RESUMO
Reactive oxygen species (ROS) have emerged as a promising treatment option for antibacterial and biofilm eradication. However, their therapeutic efficacy is significantly hampered by the unique microenvironments of diabetic wounds. In this study, we designed and synthesized porphyrin-based Fe covalent organic frameworks (Fe-COF) through a Schiff base condensation reaction. Subsequently, Fe-COF were encapsulated with hyaluronic acid (HA) through electrostatic adsorption, resulting in a novel formulation named HA-Fe-COF for diabetic wound healing. HA-Fe-COF were engineered to respond to hyaluronidase in the infected wound, leading to the controlled release of Fe-COF. Those released Fe-COF served a dual role as photosensitizers, generating singlet oxygen and localized heating when exposed to dual light sources. Additionally, they acted as peroxidase-like nanozymes, facilitating the production of ROS through enzymatic reactions. This innovative approach enabled a synergistic therapeutic effect combining photodynamic, photothermal, and chemodynamic modalities. Furthermore, the sustained release of HA from HA-Fe-COF promoted angiogenesis, collagen deposition, and re-epithelialization during the diabetic wound healing process. This "all-in-one" strategy offers a novel approach for the development of antimicrobial and biofilm eradication strategies that minimize damage to healthy tissues in vivo.
Assuntos
Ácido Hialurônico , Estruturas Metalorgânicas , Porfirinas , Cicatrização , Cicatrização/efeitos dos fármacos , Animais , Ácido Hialurônico/química , Ácido Hialurônico/farmacologia , Estruturas Metalorgânicas/química , Estruturas Metalorgânicas/farmacologia , Porfirinas/química , Porfirinas/farmacologia , Camundongos , Espécies Reativas de Oxigênio/metabolismo , Fármacos Fotossensibilizantes/química , Fármacos Fotossensibilizantes/farmacologia , Fármacos Fotossensibilizantes/administração & dosagem , Fármacos Fotossensibilizantes/síntese química , Antibacterianos/farmacologia , Antibacterianos/química , Antibacterianos/administração & dosagem , Pele/efeitos dos fármacos , Humanos , Infecção dos Ferimentos/tratamento farmacológico , Infecção dos Ferimentos/microbiologia , Ferro/química , Fotoquimioterapia/métodos , HialuronoglucosaminidaseRESUMO
Insight into effect of deuterium isotopes on organic near-IR (NIR) emitters was explored by the use of self-assembled Pt(II) complexes H-3-f and HPh-3-f, and their deuterated analogues D-3-f and DPh-3-f, respectively (Schemeâ 2). In vacuum deposited thin film, albeit having nearly identical emission spectral feature maximized at ~810â nm, H-3-f and D-3-f exhibit remarkable difference in photoluminescence quantum yield (PLQY) of 29 % and 50 %, respectively. Distinction in PLQY is also observed for HPh-3-f (800â nm, 50 %) and DPh-3-f (798â nm, 67 %). We then elucidated the theoretical differences in the impact on near-infrared (NIR) luminescence between Pt(II) complexes and organic small molecules upon deuteration. The results establish a general guideline for the deuteration on NIR emission efficiency. From a perspective of practical application, NIR OLEDs based on D-3-f and DPh-3-f emitters attain EQEmax of 15.5 % (radiance 31,287â mW Sr-1 m-2 ) and 16.6 % (radiance of 32,279â mW Sr-1 m-2 ) at 764â nm and 796â nm, respectively, both of which set new records for NIR OLEDs of >750â nm.
RESUMO
Upon fusing the pyrazinyl pyrazole entity in giving pyrazolo[3,4-f]quinoxaline chelate, the corresponding Os(II) based NIR emitter exhibited "invisible" and efficient electroluminescence with a peak maximum at 811â nm. A maximum external quantum efficiency of 0.97 % and a suppressed efficiency roll-off till a current density of 300â mA cm-2 was also exhibited.
RESUMO
BACKGROUND: Laparoscopic liver resections (LLR) have been shown a treatment approach comparable to open liver resections (OLR) in hepatocellular carcinoma (HCC). However, the influence of procedural type on body composition has not been investigated. The aim of the current study was to compare the degree of skeletal muscle loss between LLR and OLR for HCC. METHODS: By using propensity score matching (PSM) analysis, 64 pairs of patients were enrolled. The change of psoas muscle index (PMI) after the operation was compared between the matched patients in the LLR and OLR. Risk factors for significant muscle loss (defined as change in PMI > mean change minus one standard deviation) were further investigated by multivariate analysis. RESULTS: Among patients enrolled, there was no significant difference in baseline characteristics between the two groups. The PMI was significantly decreased in the OLR group (P = 0.003). There were also more patients in the OLR group who developed significant muscle loss after the operations (P = 0.008). Multivariate analysis revealed OLR (P = 0.023), type 2 diabetes mellitus, indocyanine green retention rate at 15 min (ICG-15) > 10%, and cancer stage ⧠3 were independent risk factors for significant muscle loss. In addition, significant muscle loss was associated with early HCC recurrence (P = 0.006). Metabolomic analysis demonstrated that the urea cycle may be decreased in patients with significant muscle loss. CONCLUSION: LLR for HCC was associated with less significant muscle loss than OLR. Since significant muscle loss was a predictive factor for early tumor recurrence and associated with impaired liver metabolism, LLR may subsequently result in a more favorable outcome.
Assuntos
Carcinoma Hepatocelular , Diabetes Mellitus Tipo 2 , Laparoscopia , Neoplasias Hepáticas , Humanos , Carcinoma Hepatocelular/cirurgia , Neoplasias Hepáticas/cirurgia , Laparoscopia/efeitos adversos , Músculo EsqueléticoRESUMO
This study investigated how predictability and prosodic phrasing interact in accounting for the variability of syllable duration in Taiwan Southern Min. Speech data were extracted from 8 hours of spontaneous speech. Three predictability measurements were examined: bigram surprisal, bigram informativity, and lexical frequency. Results showed that higher informativity and surprisal led to longer syllables. As for the interaction with prosodic positions, there was a general weakening of predictability effects for syllables closer to the boundary, especially in the pre-boundary position, where pre-boundary lengthening was the strongest. However, the effect of word informativity appeared to be least modulated by this effect of boundary marking. These findings are consistent with a hypothesis that prosodic structure modulates the predictability effects on phonetic variability. The robustness of informativity in predicting syllable duration also suggests a possibility of stored phonetic variants associated with a word's usual contextual predictability.
Assuntos
Fonética , Percepção da Fala , Humanos , Taiwan , FalaRESUMO
Ir(III) metal complexes and related emitters bearing all kind of cyclometalated chromophoric chelates and non-chromophoric ancillary are extensively studied during the past three decades. Many of them have been found to display bright room temperature phosphorescence from triplet excited states in both solution and solid states, offering a possible application in contemporary optoelectronic technologies, including organic light emitting diodes, electrochemiluminescence, biological imaging and chemical sensing. Among reported materials, there are Ir(III) complexes with at least one phosphorus (P)-containing ligand and/or ancillary chelate, together with cyclometalates or equivalents that are in control of the actual emission energy. Particularly, possession of P-based donor can lead to divergent structural and photophysical properties compared to the traditional designs. This review aims to provide a literature overview as well as the authors' personal account to the development of relevant Ir(III) based phosphors bearing these P-donors. To the readers' convenience, the contents are subdivided into six sessions, according to whether or not they are charge natural, or with mono- or dianionic electronic character, and in accordance to their divergent bonding modes, i. e. monodentate, bidentate and tripodal coordination. In many cases, the P-based ancillaries offer an easy accessible route to the formation of efficient sky-blue and true-blue emitters due to their π-accepting property, together with enlarged emission energy gap and destabilized upper lying quenching state.
RESUMO
Four diplatinum(II) complexes with the formula [Pt(pypm)(µ-Fn)]2 (2, 3a-c) bearing both a pyridine-pyrimidinate chelate and formamidinate bridge, where (pypm)H and FnH stand for 5-(pyridin-2-yl)-2-(trifluoromethyl)pyrimidine and functional formamidines with various substituents of iPr (n = 1), Ph (n = 2), C6H4tBu (n = 3), and C6H4CF3 (n = 4), were synthesized en route from a mononuclear intermediate represented by [Pt(pypm)Cl(F1H)] (1). Single-crystal X-ray diffraction studies confirmed the structure of 1 and 3a comprised of an individual "Pt(pypm)" unit and two "Pt(pypm)" units with a Pt···Pt distance of 2.8845(2) Å, respectively. Therefore, in contrast to the structured emission of mononuclear 1 with the first vibronic peak wavelength at 475 nm, all other diplatinum complexes with shortened Pt···Pt separation exhibited greatly red shifted and structureless metal-metal to ligand charge transfer (MMLCT) emission that extended into the near-infrared region in solid states. Their photophysical characteristics were measured under three distinctive morphological states (i.e., crystals, sublimed powders, and vacuum-deposited thin films) by steady-state UV-vis spectroscopy, while retention of Pt···Pt interactions in deposited thin films of 2 and 3a-c was confirmed using Raman spectroscopy, demonstrating lowered Pt···Pt stretching at 80-200 cm-1. Most importantly, complexes 3a-c exhibited a gradual red shift with the trends crystals < sublimed powders < vacuum-deposited thin films, a result of increased intermolecular π-π stacking interactions and Pt···Pt interactions, while crystalline samples exhibited the highest luminescence among all three morphological states due to the fewest defects in comparison to other morphologies. Finally, 3b was selected as a nondoped emitter for the fabrication of NIR-emitting OLEDs, giving an electroluminescence peak at 767 nm and a maximum external quantum efficiency of 0.14% with negligible roll-off.
RESUMO
Acute-on-chronic liver failure (ACLF) implies high short-term mortality rates and usually requires intensive care unit (ICU) admission. Proper prognosis for these patients is crucial for early referral for liver transplantation. The superiority of CLIF-C ACLF score in Asian patients with ACLF admitted to an ICU remains inconclusive when compared to other scoring systems. The purpose of the study is (i) to compare the predictive performance of original MELD, MELD-Lactate, CLIF-C ACLF, CLIF-C ACLF-Lactate, and APACHE-II scores for short-term mortality assessment. (ii) to build and validate a novel scoring system and to compare its predictive performance to that of the original five scores. Two hundred sixty-five consecutive cirrhotic patients with ACLF who were admitted to our ICU were enrolled. The prognostic values for mortality were assessed by ROC analysis. A novel model was developed and internally validated using fivefold cross-validation. Alcohol abuse was identified as the primary etiology of cirrhosis. The AUROC of the five prognostic scores were not significantly superior to each other in predicting 1-month and 3-month mortality. The newly developed prognostic model, incorporating age, alveolar-arterial gradient (A-a gradient), BUN, total bilirubin level, INR, and HE grades, exhibited significantly improved performance in predicting 1-month and 3-month mortality with AUROC of 0.863 and 0.829, respectively, as compared to the original five prognostic scores. The novel ACLF model seems to be superior to the original five scores in predicting short-term mortality in ACLF patients admitted to an ICU. Further rigorous validation is required.
Assuntos
Insuficiência Hepática Crônica Agudizada , Unidades de Terapia Intensiva , Humanos , Insuficiência Hepática Crônica Agudizada/mortalidade , Masculino , Feminino , Unidades de Terapia Intensiva/organização & administração , Unidades de Terapia Intensiva/estatística & dados numéricos , Pessoa de Meia-Idade , Prognóstico , Idoso , Adulto , Curva ROC , Índice de Gravidade de Doença , Valor Preditivo dos Testes , APACHERESUMO
Using a transfer printing technique, we imprint a layer of a designated near-infrared fluorescent dye BTP-eC9 onto a thin layer of Pt(II) complex, both of which are capable of self-assembly. Before integration, the Pt(II) complex layer gives intense deep-red phosphorescence maximized at ~740 nm, while the BTP-eC9 layer shows fluorescence at > 900 nm. Organic light emitting diodes fabricated under the imprinted bilayer architecture harvest most of Pt(II) complex phosphorescence, which undergoes triplet-to-singlet energy transfer to the BTP-eC9 dye, resulting in high-intensity hyperfluorescence at > 900 nm. As a result, devices achieve 925 nm emission with external quantum efficiencies of 2.24% (1.94 ± 0.18%) and maximum radiance of 39.97 W sr-1 m-2. Comprehensive morphology, spectroscopy and device analyses support the mechanism of interfacial energy transfer, which also is proved successful for BTPV-eC9 dye (1022 nm), making bright and far-reaching the prospective of hyperfluorescent OLEDs in the near-infrared region.
RESUMO
BACKGROUND: Patients with autoimmune diseases (AD) generally carry an increased risk of developing cancer. However, the effect of AD in hepatocellular carcinoma (HCC) patients receiving surgical treatment is uncertain. The present study aimed to investigate the potential influence of AD on the survival of HCC patients undergoing hepatectomies. METHODS: Operated HCC patients were identified from the Chang Gung Research Database, and the survival outcomes of HCC patients with or without AD were analyzed ad compared. Cox regression model was performed to identify significant risk factors associated with disease recurrence and mortality. RESULTS: From 2002 to 2018, a total of 5532 patients underwent hepatectomy for their HCC. Among them, 229 patients were identified to have AD and 5303 were not. After excluding cases who died within 30 days of surgery, the estimated median overall survival (OS) was 43.8 months in the AD (+) group and 47.4 months in the AD (-) group (P = 0.367). The median liver-specific survival and disease-free survival (DFS) were also comparable between the two groups. After Cox regression multivariate analysis, the presence of AD did not lead to a higher risk of all-cause mortality, liver-specific mortality, or disease recurrence. CONCLUSION: Our study demonstrated that autoimmune disease does not impair the OS and DFS of HCC patients undergoing liver resections. AD itself is not a risk factor for tumor recurrence after surgery. Patients eligible for liver resections, as a result, should be considered for surgery irrespective of the presence of AD. Further studies are mandatory to validate our findings.
Assuntos
Doenças Autoimunes , Carcinoma Hepatocelular , Hepatectomia , Neoplasias Hepáticas , Humanos , Neoplasias Hepáticas/cirurgia , Neoplasias Hepáticas/mortalidade , Neoplasias Hepáticas/patologia , Carcinoma Hepatocelular/cirurgia , Carcinoma Hepatocelular/mortalidade , Carcinoma Hepatocelular/patologia , Masculino , Feminino , Hepatectomia/mortalidade , Doenças Autoimunes/complicações , Doenças Autoimunes/mortalidade , Doenças Autoimunes/cirurgia , Pessoa de Meia-Idade , Idoso , Recidiva Local de Neoplasia/patologia , Recidiva Local de Neoplasia/cirurgia , Estudos Retrospectivos , Fatores de Risco , Adulto , Taxa de Sobrevida , PrognósticoRESUMO
BACKGROUND: Recurrent common bile duct stone after endoscopic retrograde cholangiopancreatography is an undesirable problem, even when a following cholecystectomy is carried out. Important factors are the composition and properties of stones; the most significant etiology among these is the lipid level. While numerous studies have established the association between serum lipid levels and gallstones, no study has previously reported on recurrent common bile duct stones after endoscopic sphincterotomy with following cholecystectomy. MATERIALS AND METHODS: We retrospectively collected 2016 patients underwent endoscopic sphincterotomy from 1 January 2015 to 31 December 2017 in Linkou Chang Gung Memorial Hospital. Finally, 303 patients whose serum lipid levels had been checked following a cholecystectomy after ERCP were included for analysis. We evaluated if metabolic factors including body weight, BMI, HbA1C, serum lipid profile, and lipid-lowering drugs may impact the rate of common bile duct stone recurrence. Furthermore, we tried to find if there is any factor that may impact time to recurrence. RESULTS: A serum HDL level ≥ 40 (p = 0.000, OR = 0.207, 95% CI = 0.114-0.376) is a protective factor, and a total cholesterol level ≥ 200 (p = 0.004, OR = 4.558, 95% CI = 1.625-12.787) is a risk factor of recurrent common bile duct stones after endoscopic sphincterotomy with cholecystectomy. Lipid-lowering drugs, specifically statins, have been shown to reduce the risk of recurrence significantly (p = 0.003, OR = 0.297, 95% CI = 0.132-0.665). No factors were found to impact the time to recurrence in this study. CONCLUSIONS: The serum lipid level could influence the recurrence of common bile duct stones after endoscopic sphincterotomy followed by cholecystectomy, and it appears that statins can reduce the risk of recurrence.
RESUMO
Fully covered self-expandable metallic stents (FCSEMSs) are inserted in patients with unresectable pancreatic ductal adenocarcinoma (PDAC) to resolve malignant distal bile duct obstructions. Some patients receive FCSEMSs during primary endoscopic retrograde cholangiopancreatography (ERCP), and others receive FCSEMSs during a later session, after the placement of a plastic stent. We aimed to evaluate the efficacy of FCSEMSs for primary use or following plastic stent placement. A total of 159 patients with pancreatic adenocarcinoma (m:f, 102:57) who had achieved clinical success underwent ERCP with the placement of FCSEMSs for palliation of obstructive jaundice. One-hundred and three patients had received FCSEMSs in a first ERCP, and 56 had received FCSEMSs after prior plastic stenting. Twenty-two patients in the primary metal stent group and 18 in the prior plastic stent group had recurrent biliary obstruction (RBO). The RBO rates and self-expandable metal stent patency duration did not differ between the two groups. An FCSEMS longer than 6 cm was identified as a risk factor for RBO in patients with PDAC. Thus, choosing an appropriate FCSEMS length is an important factor in preventing FCSEMS dysfunction in patients with PDAC with malignant distal bile-duct obstruction.
RESUMO
BACKGROUND: Acute-on-chronic-liver failure (ACLF) demonstrates high short-term mortality rates and usually requires intensive care unit (ICU) admission. Accurate prognostication of these patients is pivotal for timely referral for liver transplantation. The superiority of CLIF-C ACLF, CLIF-C ACLF lactate, and NACSELD-ACLF scores in Asian patients with ACLF admitted to an ICU remains inconclusive. AIMS: To compare the predictive performance of CLIF-C ACLF, CLIF-C ACLF lactate, and NACSELD-ACLF scores for one-month mortality. METHODS: 276 consecutive cirrhotic patients with ACLF admitted to ICU were enrolled. The prognostic values for one-month mortality were assessed by AUROC analysis. RESULTS: The primary cause of cirrhosis in this cohort was alcohol abuse (56.5%). AUROC analysis (95% confidence intervals) demonstrated that CLIF-C ACLF lactate [0.802 (0.747-0.856)] outperformed both CLIF-C ACLF [0.791 (0.733-0.848)] and NACSELD-ACLF [0.673 (0.606-0.740)] in predicting one-month mortality. However, no statistically significant difference was observed between the predictive abilities of CLIF-C ACLF and CLIF-C ACLF lactate. CONCLUSIONS: In critically ill cirrhotic patients with ACLF admitted to the hepatology ICU, CLIF ACLF-lactate outperformed CLIF-C ACLF and NACSELD-ACLF in predicting one-month mortality. Nevertheless, no statistically significant difference was observed between CLIF-C ACLF and CLIF-C ACLF lactate. Larger-scale multi-center prospective studies are warranted to validate these results.
RESUMO
In this study, we designed and synthesized three series of blue emitting homoleptic iridium(III) phosphors bearing 4-cyano-3-methyl-1-phenyl-6-(trifluoromethyl)-benzo[d]imidazol-2-ylidene (mfcp), 5-cyano-1-methyl-3-phenyl-6-(trifluoromethyl)-benzo[d]imidazol-2-ylidene (ofcp), and 1-(3-(tert-butyl)phenyl)-6-cyano-3-methyl-4-(trifluoromethyl)-benzo[d]imidazol-2-ylidene (5-mfcp) cyclometalates, respectively. These iridium complexes exhibit intense phosphorescence in the high energy region of 435-513 nm in the solution state at RT, to which the relatively large T1 â S0 transition dipole moment is beneficial for serving as a pure emitter and an energy donor to the multiresonance thermally activated delayed fluorescence (MR-TADF) terminal emitters via Förster resonance energy transfer (FRET). The resulting OLEDs achieved true blue, narrow bandwidth EL with a max EQE of 16-19% and great suppression of efficiency roll-off with ν-DABNA and t-DABNA. We obtained the FRET efficiency up to 85% using titled Ir(III) phosphors f-Ir(mfcp)3 and f-Ir(5-mfcp)3 to achieve true blue narrow bandwidth emission. Importantly, we also provide analysis on the kinetic parameters involved in the energy transfer processes and, accordingly, propose feasible ways to improve the efficiency roll-off caused by the shortened radiative lifetime of hyperphosphorescence.
RESUMO
Near-infrared organic light-emitting diodes (NIR OLEDs) have significant potential for wearable phototherapeutic applications because of the unique properties of the OLEDs, including their free-form electronics and the excellent biomedical effects of NIR emission. In spite of their tremendous promise, given that the majority of NIR OLEDs in previous research have relied on the utilization of an intrinsically brittle indium tin oxide (ITO) electrode, their practicality in the field of wearable electronics is inherently constrained. Here, we report wearable and wavelength-tunable NIR OLEDs that employ a high-performance NIR emitter and an innovative architecture by replacing the ITO with a silver (Ag) electrode. The NIR OLEDs permit wavelength tuning of emissions from 700 to 800 nm and afford stable operation even under repeated bending conditions. The NIR OLEDs provide a lowered device temperature of 37.5 °C even during continuous operation under several emission intensities. In vitro experiments were performed with freshly fabricated NIR OLEDs. The outcomes were evaluated against experimental results performed using the same procedure utilizing blue, green, and red OLEDs. When exposed to NIR light irradiation, the promoting effect of cell proliferation surpassed the proliferative responses observed under the influence of visible light irradiation. The proliferation effect of human hair follicle dermal papilla cells is clearly related to the irradiation wavelength and time, thus underscoring the potential of wavelength-tunable NIR OLEDs for efficacious phototherapy. This work will open novel avenues for wearable NIR OLEDs in the field of biomedical application.
RESUMO
(1) Background: Spontaneous bacterial peritonitis (SBP) is a major and severe complication in cirrhosis patients with ascites. Over the years, advance in antibiotic treatment has led to changes in microbial patterns in some regions, including the emergence of extended-spectrum beta-lactamases resistant (ESBL)-producing bacteria and an increase in Gram-positive bacteria (GPC). In addition, three SBP types (classic SBP, culture-negative neutrophilic ascites (CNNA), and monomicrobial non-neutrocytic bacterascites (MNB)), may also have different prognoses. Therefore, the study aimed to investigate the microbial pattern and the predictors of short-term outcomes in patients with SBP. (2) Methods: Patients discharged with a diagnosis of the first episode of SBP between January 2006 and July 2017 were enrolled. Patients' clinical, demographic, hematological, and biochemical data were obtained at diagnosis, and the model for end-stage liver disease (MELD)-based scores were calculated accordingly. Patients were followed up until February 2018 or until death. (3) Results: A total of 327 patients were analyzed. The prevalence of classic SBP was nearly equivalent to CNNA. As for the microbial pattern, Gram-negative bacillus (GNB) remained more prevalent than GPC (75 vs. 25%), with E. coli being the most common bacterial species, followed by K. Pneumoniae and then Staphylococcus. The percentage of ESBL strain in culture-positive patients was 10.9%. By univariable and multivariable logistic regression survival analysis, there was no significant difference in predicting short-term mortality among the three SBP types, neither between GNB vs. GPC nor between ESBL- and non-ESBL-producing bacteria. Only bacteremia (sepsis), hepatorenal syndrome (HRS), and serum creatinine (Cr) were independent predictors of in-hospital and 3-month mortality, whereas HRS and Cr were independent predictors of 6-month mortality. (4) Conclusions: SBP types, Gram stain result, and ESBL strain did not affect survival. Only bacteremia (sepsis), HRS, and serum Cr independently predicted the short-term mortality in patients with SBP.
RESUMO
BACKGROUND: The optimal timing of endoscopic retrograde cholangiopancreatography (ERCP) in acute cholangitis (AC) is uncertain, especially in patients with AC of varying severity. AIM: To report whether the timing of ERCP is associated with outcomes in AC patients with different severities. METHODS: According to the 2018 Tokyo guidelines, 683 patients who met the definite diagnostic criteria for AC were retrospectively identified. The results were first compared between patients receiving ERCP ≤ 24 h and > 24 h and then between patients receiving ERCP ≤ 48 h and > 48 h. Subgroup analyses were performed in patients with grade I, II or III AC. The primary outcome was 30-d mortality. Secondary outcomes were intensive care unit (ICU) admission rate, length of hospital stay (LOHS) and 30-d readmission rate. RESULTS: Taking 24 h as the critical value, compared with ERCP > 24 h, malignant biliary obstruction as a cause of AC was significantly less common in the ERCP ≤ 24 h group (5.2% vs 11.5%). The proportion of cardiovascular dysfunction (11.2% vs 2.6%), respiratory dysfunction (14.2% vs 5.3%), and ICU admission (11.2% vs 4%) in the ERCP ≤ 24 h group was significantly higher, while the LOHS was significantly shorter (median, 6 d vs 7 d). Stratified by the severity of AC, higher ICU admission was only observed in grade III AC and shorter LOHS was only observed in grade I and II AC. There were no significant differences in 30-d mortality between groups, either in the overall population or in patients with grade I, II or III AC. With 48 h as the critical value, compared with ERCP > 48 h, the proportion of choledocholithiasis as the cause of AC was significantly higher in the ERCP ≤ 48 h group (81.5% vs 68.3%). The ERCP ≤ 48 h group had significantly lower 30-d mortality (0 vs 1.9%) and shorter LOHS (6 d vs 8 d). Stratified by AC severity, lower 30-d mortality (0 vs 6.1%) and higher ICU admission rates (22.2% vs 10.2%) were only observed in grade III AC, and shorter LOHS was only observed in grade I and II AC. In the multivariate analysis, cardiovascular dysfunction and time to ERCP were two independent factors associated with 30-d mortality. CONCLUSION: ERCP ≤ 48 h conferred a survival benefit in patients with grade III AC. Early ERCP shortened the LOHS in patients with grade I and II AC.
Assuntos
Colangite , Coledocolitíase , Humanos , Colangiopancreatografia Retrógrada Endoscópica/efeitos adversos , Colangiopancreatografia Retrógrada Endoscópica/métodos , Estudos Retrospectivos , Doença Aguda , Colangite/etiologiaRESUMO
Aromatic ring fusion to porphyrins and their derivatives represents an attractive route to tune the molecular conjugation and thus expand their functionalities. Here, we report the expansion of the aromatic π-system of palladium tetraphenyltetrabenzoporphyrins (Pd-TPTBP) via surface-assisted γ-ortho cyclodehydrogenation on Ag(111). The chemical transformation of Pd-TPTBP into different products at an elevated temperature of 600 K was revealed at the single-molecule level using bond-resolved scanning tunneling microscopy with a CO-functionalized tip. We captured a series of γ-ortho cyclodehydrogenation products, wherein the maximum extent to which the reaction can progress is associated with 7-fold C-C formation to afford nearly planar γ-ortho fused porphyrins with 66 conjugated π-electrons. In addition, a small number of molecules undergo C-C bond dissociation of meso-phenyl at elevated temperature, producing fully planar γ-ortho fused products lacking one or two phenyl moieties. Scanning tunneling spectroscopy measurements and DFT calculations suggest the electronic gap of the γ-ortho fused porphyrin decreases compared to that of the precursor. The HOMO and LUMO of the planar γ-ortho fused products are localized on the partially fused benzo moieties and the meso-position, respectively.
RESUMO
Inverted perovskite solar cells (PSCs) have attracted intense attention because of their insignificant hysteresis and low-temperature fabrication process. However, the efficiencies of inverted PSCs are still inferior to those of commercialized silicon solar cells. Also, the poor stability of PSCs is one of the major impedances to commercialization. Herein, we rationally designed and synthesized a new series of electron donor (R,R-diphenylamino) and acceptor (pyridimium-(CH2) n -sulfonates) zwitterions as a boundary modulator and systematically investigated their associated interface properties. Comprehensive physical and optoelectronic studies verify that these zwitterions provide a four-in-one functionality: balancing charge carrier transport, suppressing less-coordinated Pb2+ defects, enhancing moisture resistance, and reducing ion migration. Although each functionality may have been reported by specific passivating molecules, a strategy that simultaneously regulates the charge-transfer balance and three other functionalities has not yet been developed. The results are to make an omnidirectional improvement of PSCs. Among all zwitterions, 4-(4-(4-(di-(4-methoxylphenyl)amino)phenyl)propane-1-ium-1-yl)butane-1-sulfonate (OMeZC3) optimizes the balance hole/electron mobility ratio of perovskite to 0.91, and the corresponding PSCs demonstrate a high power conversion efficiency (PCE) of up to 23.15% free from hysteresis, standing out as one of the champion PSCs with an inverted structure. Importantly, the OMeZC3-modified PSC exhibits excellent long-term stability, maintaining almost its initial PCE after being stored at 80% relative humidity for 35 days.
RESUMO
Poly(sulfosalicylic acid) and single-stranded DNA composite (PSSA-ssDNA)-modified glassy carbon electrode (GCE) was prepared by electropolymerization and then successfully used to simultaneously determine adenine (A), guanine (G), and thymine (T). The characterization of electrochemically synthesized PSSA-ssDNA film was investigated by scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). The modified electrode exhibited enhanced electrocatalytic behavior and good stability for the simultaneous determination of A, G, and T in 0.1M phosphate buffer solution (PBS, pH 7.0). Well-separated voltammetric peaks were obtained among A, G, and T presented in the analyte mixture. Under the optimal conditions, the peak currents for A, G, and T increased linearly with the increase of analyte mixture concentration in the ranges of 6.5×10(-8) to 1.1×10(-6), 6.5×10(-8) to 1.1×10(-6), and 4.1×10(-6) to 2.7×10(-5)M, respectively. The detection limits (signal/noise=3) for A, G, and T were 2.2×10(-8), 2.2×10(-8), and 1.4×10(-6)M, respectively.