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1.
J Hepatol ; 2024 Apr 16.
Artículo en Inglés | MEDLINE | ID: mdl-38636849

RESUMEN

BACKGROUND & AIMS: Ultrasonography (US) is recommended for HCC surveillance in high-risk patients but has limited performance in detecting early-stage HCC. We aimed to compare the diagnostic performance of biannual US and annual non-contrast abbreviated magnetic resonance imaging (NC-AMRI) as HCC surveillance modalities in high-risk patients. METHODS: This prospective, multicenter cohort study enrolled participants with an estimated annual risk of HCC greater than 5% between October 2015 and April 2017. Participants underwent six rounds of HCC surveillance at 6-month intervals, with both US and NC-AMRI at rounds 1, 3, and 5, and only US at rounds 2, 4, and 6. The sensitivity, diagnostic yield (DY), and false referral rate (FRR) for HCC detection by US and NC-AMRI were compared. RESULTS: In total, 208 participants underwent 980 US and 516 NC-AMRI examinations during 30 months of follow-up. Among them, 34 HCCs were diagnosed in 31 participants, with 20 (64.5%) classified as very early-stage and 11 (35.5%) as early-stage HCC. The sensitivity of annual NC-AMRI (71.0%, 22/31) was marginally higher than that of biannual US (45.2%, 14/31; p = 0.077). NC-AMRI showed a significantly higher DY than US (4.26% vs. 1.43%, p <0.001), with a similar FRR (2.91% vs. 3.06%, p = 0.885). A simulation of alternating US and NC-AMRI at 6-month intervals yielded a sensitivity of 83.9% (26/31), significantly exceeding that of biannual US (p = 0.006). CONCLUSIONS: Annual NC-AMRI showed a marginally higher sensitivity than biannual US for HCC detection in high-risk patients. The DY of annual NC-AMRI was significantly higher than that of biannual US, without increasing the FRR. Thus, alternating US and NC-AMRI at 6-month intervals could be an optimal surveillance strategy for high-risk patients. IMPACT AND IMPLICATIONS: Current guidelines permit the use of magnetic resonance imaging (MRI) as a surveillance tool for hepatocellular carcinoma in patients in whom ultrasonography (US) is inadequate. However, the specific indications, imaging sequences, and intervals for MRI surveillance remain unclear. In our study, we found that annual non-contrast abbreviated MRI exhibited marginally higher sensitivity and significantly better diagnostic yield than biannual US in patients at high risk of hepatocellular carcinoma. Alternating US and non-contrast abbreviated MRI at 6-month intervals led to significantly improved sensitivity compared to biannual US, making it a potentially optimal surveillance strategy for high-risk patients. GOV IDENTIFIER: NCT02551250.

2.
Radiology ; 311(1): e233114, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38563667

RESUMEN

Background Noninvasive diagnostic guidelines for hepatocellular carcinoma (HCC) vary across different global geographic areas, especially regarding criteria about gadoxetic acid-enhanced MRI. Purpose To compare the diagnostic performance of four different international HCC diagnosis guidelines and readers' judgment in diagnosing HCC using gadoxetic acid-enhanced MRI in patients at high risk for HCC. Materials and Methods This retrospective study included patients who had not undergone treatment, were at risk for HCC, and who underwent gadoxetic acid-enhanced MRI from January 2015 to June 2018 from 11 tertiary hospitals in South Korea. Four radiologists independently reviewed focal liver lesions (FLLs) according to four guidelines: American Association for the Study of Liver Diseases (AASLD)/Liver Imaging Reporting and Data System (LI-RADS), Korean Liver Cancer Association-National Cancer Center (KLCA-NCC), European Association for the Study of the Liver (EASL), and Asian Pacific Association for the Study of the Liver (APASL). Reader judgment (HCC or not HCC) was also recorded. Malignant FLLs were confirmed at pathology, and histologic and clinical follow-up data were used for benign FLLs. The guidelines' diagnostic performance was compared using generalized estimating equations. Additionally, the diagnostic odds ratio was assessed. Results A total of 2445 FLLs (median size, 27.4 mm) were analyzed in 2237 patients (mean age, 59 years ± 11 [SD]; 1666 male patients); 69.3% (1694 of 2445) were HCCs. KLCA-NCC showed the highest accuracy (80.0%; 95% CI: 78.7, 81.2; P = .001), with high sensitivity in Eastern guidelines (APASL, 89.1% [95% CI: 87.8, 90.3]; KLCA-NCC, 78.2% [95% CI: 76.6, 79.7]) and high specificity in Western guidelines (AASLD/LI-RADS, 89.6% [95% CI: 87.8, 91.2]; EASL, 88.1% [95% CI: 86.2, 89.9]) (P = .001). The diagnostic odds ratios were 20.7 (95% CI: 17.0, 25.3) for AASLD/LI-RADS, 18.9 (95% CI: 15.8, 22.6) for KLCA-NCC, 16.8 (95% CI: 13.8, 20.4) for EASL, and 8.9 (95% CI: 7.4, 10.7) for APASL. The readers' judgment demonstrated higher accuracy than that of the guidelines (accuracy, 86.0%; 95% CI: 84.9, 86.9; P = .001). Conclusion Among four different international HCC diagnosis guidelines, Eastern guidelines demonstrated higher sensitivity, whereas Western guidelines displayed higher specificity. KLCA-NCC achieved the highest accuracy, and AASLD/LI-RADS exhibited the highest diagnostic odds ratio. © RSNA, 2024 Supplemental material is available for this article.


Asunto(s)
Carcinoma Hepatocelular , Gadolinio DTPA , Neoplasias Hepáticas , Humanos , Masculino , Persona de Mediana Edad , Carcinoma Hepatocelular/diagnóstico por imagen , Estudios Retrospectivos , Neoplasias Hepáticas/diagnóstico por imagen , Imagen por Resonancia Magnética
3.
Biotechnol Lett ; 46(4): 521-530, 2024 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-38872071

RESUMEN

Blood coagulation mediated by pig tissue factor (TF), which is expressed in pig tissues, causes an instant blood-mediated inflammatory reaction during pig-to-human xenotransplantation. Previously, we generated a soluble pig tissue factor pathway inhibitor α fusion immunoglobulin (TFPI-Ig) which inhibits pig TF activity more efficiently than human TFPI-Ig in human plasma. In this study, we generated several pig TFPI-Ig mutants and tested the efficacy of these mutants in preventing pig-to-human xenogeneic blood coagulation. Structurally important amino acid residues of pig TFPI-Ig were changed into different residues by site-directed mutagenesis. Subsequently, a retroviral vector encoding each cDNA of several pig TFPI-Ig mutants was cloned and transduced into CHO-K1 cells. After establishing stable cell lines expressing each of the pig TFPI-Ig mutants, soluble proteins were produced and purified for evaluating their inhibitory effects on pig TF-mediated blood coagulation in human plasma. The replacement of K36 and K257 with R36 and H257, respectively, in pig TFPI-Ig more efficiently blocked pig TF activity in human plasma when compared with the wild-type pig TFPI-Ig. These results may provide additional information to understand the structure of pig TFPIα, and an improved pig TFPI-Ig variant that more efficiently blocks pig TF-mediated blood coagulation during pig-to-human xenotransplantation.


Asunto(s)
Coagulación Sanguínea , Lipoproteínas , Trasplante Heterólogo , Animales , Humanos , Porcinos , Lipoproteínas/genética , Lipoproteínas/metabolismo , Coagulación Sanguínea/genética , Células CHO , Cricetulus , Tromboplastina/genética , Tromboplastina/metabolismo , Mutagénesis Sitio-Dirigida , Análisis Mutacional de ADN
4.
Chemistry ; 29(45): e202301501, 2023 Aug 10.
Artículo en Inglés | MEDLINE | ID: mdl-37205632

RESUMEN

Antiaromatic molecules have recently received attention because of their intrinsic properties, such as high reactivity and their narrow HOMO-LUMO gaps. Stacking of antiaromatic molecules has been predicted to induce three-dimensional aromaticity via frontier orbital interactions. Here, we report a covalently linked π-π stacked rosarin dimer that has been examined experimentally by steady-state absorption and transient absorption measurements and theoretically by quantum chemical calculations, including time-dependent density functional theory, anisotropy of induced current density, and nucleus-independent chemical shift calculations. Relative to the corresponding monomer, the dimer exhibits diminished antiaromaticity upon lowering the temperature to 77 K, a finding ascribed to intramolecular interactions between the macrocyclic rosarin subunits.

5.
Chemistry ; 29(10): e202203009, 2023 Feb 16.
Artículo en Inglés | MEDLINE | ID: mdl-36464650

RESUMEN

A π-extended, diaza-triphenylene embedded, mono-anionic corrole analogue and its NiII complex were synthesized from a diaza-triphenylene precursor, which was obtained from a double one-carbon insertion into a naphthobipyrrole diester. Following conversion to the corresponding activated diol and acid-catalyzed condensation with pyrrole, subsequent reaction with pentafluorobenzaldehyde afforded mono-anionic, π-extended bipyricorrole-like macrocycle. Attempted NiII insertion with Ni(OAc)2 ⋅ 4H2 O resulted an ESR active, NiII bipyricorrole radical complex, which was converted to a stable cationic NiII complex upon treatment with [(Et3 O)+ (SbCl6 )- ]. Both complexes were characterized by 1 H and 13 C NMR, UV/Vis spectroscopy and single crystal X-ray diffraction analysis. The NiII bipyricorrole radical complex is converted to a cationic NiII complex by single-electron reduction using cobaltocene. Both the cationic NiII complex and the radical NiII complex exhibited ligand-centered redox behavior, whereas the NiII remains in the +2 oxidation state.

6.
Eur Radiol ; 33(6): 4401-4411, 2023 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-36562784

RESUMEN

OBJECTIVES: To evaluate the feasibility of simulated abbreviated MRI (AMRI) with second shot arterial phase (SSAP) for HCC surveillance and diagnosis. METHODS: A total of 129 consecutive patients (age, 58.8 ± 11.4 years; male, 71.3%) underwent gadoxetic acid-enhanced MRI using a modified injection protocol for HCC evaluation from July 2017 to February 2018. The modified injection protocol consisted of routine dynamic imaging (6 mL) and SSAP imaging (4 mL). Two radiologists independently reviewed two AMRI sets: AMRI without SSAP (surveillance set) and AMRI with SSAP (diagnosis set). A modified version of the Liver Imaging Reporting and Data System (LI-RADS) for the diagnosis set was devised by referring to contrast-enhanced ultrasound LI-RADS. RESULTS: Sixty-seven patients with HCC and 62 patients without HCC were included. In the surveillance set, sensitivity and specificity for the detection of patients with HCC were 95.5% and 96.8%, and 94.0% and 96.8% in reviewers 1 and 2, respectively. In the diagnosis set, the scores of most HCCs (76/78, 97.4%) were consistent between LI-RADS of full-protocol and modified LI-RADS of AMRI with SSAP protocol. When the HCC surveillance and diagnosis strategy was changed from strategy 1 (AMRI without SSAP) to strategy 2 (AMRI with SSAP), the recall rate significantly decreased from 52.7 to 3.9% (p < 0.001). CONCLUSIONS: The modified LI-RADS score of the AMRI with SSAP protocol showed high agreement with the LI-RADS score of the full protocol. The HCC surveillance and diagnosis strategy using the AMRI with SSAP protocol reduced the recall rate. These results may enable to diagnose HCC simultaneously with surveillance. KEY POINTS: • A modified version of LI-RADS was devised for the diagnostic algorithm using AMRI with the second shot arterial phase (SSAP) by referring to CEUS LI-RADS. • The modified LI-RADS scores using AMRI with SSAP showed a high concordance rate with the conventional LI-RADS score using full-protocol MRI. • The recall rate significantly decreased when the HCC surveillance and diagnosis strategy was changed from strategy 1 (AMRI without SSAP; surveillance then recall test) to strategy 2 (AMRI with SSAP; simultaneous surveillance and diagnosis).


Asunto(s)
Carcinoma Hepatocelular , Neoplasias Hepáticas , Humanos , Masculino , Persona de Mediana Edad , Anciano , Carcinoma Hepatocelular/diagnóstico por imagen , Neoplasias Hepáticas/diagnóstico por imagen , Medios de Contraste/farmacología , Estudios Retrospectivos , Gadolinio DTPA , Imagen por Resonancia Magnética/métodos , Sensibilidad y Especificidad
7.
Eur Radiol ; 33(9): 5965-5975, 2023 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-36988715

RESUMEN

OBJECTIVE: This prospective multicenter study aimed to evaluate the diagnostic performance of 80-kVp thin-section pancreatic CT in determining pancreatic ductal adenocarcinoma (PDAC) resectability according to the recent National Comprehensive Cancer Network (NCCN) guidelines. METHODS: We prospectively enrolled surgical resection candidates for PDAC from six tertiary referral hospitals (study identifier: NCT03895177). All participants underwent pancreatic CT using 80 kVp tube voltage with 1-mm reconstruction interval. The local resectability was prospectively evaluated using NCCN guidelines at each center and classified into three categories: resectable, borderline resectable, and unresectable. RESULTS: A total of 138 patients were enrolled; among them, 60 patients underwent neoadjuvant therapy. R0 resection was achieved in 103 patients (74.6%). The R0 resection rates were 88.7% (47/53), 52.4% (11/21), and 0.0% (0/4) for resectable, borderline resectable, and unresectable disease, respectively, in 78 patients who underwent upfront surgery. Meanwhile, the rates were 90.9% (20/22), 76.7% (23/30), and 25.0% (2/8) for resectable, borderline resectable, and unresectable PDAC, respectively, in patients who received neoadjuvant therapy. The area under curve of high-resolution CT in predicting R0 resection was 0.784, with sensitivity, specificity, and accuracy of 87.4% (90/103), 48.6% (17/35), and 77.5% (107/138), respectively. Tumor response was significantly associated with the R0 resection after neoadjuvant therapy (odds ratio [OR] = 38.99, p = 0.016). CONCLUSION: An 80-kVp thin-section pancreatic CT has excellent diagnostic performance in assessing PDAC resectability, enabling R0 resection rates of 88.7% and 90.9% for patients with resectable PDAC who underwent upfront surgery and patients with resectable PDAC after neoadjuvant therapy, respectively. KEY POINTS: • The margin-negative (R0) resection rates were 88.7% (47/53), 52.4% (11/21), and 0.0% (0/4) for resectable, borderline resectable, and unresectable pancreatic ductal adenocarcinoma (PDAC), respectively, on 80-kVp thin-section pancreatic CT in the 78 patients who underwent upfront surgery. • Among the 60 patients who underwent neoadjuvant therapy, the R0 rates were 90.9% (20/22), 76.7% (23/30), and 25.0% (2/8) for resectable, borderline resectable, and unresectable PDAC, respectively. • Tumor response, along with the resectability status on pancreatic CT, was significantly associated with the R0 resection rate after neoadjuvant therapy.


Asunto(s)
Carcinoma Ductal Pancreático , Neoplasias Pancreáticas , Humanos , Estudios Prospectivos , Neoplasias Pancreáticas/diagnóstico por imagen , Neoplasias Pancreáticas/cirugía , Neoplasias Pancreáticas/patología , Carcinoma Ductal Pancreático/diagnóstico por imagen , Carcinoma Ductal Pancreático/cirugía , Carcinoma Ductal Pancreático/patología , Tomografía Computarizada por Rayos X/métodos , Terapia Neoadyuvante , Neoplasias Pancreáticas
8.
Int J Mol Sci ; 24(2)2023 Jan 06.
Artículo en Inglés | MEDLINE | ID: mdl-36674609

RESUMEN

Transparent organic light emitting diode (OLED) display is one of the most promising devices among next-generation information displays because of beneficial characteristics, such as self-emissive and optically clear properties. Nevertheless, in conventional transparent OLED display devices, there are serious intrinsic problems in terms of the transmittance in the dark state because of empty windows in the cell, so the contrast ratio of the transparent OLED display would be deteriorated even though it can exhibit excellent bright state. In general, the transparent mode using the OLED device applies an empty area in each pixel because an emitting device could never reveal the background image, so the transparent OLED should contain the empty area in the pixel for transparent images. This may cause the optical degradation in the dark state. To solve this problem, we propose hybrid-type transparent OLED display modes that apply a liquid crystal (LC) to the transparent window part of the empty space. In this paper, we applied two dichroic LC modes- which use an electrically controlled birefringence (ECB) mode (Heilmeier type) for the polarized mode and a cholesteric LC mode (Guest-Host mode) for the non-polarized mode-to the empty area. In each hybrid mode, we have observed optical performance, including the transmittance in the dark/bright state, contrast ratio and response time as a function of cell parameters. As a result, we confirmed that the dark state and the contrast ratio could be improved by applying the proposed modes without serious decay of the transmittance in the bright state.


Asunto(s)
Cristales Líquidos , Cristales Líquidos/química
9.
Bioorg Chem ; 128: 106044, 2022 11.
Artículo en Inglés | MEDLINE | ID: mdl-35917749

RESUMEN

Novel bipyridine-based heterocyclic building block, 3,10-dichloro-benzo[f][1,10]phenanthroline and its Ruthenium(II) complex have been synthesized and fully characterized. The synthesized Ru(II)-complex is highly luminescent displaying emission at 590 nm with quantum yield of ∼0.8 in methanol. Ru(II) complex showed photocytotoxicity upon 400 nm blue light irradiation. Mechanistic study revealed that photoactivated Ru(II) complex generates reactive radical species which can damage the protein inside the cells and induce cell death even with short irradiation time.


Asunto(s)
Rutenio , Luz , Fenantrolinas , Rutenio/farmacología
10.
Org Biomol Chem ; 19(37): 8009-8013, 2021 09 29.
Artículo en Inglés | MEDLINE | ID: mdl-34236071

RESUMEN

To improve tumor selectivity, a triple-targeting delivery system (Oct-FK(PBA-Az)-Dox) carrying two anticancer agents (apoptozole (Az) and doxorubicin (Dox)) was designed and synthesized. The results showed that both anticancer agents in Oct-FK(PBA-Az)-Dox are liberated in the presence of both H2O2 and cathepsin B, which are normally present at high levels in tumors.


Asunto(s)
Peróxido de Hidrógeno
11.
Chem Soc Rev ; 49(3): 865-907, 2020 Feb 07.
Artículo en Inglés | MEDLINE | ID: mdl-31957756

RESUMEN

Supramolecular chemistry is a central topic in modern chemistry. It touches on many traditional disciplines, such as organic chemistry, inorganic chemistry, physical chemistry, materials chemistry, environmental chemistry, and biological chemistry. Supramolecular hosts, inter alia macrocyclic hosts, play critical roles in supramolecular chemistry. Calix[4]pyrroles, non-aromatic tetrapyrrolic macrocycles defined by sp3 hybridized meso bridges, have proved to be versatile receptors for neutral species, anions, and cations, as well as ion pairs. Compared to the parent system, octamethylcalix[4]pyrrole and its derivatives bearing simple appended functionalities, strapped calix[4]pyrroles typically display enhanced binding affinities and selectivities. In this review, we summarize advances in the design and synthesis of strapped calix[4]pyrroles, as well as their broad utility in molecular recognition, supramolecular extraction, separation technology, ion transport, and as agents capable of inhibiting cancer cell proliferation. Future challenges within this sub-field are also discussed.


Asunto(s)
Calixarenos/química , Calixarenos/metabolismo , Porfirinas/química , Porfirinas/metabolismo , Aniones/química , Apoptosis , Cationes/química , Permeabilidad de la Membrana Celular , Cristalización , Modelos Moleculares , Estructura Molecular , Compuestos Orgánicos/química , Relación Estructura-Actividad , Termodinámica
12.
Molecules ; 26(4)2021 Feb 15.
Artículo en Inglés | MEDLINE | ID: mdl-33672044

RESUMEN

In spite of unique structural, spectroscopic and redox properties, the synthetic variants of the planar, antiaromatic hexaphyrin (1.0.1.0.1.0) derivatives 2, has been limited due to the low yields and difficulty in access to the starting material. A chemical modification of the meso-substituents could be good alternative overcoming the synthetic barrier. Herein, we report a regio-selective nucleophilic aromatic substitution (SNAr) of meso-pentafluorophenyl group in rosarrin 2 with catechol. The reaction afforded benzodioxane fused rosarrin 3 as single product with high yield. The intrinsic antiaromatic character of the starting rosarrin 2 retained throughout the reactions. Clean, two electron reduction was achieved by treatment of 3 with SnCl2•2H2O affording 26π-electron aromatic rosarrin 4. The synthesized compounds exhibited noticeable changes in photophysical and redox properties compared with starting rosarrin 2.


Asunto(s)
Porfirinas/química , Porfirinas/síntesis química , Técnicas Electroquímicas , Espectrofotometría Ultravioleta , Estereoisomerismo
13.
J Am Chem Soc ; 142(20): 9130-9134, 2020 May 20.
Artículo en Inglés | MEDLINE | ID: mdl-32392048

RESUMEN

Nanoscale dynamic processes such as the diffusion of ions within solid-state structures are critical for understanding and tuning material properties in a wide range of areas, such as energy storage and conversion, catalysis, and optoelectronics. In the generation of new types of nanocrystals (NCs), diffusion-mediated ion exchange reactions have also been proposed as one of the most effective transformational strategies. However, retaining the original morphology and crystal structure of metal oxide NCs has been challenging because of Kirkendall void formation, and there has been no success, especially for anion exchange. Here we show that with the aid of an oxygen extracting reagent (OER), anion diffusion is dramatically accelerated and morphology-conserving anion exchange without Kirkendall void formation is possible. In the case of the conversion of Fe3O4 to Fe3S4, oxygen extraction and subsequent formation of the amorphous phase facilitate the migration of incoming sulfur anions by approximately 100-fold, which is close to the level of the outgoing cation diffusivity. We also demonstrate that the working principle of the morphology-conserving non-Kirkendall anion exchange is operative for metal oxide NCs with different shapes and crystal structures.

14.
Radiology ; 296(2): 335-345, 2020 08.
Artículo en Inglés | MEDLINE | ID: mdl-32484414

RESUMEN

Background Hepatobiliary phase (HBP) hypointense nodules without arterial phase hyperenhancement (APHE) at gadoxetic acid-enhanced MRI may indicate hepatocellular carcinoma (HCC) or nonmalignant cirrhosis-associated nodules. Purpose To assess the distribution of pathologic diagnoses of HBP hypointense nodules without APHE at gadoxetic acid-enhanced MRI and to evaluate clinical and imaging features in differentiating their histologic grades. Materials and Methods This retrospective multicenter study included pathologic analysis-confirmed HBP hypointense nodules without APHE (≤30 mm) in patients with chronic liver disease or cirrhosis screened between January 2008 and June 2016. Central pathologic review by 10 pathologists determined final histologic grades as progressed HCC, early HCC, high-grade dysplastic nodule (DN), and low-grade DN or regenerative nodule. Gadoxetic acid-enhanced MRI features were analyzed by three radiologists. Multivariable logistic regression analyses with elastic net regularization were performed to identify clinical and imaging features for differentiating histologic grades. Results There were 298 patients (mean age, 59 years ± 10; 226 men) with 334 nodules evaluated, and progressed HCCs were diagnosed in 44.0% (147 of 334), early HCCs in 20.4% (68 of 334), high-grade DNs in 27.5% (92 of 334), and low-grade DNs or regenerative nodules in 8.1% (27 of 334). Serum α-fetoprotein level 100 ng/mL or greater (odds ratio, 2.7; P = .01) and MRI features including well-defined margin (odds ratio, 5.5; P = .003), hypointensity at precontrast T1-weighted imaging (odds ratio, 3.2; P < .001), intermediate hyperintensity at T2-weighted imaging (odds ratio, 3.4; P < .001), and restricted diffusion (odds ratio, 1.9; P = .04) were independent predictors for progressed HCC at multivariable analysis. Conclusion In patients at high risk for hepatocellular carcinoma (HCC), hepatobiliary phase hypointense nodules without arterial phase hyperenhancement at gadoxetic acid-enhanced MRI corresponded mainly to progressed HCCs, early HCCs, and high-grade dysplastic nodules. High α-fetoprotein level and some imaging features at MRI helped to differentiate progressed HCC from lower grade nodules. © RSNA, 2020 Online supplemental material is available for this article. See also the editorial by Motosugi in this issue.


Asunto(s)
Medios de Contraste/química , Gadolinio DTPA/química , Neoplasias Hepáticas/diagnóstico por imagen , Neoplasias Hepáticas/patología , Imagen por Resonancia Magnética/métodos , Anciano , Medios de Contraste/uso terapéutico , Femenino , Gadolinio DTPA/uso terapéutico , Humanos , Interpretación de Imagen Asistida por Computador , Hígado/química , Hígado/diagnóstico por imagen , Hígado/patología , Neoplasias Hepáticas/química , Masculino , Persona de Mediana Edad , Estudios Retrospectivos
15.
Chemistry ; 26(69): 16434-16440, 2020 Dec 09.
Artículo en Inglés | MEDLINE | ID: mdl-32557895

RESUMEN

π-π Stacking is omnipresent not only in nature but in a wide variety of practical fields applied to our lives. Because of its importance in a performance of natural and artificial systems, such as light harvesting system and working layer in device, many researchers have put intensive effort into identifying its underlying nature. However, for the case of π-π stacked systems composed of antiaromatic units, the understanding of the fundamental mechanisms is still unclear. Herein, we synthesized a new type of planar ß,ß'-phenylene-bridged hexaphyrin (1.0.1.0.1.0), referred as naphthorosarin which possesses the 24π-electron conjugated pathway. Especially, the corresponding antiaromatic porphyrinoid shows the unique property to form dimeric species adopting the face-to-face geometry which is unprecedented in cases of known annulated naphthorosarins. In order to elucidate the intriguing properties derived from the stacked dimer, the current study focuses on the experimental support to rationalize the observed π-π interactions between the two subunits.

16.
Chemistry ; 25(14): 3525-3531, 2019 Mar 07.
Artículo en Inglés | MEDLINE | ID: mdl-30684359

RESUMEN

Peripherally substituted antiaromatic naphthorosarins have been synthesized for the first time. The synthesis was accomplished by acid-catalyzed condensation of naphthobipyrrole building blocks with aromatic aldehydes. The naphthobipyrrole building blocks were synthesized by simple oxidative coupling of the corresponding pyrrole substituted aromatics. Solid-state structural analyses of the synthesized naphthorosarins revealed that the presence of meso-2,6-dichlorophenyl- and 5,6-difluoro-substitution substantially alter the geometry and properties of the naphthorosarins. The substituents affect the redox potentials as well and, in turn, the proton-coupled electron-transfer processes leading to the formation of one- and two-electron reduced forms of the corresponding naphthorosarins. One particular naphthorosarin that bears both peripheral fluorine and meso-2,6-dichlorophenyl substituents forms a stable 25 π-electron species upon treating with TFA that was characterized by single-crystal X-ray diffraction analysis. The current study underscores how structural modifications can be used to fine-tune the electronic features of naphthorosarins, including stabilization of odd electron species.

17.
Eur Radiol ; 29(6): 2821-2829, 2019 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-30552478

RESUMEN

OBJECTIVES: Second shot arterial phase (SSAP) imaging is an additional arterial phase image obtained by re-injecting a small amount of contrast medium after routine dynamic imaging in gadoxetic acid-enhanced liver MRI. We aimed to evaluate the feasibility and additional value of a SSAP image in gadoxetic acid-enhanced liver MRI. METHODS: One hundred seventy-two patients who underwent SSAP imaging after re-injection of 4 mL of contrast material after routine dynamic imaging (original) in gadoxetic acid-enhanced liver MRIs were included. Motion artifacts on arterial phase (AP) images were rated using a 5-point scale and were compared between the original AP images and SSAP images. We evaluated visual detection rates of arterial hypervascularity on the original AP and SSAP images and their subtraction images in patients with hypervascular hepatocellular carcinoma (HCC). RESULTS: The motion artifact of the SSAP images was significantly lower than that of the original AP images (mean score, 1.76 vs 2.06; p < 0.001). In particular, motion artifacts reduced significantly in the SSAP images of patients with substantial motion artifacts in their original AP images (2.28 vs 3.28; p < 0.001). Among the 30 HCC lesions showing hypervascularity on original AP images, only four (4/30, 13.3%) appeared hyperintense on SSAP images. However, subtraction images of SSAP clearly demonstrated arterial hypervascularity in all HCCs. CONCLUSION: SSAP images showed significantly fewer motion artifacts than the original AP images. Subtraction images of SSAP maintained the detectability of arterial hypervascularity, although SSAP images showed poor visual detection of arterial hypervascularity of HCC. KEY POINTS: • Arterial phase images obtained after a second injection of a small amount of contrast medium (second shot arterial phase [SSAP]) improved motion artifacts compared to the original AP images. • The motion artifacts improved significantly in the SSAP images of patients with substantial motion artifacts in their original AP images. • Subtraction images of SSAP demonstrated the arterial hypervascularity characteristic of HCC at a level comparable to that of the original AP image.


Asunto(s)
Artefactos , Carcinoma Hepatocelular/diagnóstico por imagen , Gadolinio DTPA/farmacología , Arteria Hepática/diagnóstico por imagen , Neoplasias Hepáticas/diagnóstico por imagen , Imagen por Resonancia Magnética/métodos , Adulto , Anciano , Anciano de 80 o más Años , Carcinoma Hepatocelular/irrigación sanguínea , Medios de Contraste/farmacología , Femenino , Humanos , Neoplasias Hepáticas/irrigación sanguínea , Masculino , Persona de Mediana Edad , Estudios Retrospectivos
18.
J Org Chem ; 84(11): 6851-6857, 2019 06 07.
Artículo en Inglés | MEDLINE | ID: mdl-31081615

RESUMEN

meso-Substituted calix[4]pyrroles 2-6 containing a direct meso-ethynyl linker displayed high binding affinities and unique conformational features on halide anion binding. A general conformational bias for the equatorial alignments of the meso-(aryl)ethynyl groups was observed in the host-halide complexes which was attributed to the repulsive anion-alkyne interactions and released steric strain. Such conformational features of host-halide complexes persisted even in the case of calix[4]pyrrole 6 bearing cationic meso components, which displayed the highest binding affinity for chloride anions among known meso-aryl calix[4]pyrroles. Synthetic details, conformational features, and comparative halide anion binding properties of this series of calix[4]pyrroles are described.

19.
Analyst ; 144(16): 4826-4834, 2019 Aug 05.
Artículo en Inglés | MEDLINE | ID: mdl-31290490

RESUMEN

This study demonstrates a unique strategy for enhancing infrared (IR) spectroscopic discrimination between gall bladder (GB) polyps and cancer. This strategy includes the separation of raw bile juice into three sections of organic, aqueous, and amphiphilic phases and a cooperative combination of all IR spectral features of each separated phase for the discrimination. Raw bile juice is viscous and complex in composition because it contains fatty acids, cholesterol, proteins, phospholipids, bilirubin, and other components; therefore, the acquisition of IR spectra providing more component-discernible information is fundamental for improving discrimination. For this purpose, raw bile juice was separated into an aqueous phase, mostly containing bile salts, an organic phase with isolated lipids, and an amphiphilic phase, mainly containing proteins. The subsequent IR spectra of each separated phase were mutually characteristic and complementary to each other. When all the IR spectral features were combined, the discrimination was improved compared to that using the spectra of raw bile juice with no separation. The cooperative integration of more component-specific spectra obtained from each separated phase enhanced the discrimination. In addition, the IR spectra of the major constituents in bile juice, such as bile acids, conjugated bile salts, lecithin, and cholesterol, were recorded to explain the IR features of each separated phase.


Asunto(s)
Bilis/química , Neoplasias de la Vesícula Biliar/diagnóstico , Pólipos/diagnóstico , Ácidos y Sales Biliares/análisis , Colesterol/análisis , Diagnóstico Diferencial , Vesícula Biliar , Humanos , Lecitinas/análisis , Análisis de Componente Principal , Espectrofotometría Infrarroja/métodos
20.
J Comput Assist Tomogr ; 43(1): 46-50, 2019.
Artículo en Inglés | MEDLINE | ID: mdl-29901511

RESUMEN

OBJECTIVE: This study aimed to compare 3-dimensional T1-weighted gradient-echo sequence (CAIPIRINHA-volumetric interpolated breath-hold examination [VIBE]) with 2-dimensional T1-weighted turbo spin-echo sequence for contrast-enhanced magnetic resonance imaging (MRI) of pelvic bone metastases at 3.0 T. METHODS: Thirty-one contrast-enhanced MRIs of pelvic bone metastases were included. Two contrast-enhanced sequences were evaluated for the following parameters: overall image quality, sharpness of pelvic bone, iliac vessel clarity, artifact severity, and conspicuity and edge sharpness of the smallest metastases. Quantitative analysis was performed by calculating signal-to-noise ratio and contrast-to-noise ratio of the smallest metastases. Significant differences between the 2 sequences were assessed. RESULTS: CAIPIRINHA-VIBE had higher scores for overall image quality, pelvic bone sharpness, iliac vessel clarity, and edge sharpness of the metastatic lesions, and had less artifacts (all P < 0.05). There was no significant difference in conspicuity, signal-to-noise ratio, or contrast-to-noise ratio of the smallest metastases (P > 0.05). CONCLUSIONS: Our results suggest that CAIPIRINHA-VIBE may be superior to turbo spin-echo for contrast-enhanced MRI of pelvic bone metastases at 3.0 T.


Asunto(s)
Neoplasias Óseas/diagnóstico por imagen , Neoplasias Óseas/secundario , Medios de Contraste , Aumento de la Imagen/métodos , Interpretación de Imagen Asistida por Computador/métodos , Imagenología Tridimensional/métodos , Imagen por Resonancia Magnética/métodos , Anciano , Anciano de 80 o más Años , Contencion de la Respiración , Femenino , Humanos , Masculino , Persona de Mediana Edad , Huesos Pélvicos/diagnóstico por imagen , Reproducibilidad de los Resultados , Estudios Retrospectivos
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