Self-Assembled FeIII-TAML-Based Magnetic Nanostructures for Rapid and Sustainable Destruction of Bisphenol A.

This study focused on constructing iron(III)-tetraamidomacrocyclic ligand (FeIII-TAML)-based magnetic nanostructures via a surfactant-assisted self-assembly (SAS) method to enhance the reactivity and recoverability of FeIII-TAML activators, which have been widely employed to degrade various organic contaminants. We have fabricated FeIII-TAML-based magnetic nanomaterials (FeIII-TAML/CTAB@Fe3O4, CTAB refers to cetyltrimethylammonium bromide) by adding a mixed solution of FeIII-TAML and NH3·H2O into another mixture containing CTAB, FeCl2 and FeCl3 solutions. The as-prepared FeIII-TAML/CTAB@Fe3O4 nanocomposite showed relative reactivity compared with free FeIII-TAML as indicated by decomposition of bisphenol A (BPA). Moreover, our results demonstrated that the FeIII-TAML/CTAB@Fe3O4 composite can be separated directly from reaction solutions by magnet adsorption and reused for at least four times. Therefore, the efficiency and recyclability of self-assembled FeIII-TAML/CTAB@Fe3O4 nanostructures will enable the application of FeIII-TAML-based materials with a lowered expense for environmental implication.

Regulation of Nontraditional Intrinsic Luminescence (NTIL) in Hyperbranched Polysiloxanes by Adjusting Alkane Chain Lengths: Mechanism, Film Fabrication, and Chemical Sensing.

Biocompatible polymers with nontraditional intrinsic luminescence (NTIL) possess the advantages of environmental friendliness and facile structural regulation. To regulate the emission wavelength of polymers with NTIL, the alkane chain lengths of hyperbranched polysiloxane (HBPSi) are adjusted. Optical investigation shows that the emission wavelength of HBPSi is closely related to the alkane chain lengths; namely, short alkane chains will generate relatively long-wavelength emission. Electronic communication among functional groups is responsible for the emission. In a concentrated solution, HBPSi molecules aggregate together due to the strong hydrogen bond and amphiphilicity, and the functional groups in the aggregate are so close that their electron clouds are overlapped and generate spatial electronic delocalizations. HBPSi with shorter alkane chains will generate larger electronic delocalizations and emit longer-wavelength emissions. Moreover, these polymers show excellent applications in the fabrication of fluorescent films and chemical sensing. This work could provide a strategy for regulating the emission wavelengths of unconventional fluorescent polymers.

Flattened Gaussian focal spot with uniform phase produced by photon sieve.

The equivalent pupil and the point spread function constitute the Fourier-Bessel transform relation. Based on this, we established the equivalent pupil function theory of rotating symmetric photon sieve and derived the Fourier transform of the flattened Gaussian function. The focal spot produced by this type of photon sieve exhibits a uniform intensity and phase distribution. According to the numerical results, the flattened Gaussian field distribution is consistent with the designed function. In addition, the nonuniformity in intensity and phase is approximately 1% and less than 1/170 wavelength, respectively.

High-efficiency square-hole single-mode waveguide photon sieves for THz waves.

The photon sieve has had the problem of low diffraction efficiency since it was proposed. Dispersion from different waveguide modes in the pinholes also reduces the quality of focusing. To overcome the above drawbacks, we propose a kind of photon sieve working in the terahertz band. In a metal square-hole waveguide, the effective index is determined by the side length of the pinhole. We adjust the optical path difference by changing the effective indices of those pinholes. When the thickness of the photon sieve is fixed, the optical path in a zone is set to be a multilevel distribution from 0 to λ. In this way, the optical path differences caused by the waveguide effect of pinholes are used to compensate for those caused by the positions of pinholes. We also derive the focusing contribution of an individual square pinhole. The simulated example shows a 60 times increase in intensity than that of the equal-side-length single-mode waveguide photon sieve.

Case report of extranodal natural killer/T-cell lymphoma that induced secondary hemophagocytic syndrome-related histiocytic glomerulopathy.

Hemophagocytic syndrome (HPS) is a proliferative disease of the mononuclear macrophage system involving multiple organs and systems. We report a 50-year-old Asian woman who presented with unexplained fever and proteinuria. Laboratory tests showed cytopenia, considerably elevated serum ferritin and IL-2 receptor concentrations, and evidence of hemophagocytosis in the bone marrow. A renal biopsy showed macrophage infiltration into the glomerulus, resulting in podocyte and endothelial cell damage. We finally diagnosed the patient with extranodal natural killer/T-cell lymphoma, nasal type that induced HPS-related histiocytic glomerulopathy. Proteinuria and inflammation responded to treatment with high-dose pulsed methylprednisolone combined with VP-16 and cyclosporine. To the best of our knowledge, this is the first documented case of HPS-related histiocytic glomerulopathy triggered by a malignant tumor.

Ambulance referral of more than 2 hours could result in a high prevalence of medical-device-related pressure injuries (MDRPIs) with characteristics different from some inpatient settings: a descriptive observational study.

BACKGROUND: Medical device-related pressure injuries(MDRPI) are prevalent and attracting more attention. During ambulance transfer, the shear force caused by braking and acceleration; extensive medical equipment crowed in a narrow space add external risk factors for MDRPIs. However, there is insufficient research on the relationship between MDRPIs and ambulance transfers. This study aims to clarify the prevalence and characteristics of MDRPI during ambulance transfer. METHOD: A descriptive observational study was conducted with convenience sampling. Before starting the study, six PI specialist nurses certified by the Chinese Nursing Association trained emergency department nurses for three MDRPI and Braden Scale sessions, one hour for each session. Data and images of PIs and MDRPIs are uploaded via the OA system by emergency department nurses and reviewed by these six specialist nurses. The information collection begins on 1 July 2022 and ends on 1 August 2022. Demographic and clinical characteristics and a list of medical devices were collected by emergency nurses using a screening form developed by researchers. RESULTS: One hundred one referrals were eventually included. The mean age of participants was (58.3 ± 11.69) years, predominantly male (67.32%, n = 68), with a mean BMI of 22.48 ± 2.2. The mean referral time among participants was 2.26 ± 0.26 h, the mean BRADEN score was 15.32 ± 2.06, 53.46% (n = 54) of participants were conscious, 73.26% (n = 74) were in the supine position, 23.76% (n = 24) were in the semi-recumbent position, and only 3 (2.9%) were in the lateral position. Eight participants presented with MDRPIs, and all MDRPIs are stage 1. Patients with spinal injuries are most prone to MDRPIs (n = 6). The jaw is the area most prone to MDRPIs, caused by the cervical collar (40%, n = 4), followed by the heel (30%, n = 3) and nose bridge (20%, n = 2) caused by the respiratory devices and spinal board. CONCLUSION: MDRPIs are more prevalent during long ambulance referrals than in some inpatient settings. The characteristics and related high-risk devices are also different. The prevention of MDRPIs during ambulance referrals deserves more research.

Elevated Urinary IL-6 Predicts the Progression of IgA Nephropathy.

Introduction: Immunoglobulin A nephropathy (IgAN) is the most common glomerulonephritis worldwide. However, biomarkers for predicting the progression or regression of IgAN remain a clinical challenge. In the present study, we aim to identify promising prognostic markers of IgAN. Methods: Using the cytokine antibody array, we detected serum and urinary levels of 9 common cytokines selected from 23 IgAN-related biomarkers in 32 patients with IgAN and 16 healthy controls. The best biomarkers for distinguishing IgAN patients from healthy controls were identified and confirmed in a multicenter cohort with 222 patients with IgAN and 159 age- and sex-matched healthy controls. Their associations with IgAN progression were further explored in 762 patients with IgAN with a median follow-up of 65 months. Results: Among the 9 candidate markers, urinary interleukin-6 (IL-6) and transforming growth factor-ß1 (TGF-ß1) levels were the best for distinguishing patients with IgAN from healthy controls. In the diagnostic cohort, both urinary IL-6 and TGF-ß1 levels were elevated in patients with IgAN and showed good discriminatory power, with an area under curve (AUC) of 0.9725 (95% confidence interval: 0.9593-0.9858). Elevated urinary IL-6 level was independently and significantly correlated with the high risk of composite renal outcome (hazard ratio per log-transformed IL-6:1.420 [1.139-1.769]), but no statistical significance was observed between urinary TGF-ß1 level and IgAN progression after adjusting for multiple confounders. Conclusions: Elevated urinary IL-6 and TGF-ß1 levels predict the progression of IgAN. Urinary IL-6 is an independent risk factor and a promising noninvasive predictor for IgAN progression.

Photoaging of Typical Microplastics as Affected by Air Humidity: Mechanistic Insights into the Important Role of Water Molecules.

Recent studies showed that land is the most important sink for microplastics (MPs); however, limited information is available on the photoaging processes of land surface MPs that are exposed to the air. Herein, this study developed two in situ spectroscopic methods to systematically explore the effect of air humidity on MP photoaging using a microscope of Fourier transform infrared spectroscopy and a laser Raman microscope, which were equipped with a humidity control system. Polyethylene microplastics, polystyrene microplastics, and poly(vinyl chloride) microplastics (PVC-MPs) were used as model MPs. Our results showed that relative humidity (RH) could significantly influence the MP surface oxygen-containing moieties generated from photo-oxidation, especially for PVC-MPs. As the RH level varied from 10 to 90%, a decrease in the photogenerated carbonyl group and an increase in the hydroxyl group were observed. This could be attributed to the involvement of water molecules in the production of hydroxyl groups, which subsequently inhibited carbonyl generation. Moreover, the adsorption of coexisting contaminants (i.e., tetracycline) on photoaged MPs exhibited strong RH dependence, which could be assigned to the varied hydrogen bonding between tetracycline carbonyls and aged MP surface hydroxyls. This study reveals a ubiquitous but previously overlooked MP aging route, which may account for the changed MP surface physiochemical properties under solar irradiation.

Mechanistic insights into surface catalytic oxidation of fluoroquinolone antibiotics on sediment mackinawite.

Fluoroquinolone antibiotics (FQs) have been widely detected in the sediments due to vast production and consumption. In this study, the transformation of FQs was investigated in the presence of sediment mackinawite (FeS) under ambient conditions. Moreover, the role of dissolved oxygen was evaluated for the enhanced degradation of FQs induced by FeS. Our results demonstrated that typical FQs (i.e., flumequine, enrofloxacin and ciprofloxacin) could be efficiently adsorbed and degraded by FeS under neutral pH conditions. As indicated by the results of electron paramagnetic resonance analysis (EPR) and free radicals quenching experiments, hydroxyl radical and superoxide radical anions were identified as the dominant reactive species responsible for FQs degradation. Based on the results of product analysis and theoretical calculation, the degradation of FQs mainly occurred at the piperazine ring and quinolone structure. Our results show that FQs could be efficiently removed by FeS, which benefits understanding the transformation of antibiotics in the sediments, and even sheds light on the remediation of organic pollutants contaminated soils.

High-Efficiency Long-Wavelength Fluorescent Hyperbranched Polysiloxanes: Synthesis, Emission Mechanism, Information Encryption, and Film Preparation.

Unconventional fluorescent polymers possess the advantages of excellent biocompatibility, environmental friendliness, and facile structural regulation; however, such polymers usually have low fluorescence intensity and quantum yields in the long-wavelength range. In this work, three kinds of high-efficiency long-wavelength emissive hyperbranched polysiloxanes are obtained by introducing aromatic amino acids. These functionalized hyperbranched polysiloxanes have high fluorescence intensity and quantum yields in green, yellow, and red emission regions. Experimental results and density functional theory calculations reveal that the long-wavelength emission comes from the enhanced electronic communication among the conjugated π bonds, electron-rich atoms, and -Si(O)3 and other functional groups. Especially, the conjugated π bonds efficiently enlarge the spatial electronic delocalizations, resulting in the high-efficiency long-wavelength emission. Moreover, the prepared polymers show excellent applications in information encryption and film preparation. This work could serve as a guide to develop high-efficiency long-wavelength unconventional fluorescent polymers.

Manipulation of Subwavelength Periodic Structures Formation on 4H-SiC Surface with Three Temporally Delayed Femtosecond Laser Irradiations.

Controlling laser-induced periodic surface structures on semiconductor materials is of significant importance for micro/nanophotonics. We here demonstrate a new approach to form the unusual structures on 4H-SiC crystal surface under irradiation of three collinear temporally delayed femtosecond laser beams (800 nm wavelength, 50 fs duration, 1 kHz repetition), with orthogonal linear polarizations. Different types of surface structures, two-dimensional arrays of square islands (670 nm periodicity) and one-dimensional ripple structures (678 nm periodicity) are found to uniformly distribute over the laser-exposed areas, both of which are remarkably featured by the low spatial frequency. By altering the time delay among three laser beams, we can flexibly control the transition between the two surface structures. The experimental results are well explained by a physical model of the thermally correlated actions among three laser-material interaction processes. This investigation provides a simple, flexible, and controllable processing approach for the large-scale assembly of complex functional nanostructures on bulk semiconductor materials.

Truly Multicolor Emissive Hyperbranched Polysiloxane: Synthesis, Mechanism Study, and Visualization of Controlled Drug Release.

Unconventional fluorescent polymers have attracted increasing attention due to their facile synthesis, excellent biocompatibility, and novel photophysical properties. In this work, a truly multicolor emissive hyperbranched polysiloxane (HBPSi-ß-CD) is obtained through adjusting the distribution of electron-rich atoms and grafting ß-cyclodextrin; the quantum yields of HBPSi-ß-CD after being excited by 360, 420, 450, and 550 nm are 19.36, 31.46, 46.14 and 44.84%, respectively. The density functional theory calculations reveal that the truly multicolor emission is derived from the formed electron delocalization among the hydroxyl, amine, ether, and -Si(O)3 groups due to the strong intermolecular interaction, high density of electron-rich atoms, and low steric hindrance among functional groups. The prepared polymers could serve as a multisensitivity sensor in detecting Fe3+, Cu2+, and Co2+. The HBPSi-ß-CD shows low cytotoxicity and excellent cellular imaging capability. The self-assembly of HBPSi-ß-CD also possesses high drug loading capacity and pH-controlled drug release, especially, the drug delivery system could be applied in the visualization of controlled drug delivery.

A possible case of carbamazepine-induced renal phospholipidosis mimicking Fabry disease.

Fabry disease (FD) is a genetic disorder caused by a-galactosidase A gene mutation. Ultrastructural analysis revealing zebra bodies are the typical morphological characteristics. However, certain tricyclic antidepressants and some other medications could induce renal phospholipidosis mimicking FD. We report a 33-year-old man has been taking carbamazepine intermittently for around 10 years whenever he experiences pain and paresthesia in his fingers. He experienced mild edema on both lower limbs half a year ago. Laboratory tests revealed a fluctuating urine protein between + and ++. Electron microscopy revealed laminated "zebra body" in podocytes, which is typical of FD. However, the patient had no family history and the sequencing of the a-galactosidase gene revealed no mutations. The a-galactosidase A enzyme activity was normal at 6.03 µmol/mL/h (normal 2.40-17.65 µmol/mL/h), and low expression of globotriaosylceramide (Gb3) was detected in the renal tissue of this patient. Therefore, the diagnosis of Fabry disease was excluded. Considering the patient's long-term treatment with carbamazepine (blood level 1.8 µg/ml), we speculated whether the pathological features could be associated with renal phospholipidosis caused by carbamazepine. The follow-up data showed that proteinuria was improved (fluctuated at + ~ -) after discontinuing carbamazepine for six months, which further seemed to support the above diagnosis. Therefore, we concluded that a possible case of carbamazepine-induced renal phospholipidosis, mimicking that observed in FD, has been associated with its nephrotoxicity.

Structure-dependent surface catalytic degradation of cephalosporin antibiotics on the aged polyvinyl chloride microplastics.

Microplastics (MPs) have been recognized as a global concern due to their potential health effect, as MPs could adsorb and carry various pollutants in aquatic environment. In the present study, a new environmental behavior related to polyvinyl chloride microplastics (PVC-MPs) and the underlying mechanism were described. Our results showed that the photo-aged PVC-MPs could affect the transformation of cephalosporin antibiotics. For instance, the presence of altered PVC-MPs significantly accelerated the hydrolysis of cefazolin (CFZ), but exhibited negligible effect on the degradation of cephalexin (CFX). As indicated by in situ Fourier transform infrared spectra and theoretical calculations, hydrogen bonds could be formed between ß-lactam carbonyl of CFZ and the oxygen-containing moieties on the aged PVC-MP surfaces. The hydrogen-bonding was able to significantly increase the positive atomic Mulliken charge on the ß-lactam carbonyl carbon, thus narrowing the energy gap of CFZ hydrolysis and subsequently enhancing the disruption of ß-lactam ring. While for CFX, instead of the ß-lactam carbonyl, the amide amino group was involved in the hydrogen-bonding due to the structural difference. Therefore, in addition to increasing the adsorption capacity, the aged PVC-MPs could act as the catalyst to mediate the transformation of antibiotics. Our study would help improve the understanding for interactions between contaminants and MPs in natural environments.

Enhanced UV Emission from ZnO on Silver Nanoparticle Arrays by the Surface Plasmon Resonance Effect.

Periodical silver nanoparticle (NP) arrays were fabricated by magnetron sputtering method with anodic aluminum oxide templates to enhance the UV light emission from ZnO by the surface plasmon resonance effect. Theoretical simulations indicated that the surface plasmon resonance wavelength depended on the diameter and space of Ag NP arrays. By introducing Ag NP arrays with the diameter of 40 nm and space of 100 nm, the photoluminescence intensity of the near band-edge emission from ZnO was twofold enhanced. Time-resolved photoluminescence measurement and energy band analysis indicated that the UV light emission enhancement was attributed to the coupling between the surface plasmons in Ag NP arrays and the excitons in ZnO with the improved spontaneous emission rate and enhanced local electromagnetic fields.

Energy-Transfer-Induced Multiexcitation and Enhanced Emission of Hyperbranched Polysiloxane.

Fluorescent hyperbranched polysiloxane (HBPSi) has attracted increasing attention due to its good biocompatibility. However, its emission mechanism remains an open question. Unfortunately, the excitation spectra of HBPSi are rarely systematically investigated and show a narrow excitation band, which hinders the emission mechanism study. Herein, we synthesized a series of novel HBPSi containing l-glutamic acid (HBPSi-GA). Surprisingly, these polymers have four excitation peaks and two emission peaks, which are caused by the energy transfer from free functional groups to heterogeneous electron delocalizations in different clusters. Meanwhile, the fluorescence and biocompatibility of HBPSi-GA are significantly improved with increasing l-glutamic acid. Furthermore, HBPSi-GA exhibits dual stimuli-responsive fluorescence to temperature and Fe3+ as well as potential application in cell imaging. This research possesses important guidance to develop multiexcitation unconventional fluorescent polymers.

High Fluorescent Hyperbranched Polysiloxane Containing ß-Cyclodextrin for Cell Imaging and Drug Delivery.

Hyperbranched polysiloxane (HBPSi) is attracting increasing attention due to its intrinsic fluorescence and good biocompatibility. However, it is very challenging to explore its biological applications because of the low fluorescence intensity and quantum yield. Herein, we introduced rigid ß-cyclodextrin to the end of flexible polysiloxane chain to synthesize a novel fluorescent polymer (HBPSi-CD) and explore its biological applications. Results showed that the fluorescence intensity and quantum yield of HBPSi-CD, compared with HBPSi, were significantly enhanced. Theoretical calculations and transmission electron microscopy demonstrated that the synergy effect of intra/intermolecular hydrogen bonds and hydrophobic effect promoted the formation of large supramolecular self-assemblies and space electron delocalization systems, leading to intense fluorescence. Notably, the biocompatible HBPSi-CD not only lighted up mouse fibroblast cells, but also possessed high ibuprofen loading capacity (160 mg g-1) and superior pH-responsive drug release performance. This work promoted the development of biological applications of HBPSi.

Synergic effect of graphene and core-shells structured Au NR@SiO2@TiO2 in dye-sensitized solar cells.

Graphene and Au nanorods (AuNRs) coated with SiO2@TiO2 double shells (AuNR@SiO2@TiO2) were incorporated to form novel composite photoanodes in dye sensitized solar cells (DSSCs). The performances of the photoanodes and DSSCs are studied systematically. The short circuit current density (J sc) and power conversion efficiency (PCE) of these composited DSSCs were greatly enhanced and the influences of the graphene, AuNRs and the SiO2@TiO2 double shells were revealed. The optimal properties with the maximal J sc of 16.26 mA cm-2 and PCE of 8.08% are obtained in the DSSC co-doped with graphene and AuNR@SiO2@TiO2, significantly higher than those of the conventional DSSC with pure TiO2 photoanode by 37.7% and 32.9%, respectively. These significant enhancements in J sc and PCE are attributed to the synergistic effect of graphene, the local surface plasma resonance of AuNRs, as well as the outer SiO2@TiO2 double shells, which result in the increased specific surface area and dye adsorption, the increased light absorption, the decreased charge transfer resistance R 2 and electron recombination and thus the increased J sc and PCE of the DSSCs.

Unprecedented Multicolor Photoluminescence from Hyperbranched Poly(amino ester)s.

A novel kind of water-soluble fluorescent hyperbranched poly(amino ester) (PAE) is prepared through a one-pot polycondensation reaction of citric acid (CA) and N-methyldiethanolamine (NMDEA). The PAE exhibits enhanced and red-shift fluorescence with increasing solution concentration, showing distinct aggregation-induced emission character. Interestingly, the resulting PAE exhibits tunable photoluminescence from blue, cyan, and green to red irradiated by altering the excitation wavelengths. Such unique emission of non-conjugated PAE is attributed to the clustering of ester and tertiary amine groups derived from PAE self-assembly aggregates. Moreover, the fluorescence of PAE is very sensitive to Fe3+ ions. The facile preparation and unique optical features make PAE potentially useful in numerous applications such as multicolor cellular imaging, Fe3+ ions probe, and light-emitting diodes.

BrCl+ elimination from Coulomb explosion of 1,2-bromochloroethane induced by intense femtosecond laser fields.

By using a dc-slice imaging technique, photodissociation of 1,2-C2H4BrCl was investigated at 800 nm looking for heteronuclear unimolecular ion elimination of BrCl+ in an 80 fs laser field. The occurrence of fragment ion BrCl+ in the mass spectrum verified the existence of a unimolecular decomposition channel of BrCl+ in this experiment. The relative quantum yield of the BrCl+ channel was measured to be 0.8%. By processing and analyzing the velocity and angular distributions obtained from the corresponding sliced images of BrCl+ and its partner ion C2H4 +, we concluded that BrCl+ came from Coulomb explosion of the 1,2-bromochloroethane dication 1,2-C2H4BrCl2+. With the aid of quantum chemical calculations at the M06-2X/def2-TZVP level, the potential energy surface for BrCl+ detachment from 1,2-C2H4BrCl2+ has been examined in detail. According to the ab initio calculations, two transition state structures tended to correlate with the reactant 1,2-C2H4BrCl2+ and the products BrCl+ + C2H4 +. In this entire dissociation process, the C-Br and C-Cl bond lengths were observed to elongate asymmetrically, that is, the C-Br chemical bond broke firstly, and subsequently a new Br-Cl chemical bond started to emerge while the C-Cl bond continued to exist for a while. Hence, an asynchronous concerted elimination mechanism was favored for BrCl+ detachment.