Your browser doesn't support javascript.
loading
Show: 20 | 50 | 100
Results 1 - 20 de 184
Filter
Add more filters

Country/Region as subject
Publication year range
1.
Nature ; 567(7749): 496-499, 2019 03.
Article in English | MEDLINE | ID: mdl-30894751

ABSTRACT

Chirality-the geometric property of objects that do not coincide with their mirror image-is found in nature, for example, in molecules, crystals, galaxies and life forms. In quantum field theory, the chirality of a massless particle is defined by whether the directions of its spin and motion are parallel or antiparallel. Although massless chiral fermions-Weyl fermions-were predicted 90 years ago, their existence as fundamental particles has not been experimentally confirmed. However, their analogues have been observed as quasiparticles in condensed matter systems. In addition to Weyl fermions1-4, theorists have proposed a number of unconventional (that is, beyond the standard model) chiral fermions in condensed matter systems5-8, but direct experimental evidence of their existence is still lacking. Here, by using angle-resolved photoemission spectroscopy, we reveal two types of unconventional chiral fermion-spin-1 and charge-2 fermions-at the band-crossing points near the Fermi level in CoSi. The projections of these chiral fermions on the (001) surface are connected by giant Fermi arcs traversing the entire surface Brillouin zone. These chiral fermions are enforced at the centre or corner of the bulk Brillouin zone by the crystal symmetries, making CoSi a system with only one pair of chiral nodes with large separation in momentum space and extremely long surface Fermi arcs, in sharp contrast to Weyl semimetals, which have multiple pairs of Weyl nodes with small separation. Our results confirm the existence of unconventional chiral fermions and provide a platform for exploring the physical properties associated with chiral fermions.

2.
Bioorg Chem ; 150: 107565, 2024 Jun 15.
Article in English | MEDLINE | ID: mdl-38905884

ABSTRACT

The signal transducer and activator of transcription 3 (STAT3) has been established as a crucial drug target in the development of antitumor agents. In this study, a series of 21 derivatives of the STAT3 inhibitor napabucasin were designed and synthesized. Through preliminary screening against tumor cell lines, SZ6 emerged as the most potent compound with half maximal inhibitory concentration (IC50) values of 46.3 nM, 66.4 nM, and 53.8 nM against HCT116, HepG2, and Hela cells respectively. Furthermore, SZ6 effectively suppressed tumor invasion and migration in HCT116 cell assays by inducing S-phase arrest and apoptosis through inhibition of Protein Kinase B (PKB/AKT) activity and induction of reactive oxygen species (ROS). The mechanism underlying SZ6's action involves inhibition of STAT3 phosphorylation, which was confirmed by western blotting analysis. Additionally, surface plasmon resonance (SPR) and cellular thermal shift assay (CETSA) demonstrated direct binding between SZ6 and STAT3. Notably, in vivo studies revealed that SZ6 significantly inhibited tumor growth without any observed organ toxicity. Collectively, these findings identify SZ6 as a promising STAT3 inhibitor for colorectal cancer treatment.

3.
J Am Chem Soc ; 145(24): 13134-13146, 2023 Jun 21.
Article in English | MEDLINE | ID: mdl-37278596

ABSTRACT

Stable metal nitrides (MN) are promising materials to fit the future "green" ammonia-hydrogen nexus. Either through catalysis or chemical looping, the reductive hydrogenation of MN to MN1-x is a necessary step to generate ammonia. However, encumbered by the formation of kinetically stable M-NH1─3 surface species, this reduction step remains challenging under mild conditions. Herein, we discovered that deleterious Ti-NH1─3 accumulation on TiN can be circumvented photochemically with supported single atoms and clusters of platinum (Pt1-Ptn) under N2-H2 conditions. The photochemistry of TiN selectively promoted Ti-NH formation, while Pt1-Ptn effectively transformed any formed Ti-NH into free ammonia. The generated ammonia was found to originate mainly from TiN reduction with a minor contribution from N2 activation. The knowledge accrued from this fundamental study could serve as a springboard for the development of MN materials for more efficient ammonia production to potentially disrupt the century-old fossil-powered Haber-Bosch process.

4.
Small ; 19(36): e2302357, 2023 Sep.
Article in English | MEDLINE | ID: mdl-37127849

ABSTRACT

Low-dimensional hybrid metal halide (LDHMH) materials have attracted considerable attention owing to their intriguing optical properties. To the best of the knowledge, this is the first study to successfully demonstrate both self-trap exciton (STE) and afterglow emissions in Zr-based LDHMH materials. The obtained pure (Ph3 S)2 ZrCl6 crystals showed near-ultraviolet phosphorescence and a green afterglow owing to the organic cation Ph3 S+ , while the Bi-doped and Sb-doped crystals exhibited both STE and afterglow emissions. However, the Te-doped crystals showed only a broad yellow STE emission owing to the [TeCl6 ]2- octahedron. In addition, all the crystals showed good stability. Notably, Sb-doped crystals produced white light, which can be adjusted between cold white and warm white using different excitations. Finally, this strategy for both STE and afterglow emissions can be applied to other LDHMH materials for optical applications.

5.
Langmuir ; 39(10): 3792-3799, 2023 Mar 14.
Article in English | MEDLINE | ID: mdl-36853231

ABSTRACT

Low-dimension perovskite materials have attracted wide attention due to their excellent optical properties and stability. Herein, Sb3+-doped Cs2ZrCl6 crystals are synthesized by a coprecipitation method in which Sb3+ ions partially replace Zr4+ ions. The Cs2ZrCl6:xSb3+ powder shows blue and orange-red emissions under a 254 and 365 nm light, respectively, due to the [ZrCl6]2- octahedron and [SbCl6]3- octahedron. The photoluminescence quantum yield (PLQY) of Cs2ZrCl6:xSb3+ (x = 0.1) crystals is up to 52.5%. According to experimental and computational results, the emission mechanism of the Cs2ZrCl6:xSb3+ crystals is proposed. On the one hand, a wide blue emission with a large Stokes shift is caused by the self-trapping excitons of [ZrCl6]2- octahedra under a 260 nm excitation. On the other hand, the luminescence mechanism of [SbCl6]3- octahedron is divided into two parts: 1P1 → 1S0 (490 nm) and 3P1 → 1S0 (625 nm). The broad-band emission, high PLQY, and excellent stability endow the Cs2ZrCl6:xSb3+ powders with the potential for the fabrication of white light-emitting diodes (WLEDs). A WLED device is fabricated using a commercial 310 nm NUV chip, which shows a high color rendering index of 89.7 and a correlated color temperature of 5333 K. In addition, the synthesized Cs2ZrCl6:xSb3+ crystals can be also successfully used for information encryption. Our work will provide a deep understanding of the photophysical properties of Sb3+-doped perovskites and facilitate the development of Cs2ZrCl6:xSb3+ crystals in encrypting multilevel optical codes and WLEDs.

6.
Oral Dis ; 29(5): 2096-2106, 2023 Jul.
Article in English | MEDLINE | ID: mdl-35593110

ABSTRACT

OBJECTIVES: Sialin is a multifunctional molecule with a well-described role in physiological equilibrium regulation. The aim of this study was to elucidate the role of sialin in salivary glands regeneration. MATERIALS AND METHODS: Submandibular gland duct ligation/deligation of rat was performed to develop a rat model of submandibular gland regeneration. Phenotype changes were investigated using Western blotting and quantitative real-time polymerase chain reaction, as well as immunohistochemical staining. LV-slc17a5-RNAi vectors were injected into the submandibular glands via retroductal instillation to establish a stable sialin-knockdown model. RESULTS: Submandibular gland tissue structure could completely restore 28 days after duct deligation, when the duct had been ligated for 7 days. The expression of sialin, polysialic acid, and polysialyltransferase IV was significantly increased on Day 0 after duct deligation, and it returned to the level of the control group at Day 28. Moreover, sialin knockdown could weakened gland regeneration by reducing polysialic acid synthesis. Supplementing drinking water with polysialic acid precursors (ManNAc) in drinking water could partially rescue submandibular gland regeneration in sialin-knockdown rats. CONCLUSION: These data indicated that sialin was vital for submandibular gland regeneration which mediated the process of gland regeneration by affecting the polysialic acid synthesis.


Subject(s)
Drinking Water , Submandibular Gland , Rats , Animals , Submandibular Gland/metabolism , Drinking Water/analysis , Drinking Water/metabolism , Salivary Ducts , Regeneration
7.
Pharm Biol ; 61(1): 1054-1064, 2023 Dec.
Article in English | MEDLINE | ID: mdl-37416997

ABSTRACT

CONTEXT: Hydroxysafflor yellow A (HSYA) is the main bioactive ingredient of safflower (Carthamus tinctorius L., [Asteraceae]) for traumatic brain injury (TBI) treatment. OBJECTIVE: To explore the therapeutic effects and underlying mechanisms of HSYA on post-TBI neurogenesis and axon regeneration. MATERIALS AND METHODS: Male Sprague-Dawley rats were randomly assigned into Sham, controlled cortex impact (CCI), and HSYA groups. Firstly, the modified Neurologic Severity Score (mNSS), foot fault test, hematoxylin-eosin staining, Nissl's staining, and immunofluorescence of Tau1 and doublecortin (DCX) were used to evaluate the effects of HSYA on TBI at the 14th day. Next, the effectors of HSYA on post-TBI neurogenesis and axon regeneration were screened out by pathology-specialized network pharmacology and untargeted metabolomics. Then, the core effectors were validated by immunofluorescence. RESULTS: HSYA alleviated mNSS, foot fault rate, inflammatory cell infiltration, and Nissl's body loss. Moreover, HSYA increased not only hippocampal DCX but also cortical Tau1 and DCX following TBI. Metabolomics demonstrated that HSYA significantly regulated hippocampal and cortical metabolites enriched in 'arginine metabolism' and 'phenylalanine, tyrosine and tryptophan metabolism' including l-phenylalanine, ornithine, l-(+)-citrulline and argininosuccinic acid. Network pharmacology suggested that neurotrophic factor (BDNF) and signal transducer and activator of transcription 3 (STAT3) were the core nodes in the HSYA-TBI-neurogenesis and axon regeneration network. In addition, BDNF and growth-associated protein 43 (GAP43) were significantly elevated following HSYA treatment in the cortex and hippocampus. DISCUSSION AND CONCLUSIONS: HSYA may promote TBI recovery by facilitating neurogenesis and axon regeneration through regulating cortical and hippocampal metabolism, BDNF and STAT3/GAP43 axis.


Subject(s)
Brain Injuries, Traumatic , Chalcone , Rats , Male , Animals , Rats, Sprague-Dawley , Brain-Derived Neurotrophic Factor , Axons , Nerve Regeneration , Brain Injuries, Traumatic/drug therapy , Quinones/pharmacology , Chalcone/pharmacology , Metabolomics
8.
Entropy (Basel) ; 25(8)2023 Aug 09.
Article in English | MEDLINE | ID: mdl-37628212

ABSTRACT

Remote sensing images are important data sources for land cover mapping. As one of the most important artificial features in remote sensing images, buildings play a critical role in many applications, such as population estimation and urban planning. Classifying buildings quickly and accurately ensures the reliability of the above applications. It is known that the classification accuracy of buildings (usually indicated by a comprehensive index called F1) is greatly affected by image quality. However, how image quality affects building classification accuracy is still unclear. In this study, Boltzmann entropy (an index considering both compositional and configurational information, simply called BE) is employed to describe image quality, and the potential relationships between BE and F1 are explored based on images from two open-source building datasets (i.e., the WHU and Inria datasets) in three cities (i.e., Christchurch, Chicago and Austin). Experimental results show that (1) F1 fluctuates greatly in images where building proportions are small (especially in images with building proportions smaller than 1%) and (2) BE has a negative relationship with F1 (i.e., when BE becomes larger, F1 tends to become smaller). The negative relationships are confirmed using Spearman correlation coefficients (SCCs) and various confidence intervals via bootstrapping (i.e., a nonparametric statistical method). Such discoveries are helpful in deepening our understanding of how image quality affects building classification accuracy.

9.
Small ; 18(44): e2204198, 2022 Nov.
Article in English | MEDLINE | ID: mdl-36148829

ABSTRACT

Lead-free perovskites have gained much interest for photovoltaic and optoelectronic applications. But instability and low quantum efficiency significantly limit their prospects for future applications. Here, a general route is reported to synthesize highly stable lead-free perovskites on a large scale with remarkably enhanced quantum efficiency. Two typical vacancy-ordered double perovskites (Cs2 ZrCl6 and Cs2 SnCl6 ) and their corresponding Bi3+ or Sb3+ doped samples are synthesized in ionic liquids (ILs) solutions via a simple solution method. These prepared perovskite samples all exhibit high-quality crystalline structures and their photoluminescence quantum yields (PLQYs) all show an increase close to 200% compared to the samples prepared in the hydrochloric acid system. The PLQY of Sb-doped Cs2 ZrCl6 with excellent thermal stability can reach up to 90.2%, which is the highest value reported for this system (Cs2 ZrCl6 :Sb). Density functional theory calculations reveal that the corresponding interaction between the ILs and the samples can effectively improve the crystal quality and reduce energy loss. The potential applications of the prepared samples for high-performance white light-emitting diodes and optical anti-counterfeiting are also demonstrated. The findings provide a straightforward way to obtain ultrahigh quantum efficiency vacancy-ordered double perovskites with good thermal stability and excellent optoelectronic properties.

10.
Small ; 18(26): e2201589, 2022 Jul.
Article in English | MEDLINE | ID: mdl-35638221

ABSTRACT

Developing intrinsically stretchable organic solar cells (OSCs) with excellent mechanical robustness and long-term operation stability is highly demanded for practical applications. Here, the representative PM6/Y6 active layer film, crosslinked by a photo-crosslinkable small molecule 2,6-bis(4-azidobenzylidene)cyclohexanone (BAC) containing azide groups, exhibits a significantly enhanced stretchability of 18% and toughness of 6.94 MJ m-3 , compared to non-crosslinked film (stretchability of 4.5% and toughness of 0.75 MJ m-3 ). It is found that controlling the crosslinking density, including crosslinker concentration and crosslinking time, plays a vital impact on the stretchability and mechanical toughness of active layer film. The resulting intrinsically stretchable OSCs achieve a high power conversion efficiency (PCE) of 13.4% and retain 80% of its performance even under the large strain of 20%. To date, this is the highest PCE for intrinsically stretchable OSCs based on small molecular acceptors. Moreover, crosslinking of active layer film suppresses the crystallization of PM6 polymer chains and avoids the excessive aggregation of small molecular acceptors under thermal heating or light illumination, leading to a stabilized film morphology and significantly improved device stability. Overall, these results provide a universal strategy to simultaneously enhance the mechanical properties and stability of OSCs without sacrificing their photovoltaic performance.

11.
Inorg Chem ; 61(35): 14095-14101, 2022 Sep 05.
Article in English | MEDLINE | ID: mdl-35994396

ABSTRACT

Due to the toxicity and instability issues of lead halide perovskites, lead-free perovskites have recently emerged as a viable alternative. However, significant optical band gaps of lead-free perovskites exert influence on their luminescent properties. Fortunately, the addition of dopants becomes an efficacious solution. The current widely utilized methods for synthesizing perovskites almost require high temperatures, a long period, and atmosphere protection, which cost more energy and resources. In this paper, we report that Rb2ZrCl6:xSb3+ perovskite phosphors can be easily prepared by a wet grinding approach at room temperature, which is a more efficient and facile process. Due to the self-trapped excitons of the host structure and Sb3+ ions, the produced samples display blue-white and orange fluorescence under UV lamp irradiation at 254 and 365 nm, respectively. In the photoluminescence spectrum, the doped perovskite exhibits an emission peak at 630 nm under excitation at 365 nm. Importantly, the prepared phosphors have tunable emissions related to the excitation wavelength. In addition, our produced powders show remarkable stability at room temperature, laying the foundations for this approach to be widely used in perovskite production.

12.
Environ Res ; 207: 112227, 2022 05 01.
Article in English | MEDLINE | ID: mdl-34666018

ABSTRACT

Although humans are generally exposed to second-hand smoke (SHS), volatile organic compounds (VOCs) exposure derived from SHS and its health hazard to non-smokers are rarely investigated. Thus, we examined the effects of SHS on VOCs exposure and oxidative stress damage via a passive smoking simulation experiment in 6 children and 7 adults. To further validate the studied urinary VOC metabolites as biomarkers for passive smoking, 259 children were recruited. The levels of 8-hydroxy-2'-deoxyguanosine (8-OHdG), malonaldehyde (MDA), trans-3'-hydroxycotinine (OH-Cot) and 31 VOC metabolites in urine were determined. The results showed that the geomean concentrations of 17 VOC metabolites in urine of children were 26.5%-138% higher than those of adults after passive smoking. The levels of urinary 8-OHdG, MDA and OH-Cot increased by 24.6%, 18.8% and 600% in children, but only 1.25%, 10.3% and 116% in adults, respectively. Therefore, children are more vulnerable to SHS than adults. After exposure to SHS, the levels of 8 urinary VOC metabolites of benzene, acrylonitrile, 1-bromopropane, propylene oxide, toluene, methyl methacrylate and cyanide increased by 60.9%-538% within 23 h. These 8 VOC metabolites were also significantly associated with 8-OHdG or MDA in urine (p < 0.01). Therefore, exposure to VOCs caused by SHS increases body oxidative stress damage. OH-Cot level higher than 2.00 µg/g Cr can be used as a threshold of passive smoking. The levels of urinary s-benzylmercapturic acid (BMA) and s-phenylmercapturic acid (PMA) in children increased by 494% and 728% within 6 h after passive smoking, respectively. Population validation study indicated that BMA and PMA levels were significantly elevated in children exposed to SHS. Therefore, in addition to OH-Cot, urinary BMA and PMA are potentially useful short-term biomarkers of passive smoking. Future studies should focus on the differences in VOC metabolism and detoxification mechanisms between children and adults.


Subject(s)
Tobacco Smoke Pollution , Volatile Organic Compounds , 8-Hydroxy-2'-Deoxyguanosine , Adult , Biomarkers/urine , Child , Humans , Oxidative Stress , Tobacco Smoke Pollution/adverse effects , Tobacco Smoke Pollution/analysis
13.
Pestic Biochem Physiol ; 183: 105085, 2022 May.
Article in English | MEDLINE | ID: mdl-35430075

ABSTRACT

Nootkatone, a sesquiterpenoid isolated from Alaskan yellow cedar (Cupressus nootkatensis), is known to possess insect repellent and acaricidal properties and has recently been registered for commercial use by the Environmental Protection Agency. Previous studies failed to elucidate the mechanism of action of nootkatone, but we found a molecular overlay of picrotoxinin and nootkatone indicated a high degree of structural and electrostatic similarity. We therefore tested the hypothesis that nootkatone was a GABA-gated chloride channel antagonist, similar to picrotoxinin. The KD50 and LD50 of nootkatone on the insecticide-susceptible strain of Drosophila melanogaster (CSOR) showed resistance ratios of 8 and 11, respectively, compared to the cyclodiene-resistant strain of RDL1675, indicating significant cross-resistance. Nootkatone reversed GABA-mediated block of the larval CSOR central nervous system; nerve firing of 78 ± 17% of baseline in the CSOR strain was significantly different from 24 ± 11% of baseline firing in the RDL1675 strain (p = 0.035). This finding indicated that the resistance was expressed within the nervous system. Patch clamp recordings on D. melanogaster central neurons mirrored extracellular recordings where nootkatone inhibited GABA-stimulated currents by 44 ± 9% at 100 µM, whereas chloride current was inhibited 4.5-fold less at 100 µM in RDL1675. Taken together, these data suggest nootkatone toxicity in D. melanogaster is mediated through GABA receptor antagonism.


Subject(s)
Drosophila melanogaster , Insecticides , Animals , Insecticide Resistance , Insecticides/toxicity , Polycyclic Sesquiterpenes , Receptors, GABA , gamma-Aminobutyric Acid/pharmacology
14.
J Craniofac Surg ; 33(6): 1698-1704, 2022 Sep 01.
Article in English | MEDLINE | ID: mdl-35184105

ABSTRACT

ABSTRACT: Real-time surgical navigation systems are important for preoperative planning and intraoperative navigation. Automatic preoperative multimodal data registration and postoperative spatial registration are extremely crucial in such surgical navigation systems. However, existing automatic multimodal data registration methods have extremely limited application scope due to the lack of accuracy and speed. In addition, the registration results obtained by existing methods are practically lacking and are rarely applied in clinics. To address the above issues, this paper proposes a novel real-time teeth registration algorithm with computed tomography (CT) data and optical tracking scanning data. The proposed method is based on the weighted iterative closest point (ICP) algorithm with 3 improvements: (1) the multilayer spherical point set is generated inside the laser scanning marker sphere, (2) the weight decreases from inside to outside layer by layer, and (3) the weight of the voxel center point set is combined with the CT data of the marker sphere. Specifically, the proposed iCP registration method can overcome the limitation of surface point set registration and tackle the problem of high surface deformity of laser scanning marker spheres. For the registration result of CT and scanning data, the authors employ the real-time spatial registration algorithm based on optical tracking to complete the navigation of the simulated surgical instruments on the multimodal fusion image. The experimental results show that the proposed ICP algorithm reduces the mean square error by 1 order of magnitude and that our method has strong practical value.


Subject(s)
Surgery, Computer-Assisted , Surgery, Oral , Algorithms , Humans , Imaging, Three-Dimensional/methods , Surgery, Computer-Assisted/methods , Tomography, X-Ray Computed/methods
15.
Phys Rev Lett ; 126(23): 236601, 2021 Jun 11.
Article in English | MEDLINE | ID: mdl-34170154

ABSTRACT

Weyl semimetals host a variety of exotic effects that have no counterpart in conventional materials, such as the chiral anomaly and magnetic monopole in momentum space. These effects give rise to unusual transport properties, including a negative magnetoresistance and a planar Hall effect, etc. Here, we report a new type of Hall and magnetoresistance effect in a magnetic Weyl semimetal. Unlike antisymmetric (with respect to either magnetic field or magnetization) Hall and symmetric magnetoresistance in conventional materials, the discovered magnetoresistance and Hall effect are antisymmetric in both magnetic field and magnetization. We show that the Berry curvature, the tilt of the Weyl node, and the chiral anomaly synergically produce these phenomena. Our results reveal a unique property of Weyl semimetals with broken time reversal symmetry.

16.
World J Urol ; 39(3): 921-927, 2021 Mar.
Article in English | MEDLINE | ID: mdl-32447440

ABSTRACT

PURPOSE: The purpose of this study was to evaluate the safety and efficiency of multiple-tract percutaneous nephrolithotomy (PCNL) as a day surgery for the treatment of complex renal stones. PATIENTS AND METHODS: A mature protocol for day surgery was implemented. Forty-six patients who underwent planned day-surgery PCNL via multiple tracts for the treatment of complex renal stones were retrospectively reviewed. All procedures were performed by an experienced surgeon. The outcomes were recorded. RESULTS: The mean stone size and burden were 4.8 cm and 990.2 mm2, respectively. There were 26 (56.5%) and 20 (43.5%) patients with staghorn stones and multiple stones, respectively. Totals of two, three, and more than three tracts (with up to 7 tracts) were established in 22, 11, and 13 patients, respectively. The tract sizes ranged from 14 to 24 Fr. One to four nephrostomy tubes were placed in most patients, and a tubeless process was accomplished in only 3 (6.5%) patients. The mean surgery time was 116 min with a hemoglobin drop of 22.1 ± 16.8 g/L. Eight (17.4%) patients developed postoperative complications, with severe complications (Clavien grades III-IV) in two cases (4.4%). 39 (84.8%) patients were discharged within 24 h after surgery, and 7 (15.2%) patients were fully admitted. Only 1 (2.2%) patient required readmission. The stone clearance rate was 84.8%. CONCLUSIONS: Day-surgery PCNL can be safely performed via multiple percutaneous tracts by experienced surgeons and is an efficient strategy for the treatment of complex renal stones.


Subject(s)
Ambulatory Surgical Procedures , Kidney Calculi/surgery , Nephrolithotomy, Percutaneous/methods , Adult , Aged , Female , Humans , Kidney Calculi/pathology , Male , Middle Aged , Nephrolithotomy, Percutaneous/adverse effects , Postoperative Complications/epidemiology , Retrospective Studies , Treatment Outcome , Young Adult
17.
Phys Chem Chem Phys ; 23(10): 6204-6212, 2021 Mar 18.
Article in English | MEDLINE | ID: mdl-33687420

ABSTRACT

Density functional theory (DFT) calculations (M06-2X) have been employed to disclose the mechanisms and regio- and stereo-selectivities of the N-heterocyclic carbene (NHC)-catalyzed reaction of 2-benzothiazolimines and α-chloroaldehydes. The preferred mechanism is initiated by the nucleophilic attack of NHC on α-chloroaldehyde (first step), followed by 1,2-proton transfer which was assisted by the Brønsted acid DABCO·H+ to generate the Breslow intermediate (second step). The cleavage of the C-Cl bond (third step) and deprotonation (fourth step) form the enolate intermediate. This further reacts with 2-benzothiazolimine which leads to the formation of a new C-C bond (fifth step). Subsequent cyclization takes place via the formation of a new C-N bond (sixth step). Catalyst regeneration completes the whole catalytic cycle and affords the final product (seventh step). The DFT results indicate that the fifth step determines the stereochemistry of the reaction and leads to benzothiazolopyrimidinone with the SS configuration, which agrees well with experimental observations. Intramolecular cyclization is found to be the regioselectivity-determining step, for which the [4+2] annulation pathway is more preferred than that via [2+2] annulation, which again agrees well with experimental observations. Based on the mechanism proposed, the origins of regio- and stereoselectivities have also been investigated by performing distortion/interaction, natural bond orbital (NBO) and non-covalent interaction (NCI) analyses. The mechanistic insights gained in this work should be helpful in the rational design of potential catalysts for analogous reactions.

18.
Ecotoxicol Environ Saf ; 210: 111864, 2021 Mar 01.
Article in English | MEDLINE | ID: mdl-33412282

ABSTRACT

Volatile organic compounds (VOCs) are important and ubiquitous air pollutants, which may lead to a significant increase in the prevalence of respiratory diseases. To investigate the relationships between VOCs exposure and childhood asthma, 252 asthmatic children and 69 healthy children were recruited. Urinary 8-hydroxy-2'-deoxyguanosine (8-OHdG, a biomarker of oxidative DNA damage), trans-3'-hydroxycotinine (OH-Cot, a biomarker of passive smoking) and 27 VOC metabolites were simultaneously determined by an ultra-high-performance liquid chromatography-tandem mass spectrometer. Results showed that levels of 8-OHdG and most VOC metabolites in asthmatic children were significantly higher than those in healthy children. More than half of the VOC metabolites were significantly and positively associated with OH-Cot with maximal ß coefficient of 0.169, suggesting that second-hand smoking is one important source of VOCs exposure for children in Guangzhou. Significant dose-response relationships between most VOC metabolites and 8-OHdG were observed. Each unit increase in ln-transformed VOC metabolite levels was significantly associated with 5.5-32% increase in ln-transformed 8-OHdG level. Moreover, each unit increase in ln-transformed 8-OHdG level was associated with an 896% increased odd ratios (OR) of asthma in children (OR = 9.96, 95% confidence intervals (CI): 4.75, 20.9), indicating that oxidative stress induced by VOCs exposure may have a significant impact on childhood asthma. Urinary 3-&4-Methylhippuric acid (3-&4-MHA, OR: 5.78, 95% CI: 3.50, 9.54), rac 2-Aminothiazoline-4-carboxylic acid (ATCA, OR: 2.90, 95% CI: 1.69, 4.99) and N-Acetyl-S-(3,4-dihydroxybutyl)-L-cysteine (DHBMA, OR: 2.76, 95% CI: 1.73, 4.43) which may derive from m/p-xylene, cyanide and 1,3-butadiene exposure, respectively, could significantly and maximally increase the odds of asthma. Interestingly, they also had the strongest associations with 8-OHdG among all investigated VOC metabolites. Moreover, DHBMA strongly correlated with most VOC metabolites. Hence, DHBMA is a suitable biomarker to indicate not only VOCs exposure profile, but also the DNA damage-mediated asthma induced by VOCs.


Subject(s)
Asthma/urine , Environmental Pollutants/urine , Oxidative Stress , Tobacco Smoke Pollution/adverse effects , Volatile Organic Compounds/urine , 8-Hydroxy-2'-Deoxyguanosine/urine , Asthma/epidemiology , Biological Monitoring , Biomarkers/urine , Child , China/epidemiology , Cotinine/analogs & derivatives , Cotinine/urine , Environmental Pollutants/metabolism , Female , Humans , Male , Volatile Organic Compounds/metabolism
19.
Clin Otolaryngol ; 46(2): 395-405, 2021 Mar.
Article in English | MEDLINE | ID: mdl-33321001

ABSTRACT

OBJECTIVES: We aimed to determine the prognostic value of the neutrophil-to-lymphocyte ratio (NLR), platelet-to-lymphocyte ratio (PLR) and systemic immune-inflammation index (SII) in patients with laryngeal squamous cell carcinoma (LSCC). DESIGN AND SETTING: A retrospective analysis of patients with LSCC was conducted in our hospitals. Clinical information, including age, sex, TNM classification and other demographic and clinical data, was acquired and analysed. Progression-free survival (PFS) and overall survival (OS) were calculated and compared using the Kaplan-Meier method and log-rank test. PARTICIPANTS: A total of 147 patients with LSCC were included. RESULTS: According to the receiver operating characteristic (ROC) curve, the optimal cut-off points for NLR, PLR and SII were 1.88, 117.36 and 517.64. The analysis revealed NLR, PLR and SII to be independent predictors for OS and PFS (P < .05). CONCLUSIONS: Preoperative NLR, PLR and SII are promising prognostic predictors for patients with LSCC.


Subject(s)
Blood Platelets/immunology , Carcinoma, Squamous Cell/immunology , Laryngeal Neoplasms/immunology , Lymphocytes/immunology , Neutrophils/immunology , Adult , Aged , Aged, 80 and over , Carcinoma, Squamous Cell/mortality , Female , Humans , Inflammation/immunology , Laryngeal Neoplasms/mortality , Male , Middle Aged , Prognosis , Retrospective Studies , Survival Analysis
20.
World J Urol ; 38(5): 1323-1328, 2020 May.
Article in English | MEDLINE | ID: mdl-31522237

ABSTRACT

PURPOSE: Percutaneous nephrolithotomy (PCNL) is traditionally performed on an inpatient basis. We determine the safety and outcome of day-surgery PCNL by experienced surgeon hands. PATIENTS AND METHODS: A protocol for day-surgery PCNL was undertaken. A retrospective analysis of all 86 cases of planned day-surgery PCNL accomplished by an experienced surgeon who followed this protocol between May 2017 and March 2019 was performed. Patient demographics, operative data, complications, and readmission rates were recorded. Day-surgery PCNL was defined as discharge of patients either the same day or within 24 h after surgery. RESULTS: The average stone burden was 361.1 mm2 and 70 (81.4%) of patients had multiple stones or staghorn stones. 82 (95.4%) patients achieved same-day discharge or received overnight observation prior to discharge, and 4 patients (4.6%) required full admission (longer than 24 h). The readmission rate was 2.3% (2 patients). The postoperative complications occurred in 10 (11.6%) patients, including 7, 2, 2 of grade I, II, III complications. The average operation time was 64 min and the hemoglobin drop was 15.7 ± 16.9 g/L. The established tracts size ranged from 16 to 22Fr. The stone clearance rate was 90.7%. The tubeless without nephrostomy tube was performed in 60.5%. Eight cases were performed by multiple-tracts PCNL with 2-4 tracts, with only two case required full admission. CONCLUSION: Experienced surgeons who performed day-surgery PCNL experience excellent patient outcomes in appropriately selected patients. Most complications can be treated conservatively and only a few required intervention or readmission.


Subject(s)
Ambulatory Surgical Procedures , Kidney Calculi/surgery , Nephrolithotomy, Percutaneous , Adult , Female , Hospitals, High-Volume , Humans , Male , Middle Aged , Nephrolithotomy, Percutaneous/adverse effects , Nephrolithotomy, Percutaneous/methods , Retrospective Studies , Treatment Outcome
SELECTION OF CITATIONS
SEARCH DETAIL