl]cyclohexane, 50 nm)/Ir(tfmpqz)2(acac) (1 wt%):TcTa (4,4',4''-tris(carbazole-9-yl)triphenylamine, 10 nm)/Ir(tfmpqz)2(acac) (1 wt%):2,6DCzPPy (2,6-bis(3-(carbazol-9-yl)phenyl)pyridine, 10 nm)/TmPyPB (1,3,5-tri(m-pyrid-3-yl-phenyl)benzene, 50 nm)/LiF (1 nm)/Al (100 nm) displays good electroluminescence performances with a maximum luminance of 96 609 cd m-2, a maximum current efficiency of 59.09 cd A-1, a maximum external quantum efficiency of 20.2%, a maximum power efficiency of 53.61 lm W-1, and the efficiency roll-off ratio is mild.

Novel Design of Iridium Phosphors with Pyridinylphosphinate Ligands for High-Efficiency Blue Organic Light-emitting Diodes.

Due to the high quantum efficiency and wide scope of emission colors, iridium (Ir) (III) complexes have been widely applied as guest materials for OLEDs (organic light-emitting diodes). Contrary to well-developed Ir(III)-based red and green phosphorescent complexes, the efficient blue emitters are rare reported. Like the development of the LED, the absence of efficient and stable blue materials hinders the widely practical application of the OLEDs. Inspired by this, we designed two novel ancillary ligands of phenyl(pyridin-2-yl)phosphinate (ppp) and dipyridinylphosphinate (dpp) for efficient blue phosphorescent iridium complexes (dfppy)2Ir(ppp) and (dfppy)2Ir(dpp) (dfppy = 2-(2,4-difluorophenyl)pyridine) with good electron transport property. The devices using the new iridium phosphors display excellent electroluminescence (EL) performances with a peak current efficiency of 58.78 cd/A, a maximum external quantum efficiency of 28.3%, a peak power efficiency of 52.74 lm/W and negligible efficiency roll-off ratios. The results demonstrated that iridium complexes with pyridinylphosphinate ligands are potential blue phosphorescent materials for OLEDs.

Syntheses, photoluminescence and electroluminescence of two novel platinum(ii) complexes.

Two new platinum(ii) cyclometalated complexes with 2-(4-trifluoromethyl)phenylpyridine (4-tfmppy) as the main ligand and tetraphenylimidodiphosphinate (tpip) (Pt-tpip) and tetra(4-fluorophenyl)imidodiphosphinate (ftpip) (Pt-ftpip) as ancillary ligands were developed. Both complexes were green phosphors with photoluminescence quantum efficiency yields of 71.5% and 79.2% in CH2Cl2 solution at room temperature, respectively. The organic light-emitting diodes with a double emissive layers structure of ITO/TAPC (1,1-bis(4-(di-p-tolylamino)phenyl)cyclohexane), 40 nm/Pt-tpip or Pt-ftpip: TcTa (4,4',4''-tri(9-carbazoyl)-triphenylamine) (5 wt%, 10 nm)/Pt-tpip or Pt-ftpip: 2,6DCzPPy (2,6-bis(3-(carbazol-9-yl)phenyl)pyridine) (5 wt%, 10 nm)/TmPyPB (1,3,5-tri(m-pyrid-3-yl-phenyl)benzene, 40 nm)/LiF (1 nm)/Al (100 nm) showed good performances. In particular, the device based on the Pt-ftpip complex with a 5 wt% doped concentration showed superior performance with a low drive voltage of 3.3 V, a maximum current efficiency of 48.3 cd A-1, a maximum external quantum efficiency of 14.0%, and a maximum power efficiency of 35.7 lm W-1, respectively. Even at a brightness of 1000 cd m-2, a current efficiency of 47.0 cd A-1 could still be obtained, suggesting that the ancillary ligands (tpip and ftpip) can be employed well in Pt(ii) complexes, which could find potential applications in OLEDs.

N-Heterocyclic carbenes: versatile second cyclometalated ligands for neutral iridium(III) heteroleptic complexes.

With 2-(2,4-difluorophenyl)pyridine (dfppy) as the first cyclometalated ligand and different monoanionic N-heterocyclic carbenes (NHCs) as the second cyclometalated ligands, 16 blue or greenish-blue neutral iridium(III) phosphorescent complexes, (dfppy)2Ir(NHC), were synthesized efficiently. The obtained Ir(III) complexes display typical phosphorescence of 455-485 nm with quantum yields up to 0.73. By modifying the phenyl moiety in the NHCs with electron-withdrawing substituents (e.g., -F or -CF3) or replacing it with N-heteroaromatic rings (pyridine or pyrimidine), the HOMO-LUMO gaps are broadened, and the emissions shift to the more blue region accordingly. Furthermore, to extend the application scope of NHCs as the second cyclometalated ligands, five other Ir(III) complexes from blue to red were synthesized with different first cyclometalated ligands. Finally, the organic light-emitting diodes using one blue emitter exhibit a maximum current efficiency of 37.83 cd A(-1), an external quantum efficiency of 10.3%, and a maximum luminance of 8709 cd m(-2). Our results demonstrate that NHCs as the second cyclometalated ligands are good candidates for the achievement of efficient phosphorescent Ir(III) complexes and corresponding devices.

Survey of heavy metal pollution in four chinese crude drugs and their cultivated soils.

A two-year survey on the residues of heavy metals in four Chinese crude drugs and their cultivated soils was conducted. Targeted heavy metals were copper (Cu), arsenic (As), lead (Pb), nickel (Ni), and cadmium (Cd). Herbs surveyed include White Peony Root (Radix Paeoniae Alba), Turmeric Root Tuber (Radix Curcumae), Thunberg Fritillary Bulb (Bulbus Fritillariae Thumbergii), and Tuber of Dwarf Lilyturf (Radix Ophiopogonis). Concentrations of all heavy metals were under the permitted levels except cadmium, which exceeded the permitted level in some samples of Thunberg Fritillary Bulb, White Peony Root, and Turmeric Root Tuber. Concentration coefficients were less than 1.0 for all heavy metals except cadmium. The concentration coefficient of cadmium in Turmeric Root Tuber was 14.0. Lower pH and high Zn concentration in the soil may facilitate the transfer of cadmium from cultivated soil into the herbs.

[Investigation of organophosphorous insecticides residue in Chinese crude drugs].

OBJECTIVE: To study eleven organophosphorus insecticides residuals in four kinds of Chinese crude drugs. METHOD: The organophosphorus insecticides were extracted with dichloromethane and cleaned-up with a mixture of Celite 545-activated carbon. The extracts were analyzed by gas chromatography equipped with a flame photometric detector (FPD). RESULT: Analysis of fortified Chinese crude drug showed that the average recoveries ranged from 77.5% -112.3% at three different levels, the RSDs were below 10% (n = 4). Trace organophosphorous pesticide residues were found in samples of Rhizoma Atractylodis Macrocephalae and Flos Chrysanthemi. CONCLUSION: A method was established for determination multi-residues in Rhizma Atractylodis Macrocephalae, Radix Curcumae, Bulbus Fritillariae Thunbergii and Flos Chrysanthemi. It provides a method for the risk assessment of organophosphorous pesticide in Chinese crude drugs.