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1.
Inorg Chem ; 63(11): 5175-5184, 2024 Mar 18.
Artículo en Inglés | MEDLINE | ID: mdl-38427020

RESUMEN

Nowadays, the utilization of noncontact temperature and pressure sensing is experiencing growing popularity. In this work, Bi3+, Eu3+-doped Ca5(BO3)3F (CBOF) phosphors were synthesized via an ionic liquid-assisted electrospinning approach. The effect of molecular weight of polyvinylpyrrolidone on the morphology of CBOF was investigated, and a comprehensive analysis of its formation mechanism was presented. The luminescence properties of CBOF: Bi3+, Eu3+ were studied systematically. The temperature-dependent emission of CBOF: Bi3+, Eu3+ phosphor was discussed, and it displayed thermal sensitivity, which can be attributed to the distinct thermal response emission behaviors of Bi3+ and Eu3+. The investigation of the pressure-dependent emission behavior of the CBOF: Bi3+ phosphor revealed an anomalous phenomenon: with the increase of pressure, the emission peak showed a trend of first a blue shift and then a red shift. This anomaly was discussed in detail. The phosphor exhibits visual color change (blue to cyan), remarkable pressure sensitivity (4.76 nm/GPa), and a high upper pressure limit (24.2 GPa), indicating its potential use as an optical pressure sensor. Consequently, this study presents an innovative synthetic approach for fabricating CBOF, presenting a bifunctional material with promising prospects in the fields of temperature and pressure sensing.

2.
J Am Chem Soc ; 146(13): 9444-9454, 2024 Apr 03.
Artículo en Inglés | MEDLINE | ID: mdl-38513075

RESUMEN

The 3d transition metal-catalyzed enantioconvergent radical cross-coupling provides a powerful tool for chiral molecule synthesis. In the classic mechanism, the bond formation relies on the interaction between nucleophile-sequestered metal complexes and radicals, limiting the nucleophile scope to sterically uncongested ones. The coupling of sterically congested nucleophiles poses a significant challenge due to difficulties in transmetalation, restricting the reaction generality. Here, we describe a probable outer-sphere nucleophilic attack mechanism that circumvents the challenging transmetalation associated with sterically congested nucleophiles. This strategy enables a general copper-catalyzed enantioconvergent radical N-alkylation of aromatic amines with secondary/tertiary alkyl halides and exhibits catalyst-controlled stereoselectivity. It accommodates diverse aromatic amines, especially bulky secondary and primary ones to deliver value-added chiral amines (>110 examples). It is expected to inspire the coupling of more nucleophiles, particularly challenging sterically congested ones, and accelerate reaction generality.

3.
Inorg Chem ; 63(9): 4288-4298, 2024 Mar 04.
Artículo en Inglés | MEDLINE | ID: mdl-38369784

RESUMEN

Ba3Lu(BO3)3(BLB):Ce3+,Tb3+/Mn2+ phosphors were designed to explore effective and multifunctional applications. Under the excitation of near-ultraviolet (n-UV) light, the BLB:Ce3+ phosphor showed broad-band blue emission. After codoping with Mn2+ ions, the single-phase white light phosphor is achieved through the energy transfer (ET) between Ce3+ and Mn2+. In addition, thermal stability is significantly enhanced by the addition of Tb3+ (BLB:0.02Ce3+,0.20Tb3+) compared to that codoped with Mn2+ (BLB:0.02Ce3+,0.10Mn2+). The light-emitting diode (LED) device with warm white light emission is fabricated with UV-chip-coated BLB:0.02Ce3+,0.05Tb3+ and Sr2Si5N8:Eu2+ phosphors, showing a good potential application value for LEDs. Additionally, the spectral properties of borate-based phosphors (BLB:0.02Ce3+) under high pressure were studied for the first time. Surprisingly, the change of pressure enabled the emission peak of BLB:0.02Ce3+ to be tuned from 485 to 552 nm, and dλ/dP is 3.51 nm GPa-1. The color changes from blue to yellow with an increase of pressure. Compared with the reported data, the pressure-sensing sensitivity based on the central peak shift in this work is the highest in all Ce3+ single-doped samples. In addition, the emitting color and intensity were gradually regained after decompression. The intensity can reach 80% of the initial intensity. All data demonstrate that the BLB:0.02Ce3+ phosphor has the potential to be utilized as an optical pressure sensor due to the high-pressure sensitivity and visible color tuning.

4.
Inorg Chem ; 63(8): 3882-3892, 2024 Feb 26.
Artículo en Inglés | MEDLINE | ID: mdl-38358930

RESUMEN

Optical pressure sensing by phosphors is a growing area of research. However, the main pressure measurement methods rely on the movement of the central peak position, which has significant drawbacks for practical applications. This paper demonstrates the feasibility of using the fluorescence intensity ratio (FIR) of different emission peaks for pressure sensing. The FIR (IBi3+/ILn3+) values of the synthesized YNbO4:Bi3+/Ln3+ (Ln = Eu or Sm) phosphors are all first-order exponentially related to pressure, and YNbO4:Bi3+/Ln3+ (Ln = Eu or Sm) phosphors have high pressure-sensing sensitivities (Sp and Spr), which are 6 times higher than those from our previously reported work. In addition, the changes in FIR values during the decompression process were also calculated, and the trend was similar to that during the compression process. The YNbO4:Bi3+,Eu3+ phosphor has better pressure recovery performance. In summary, the YNbO4:Bi3+/Ln3+ (Ln = Eu or Sm) phosphors reported in this paper are expected to be applied in the field of optical pressure sensing, and this study provides a new approach and perspective for designing new phosphors for pressure measurement.

5.
BMC Pregnancy Childbirth ; 24(1): 109, 2024 Feb 05.
Artículo en Inglés | MEDLINE | ID: mdl-38317068

RESUMEN

BACKGROUND: Hypertensive disorders of pregnancy (HDP) is the most common cause of indicated preterm delivery, but the impact of prenatal steroid exposure on the outcomes of preterm infants born to HDP mothers, who may be at risk for intrauterine hypoxia-ischemia, remains uncertain. The study objective is to evaluate the mortality and morbidities in HDP for very preterm infants (VPIs) exposed to different course of ANS. METHODS: This is a prospective cohort study comprising infants with < 32 weeks gestation born to women with HDP only from 1 Jan. 2019 to 31 Dec. 2021 within 40 participating neonatal intensive care units (NICUs) in Sino-northern network. ANS courses included completed, partial, repeated, and no ANS. Univariate and multivariable analyses were performed on administration of ANS and short-term outcomes before discharge. RESULTS: Among 1917 VPIs born to women with HDP only, 987(51.4%) received a complete course of ANS within 48 h to 7 days before birth, 560(29.2%) received partial ANS within 24 h before delivery, 100(5.2%) received repeat ANS and 270 (14.1%) did not receive any ANS. Compared to infants who received complete ANS, infants unexposed to ANS was associated with higher odds of death (AOR 1.85; 95%CI 1.10, 3.14), Severe Neurological Injury (SNI) or death (AOR 1.68; 95%CI 1.29,3.80) and NEC or death (AOR 1.78; 95%CI 1.55, 2.89), the repeated ANS group exhibits a significant negative correlation with the duration of oxygen therapy days (correlation coefficient - 18.3; 95%CI-39.2, -2.1). However, there were no significant differences observed between the full course and partial course groups in terms of outcomes. We can draw similar conclusions in the non-SGA group, while the differences are not significant in the SGA group. From KM curve, it showed that the repeated group had the highest survival rate, but the statistical analysis did not indicate a significant difference. CONCLUSIONS: Even partial courses of ANS administered within 24 h before delivery proved to be protective against death and other morbidities. The differences mentioned above are more pronounced in the non-SGA group. Repeat courses demonstrate a trend toward protection, but this still needs to be confirmed by larger samples.


Asunto(s)
Hipertensión Inducida en el Embarazo , Enfermedades del Prematuro , Preeclampsia , Lactante , Recién Nacido , Embarazo , Humanos , Femenino , Recien Nacido Prematuro , Estudios Prospectivos , Hipertensión Inducida en el Embarazo/epidemiología , Corticoesteroides/uso terapéutico , Enfermedades del Prematuro/prevención & control , Edad Gestacional , Retardo del Crecimiento Fetal , Morbilidad
6.
Angew Chem Int Ed Engl ; 63(11): e202319850, 2024 Mar 11.
Artículo en Inglés | MEDLINE | ID: mdl-38273811

RESUMEN

In contrast with the well-established C(sp2 )-SCF3 cross-coupling to forge the Ar-SCF3 bond, the corresponding enantioselective coupling of readily available alkyl electrophiles to forge chiral C(sp3 )-SCF3 bond has remained largely unexplored. We herein disclose a copper-catalyzed enantioselective radical C(sp3 )-SCF3 coupling of a range of secondary/tertiary benzyl radicals with the easily available (Me4 N)SCF3 reagent. The key to the success lies in the utilization of chiral phosphino-oxazoline-derived anionic N,N,P-ligands through tuning electronic and steric effects for the simultaneous control of the reaction initiation and enantioselectivity. This strategy can successfully realize two types of asymmetric radical reactions, including enantioconvergent C(sp3 )-SCF3 cross-coupling of racemic benzyl halides and three-component 1,2-carbotrifluoromethylthiolation of arylated alkenes under mild reaction conditions. It therefore provides a highly flexible platform for the rapid assembly of an array of enantioenriched SCF3 -containing molecules of interest in organic synthesis and medicinal chemistry.

7.
Nat Chem ; 16(3): 466-475, 2024 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-38057367

RESUMEN

Although α-chiral C(sp3)-S bonds are of enormous importance in organic synthesis and related areas, the transition-metal-catalysed enantioselective C(sp3)-S bond construction still represents an underdeveloped domain probably due to the difficult heterolytic metal-sulfur bond cleavage and notorious catalyst-poisoning capability of sulfur nucleophiles. Here we demonstrate the use of chiral tridentate anionic ligands in combination with Cu(I) catalysts to enable a biomimetic enantioconvergent radical C(sp3)-S cross-coupling reaction of both racemic secondary and tertiary alkyl halides with highly transformable sulfur nucleophiles. This protocol not only exhibits a broad substrate scope with high enantioselectivity but also provides universal access to a range of useful α-chiral alkyl organosulfur compounds with different sulfur oxidation states, thus providing a complementary approach to known asymmetric C(sp3)-S bond formation methods. Mechanistic results support a biomimetic radical homolytic substitution pathway for the critical C(sp3)-S bond formation step.

8.
Sci Rep ; 13(1): 22702, 2023 Dec 19.
Artículo en Inglés | MEDLINE | ID: mdl-38123568

RESUMEN

One crucial component of ghost imaging (GI) is the encoded mask. Higher-quality reconstruction at lower sampling rates is still a major challenge for GI. Inspired by deep learning, max-projection method is proposed in the paper to reorder the Hadamard masks for its efficient and rapid reconstruction. The simulations demonstrated that max-projection ordering with only 20 face training images yielded excellent reconstruction outcomes. In noise-free simulations, at an ultralow sampling rate of 5%, the PSNR of the max-projection ordering was 1.1 dB higher than that of the cake-cutting ordering with the best performance in the reference group. In noisy simulations, at ultralow sampling rates, the retrieved images remained almost identical to their noise-free counterparts. Irrespective of the presence or absence of noise, the max-projection ordering guaranteed the highest fidelity of image reconstruction at ultralow sampling rates. The reconstruction time was reduced to mere milliseconds, thereby enabling swift visualization of dynamic phenomena. Accordingly, the max-projection ordering Hadamard matrix offers a promising solution for real-time GI due to its higher reconstruction quality, stronger noise immunity and millisecond reconstruction time.

9.
BMJ Open ; 13(12): e074309, 2023 12 28.
Artículo en Inglés | MEDLINE | ID: mdl-38154879

RESUMEN

BACKGROUND: Recently, with the rapid development of the perinatal medical system and related life-saving techniques, both the short-term and long-term prognoses of extremely preterm infants (EPIs) have improved significantly. In rapidly industrialising countries like China, the survival rates of EPIs have notably increased due to the swift socioeconomic development. However, there is still a reasonably lower positive response towards the treatment of EPIs than we expected, and the current situation of withdrawing care is an urgent task for perinatal medical practitioners. OBJECTIVE: To develop and validate a model that is practicable for EPIs as soon as possible after birth by regression analysis, to assess the risk of mortality and chance of survival. METHODS: This multicentre prospective cohort study used datasets from the Sino-Northern Neonatal Network, including 46 neonatal intensive care units (NICUs). Risk factors including maternal and neonatal variables were collected within 1 hour post-childbirth. The training set consisted of data from 41 NICUs located within the Shandong Province of China, while the validation set included data from 5 NICUs outside Shandong Province. A total of 1363 neonates were included in the study. RESULTS: Gestational age, birth weight, pH and lactic acid in blood gas analysis within the first hour of birth, moderate-to-severe hypothermia on admission and adequate antenatal corticosteroids were influencing factors for EPIs' mortality with important predictive ability. The area under the curve values for internal validation of our prediction model and Clinical Risk Index for Babies-II scores were 0.81 and 0.76, and for external validation, 0.80 and 0.51, respectively. Moreover, the Hosmer-Lemeshow test showed that our model has a constant degree of calibration. CONCLUSIONS: There was good predictive accuracy for mortality of EPIs based on influencing factors prenatally and within 1 hour after delivery. Predicting the risk of mortality of EPIs as soon as possible after birth can effectively guide parents to be proactive in treating more EPIs with life-saving value. TRIAL REGISTRATION NUMBER: ChiCTR1900025234.


Asunto(s)
Recien Nacido Extremadamente Prematuro , Unidades de Cuidado Intensivo Neonatal , Lactante , Recién Nacido , Humanos , Femenino , Embarazo , Estudios Prospectivos , Edad Gestacional , Pronóstico
10.
China CDC Wkly ; 5(44): 978-983, 2023 Nov 03.
Artículo en Inglés | MEDLINE | ID: mdl-38023392

RESUMEN

What is already known about this topic?: Numerous studies conducted in China have reported on the prevalence of birth defects (BDs). However, the limited surveillance periods in select studies curtail comprehensive trends and cause evaluation. Accordingly, the surveillance duration of BDs is extended, and a comprehensive analysis of their prevailing trends is conducted to provide a basis for government intervention and policy implementation. What is added by this report?: There is a distinct increase in the incidence of BDs observed in Jinan. In rural areas, a pronounced upward trend was observed, and the increase was more rapid than in urban areas. BD prevalence among mothers over 35 years old and under 20 years old was substantially higher than BD prevalence rates in other maternal age brackets. Specifically, the period from 2005 to 2022 saw the prevalence of congenital heart disease surge, the fastest average annual growth rate among all birth defects. What are the implications for public health practice?: It's essential to prioritize pregnant women in rural areas and those at both ends of the maternal age spectrum. Implementing comprehensive initiatives is crucial to address the high prevalence of congenital heart disease.

11.
Appl Opt ; 62(18): 4793-4796, 2023 Jun 20.
Artículo en Inglés | MEDLINE | ID: mdl-37707253

RESUMEN

One of the most critical parameters in synchrotron radiation (SR) experiments is the stability of the photon energy, which is primarily affected by the stability of the light source and the optical elements in the beamline. Due to the characteristics of SR and the use of dispersive elements such as monochromators in the beamline, the change of the beam position is usually accompanied by the change of energy and flux, while most traditional beam monitoring methods are based on the direct or indirect measurement of total flux, and are therefore sensitive to the beam position only, having no energy resolution. In this paper, an in situ monitoring system has been designed to measure the short-term (jitter) and long-term (drift) characteristics of the energy variation in the SR beamline. The system consists of a double-crystal monochromator, an orthogonal analysis crystal, and an X-ray imaging detector, which could decouple the angle and energy spread of the photon beam based on the dispersion effect in Bragg diffraction. The time response and the energy resolution of the system could reach millisecond and millielectron volt level, respectively.

12.
Thyroid ; 33(9): 1055-1063, 2023 09.
Artículo en Inglés | MEDLINE | ID: mdl-37566523

RESUMEN

Background: Preterm infants presented a high prevalence of congenital hypothyroidism (CH), while the optimal screening pattern is still under debate. This study aimed at evaluating the characteristics of thyroid function by conducting weekly screening during the first month of life in very preterm infants (VPIs) to achieve timely diagnosis and treatment of CH. Methods: A prospective cohort study was carried out on VPIs born with gestational age (GA) <32 weeks (w) and admitted to the participating institutes from January 1, 2019 to December 31, 2022. Serial serum thyroid hormone levels were measured weekly within the first month after birth, and at 36 w of corrected age, or before discharge. Datasets for serial thyroid hormone levels and general information were obtained. Results: A total of 5992 VPIs were enrolled in this study, of which 456 (7.6%) [95% confidence interval (CI), 6.9-8.3%] were diagnosed with CH. The incidence of CH increased with lower GA, moving from 4.8% [CI, 3.4-6.1%] at GA 31 w to 16.9% [CI, 8.3-25.4%] at GA <26 w. Among the CH subjects, 57.7% [CI, 53.1-62.2%] were identified after the first screening and classified as delayed thyrotropin elevation (dTSH). With the decrease of GA, the proportion of dTSH also increased, moving from 38.1% [CI, 27.5-48.7%] at GA 31 w to 82.6% [CI, 65.8-99.4%] at GA <26 w. Through conducting weekly screening of thyroid function, it was remarkable that only 42.3% [CI, 37.8-46.9%] of CH subjects were diagnosed during the first screening. The cumulative rate of CH identified by rescreening performed at the second, third, and fourth week was 76.1% [CI, 72.2-80.0%], 90.6% [CI, 87.9-93.3%], and 98.9% [CI, 97.9-99.9%], respectively. Conclusion: The incidence of CH and dTSH both increase with lower GA in VPIs. Dynamic screening of thyroid function by weeks within the first month of life is crucial for the timely diagnosis and treatment of CH in VPIs, and it might effectively reduce the implications of missed diagnosis and delayed treatment. Clinical Trials Registration: ChiCTR1900025234 and ChiCTR2000037918 (Registration number).


Asunto(s)
Hipotiroidismo Congénito , Lactante , Recién Nacido , Humanos , Hipotiroidismo Congénito/diagnóstico , Hipotiroidismo Congénito/epidemiología , Recien Nacido Prematuro , Estudios Prospectivos , Tiroxina , Tamizaje Neonatal , Hormonas Tiroideas/uso terapéutico , Tirotropina
13.
Nanomaterials (Basel) ; 13(16)2023 Aug 10.
Artículo en Inglés | MEDLINE | ID: mdl-37630886

RESUMEN

As an encouraging photocatalyst, crystalline carbon nitride (CCN) exhibits unsatisfactory photocatalytic activity and stability due to its rapid recombination of photo-generative carriers. Herein, high-crystalline g-C3N4 was prepared, including CCN obtained in KCl (K-CCN), LiCl-KCl mixture (Li/K-CCN), and LiCl-NaCl-KCl mixture (Li/Na/K-CCN), via the molten salt strategy using pre-prepared bulk carbon nitride (BCN) as a precursor. The obtained BCN sample was formed by heptazine-based units, which convert into triazine-based units for K-CCN. Heptazine and triazine are two isotypes that co-exist in the Li/K-CCN and Li/Na/K-CCN samples. Compared with BCN and other CCN samples, the as-prepared Li/Na/K-CCN sample exhibited the optimal photocatalytic hydrogen evolution rates (3.38 mmol·g-1·h-1 under simulated sunlight and 2.25 mmol·g-1·h-1 under visible light) and the highest apparent quantum yield (10.97%). The improved photocatalytic performance of the Li/Na/K-CCN sample is mainly attributed to the construction of type-II heterojunction and the institution of the built-in electric field between triazine-based CCN and heptazine-based BCN. This work provides a new strategy for the structural optimization and heterostructure construction of crystalline carbon nitride photocatalysts.

14.
J Am Chem Soc ; 145(27): 14686-14696, 2023 Jul 12.
Artículo en Inglés | MEDLINE | ID: mdl-37392183

RESUMEN

The enantioconvergent C(sp3)-N cross-coupling of racemic alkyl halides with (hetero)aromatic amines represents an ideal means to afford enantioenriched N-alkyl (hetero)aromatic amines yet has remained unexplored due to the catalyst poisoning specifically for strong-coordinating heteroaromatic amines. Here, we demonstrate a copper-catalyzed enantioconvergent radical C(sp3)-N cross-coupling of activated racemic alkyl halides with (hetero)aromatic amines under ambient conditions. The key to success is the judicious selection of appropriate multidentate anionic ligands through readily fine-tuning both electronic and steric properties for the formation of a stable and rigid chelating Cu complex. Thus, this kind of ligand could not only enhance the reducing capability of a copper catalyst to provide an enantioconvergent radical pathway but also avoid the coordination with other coordinating heteroatoms, thereby overcoming catalyst poisoning and/or chiral ligand displacement. This protocol covers a wide range of coupling partners (89 examples for activated racemic secondary/tertiary alkyl bromides/chlorides and (hetero)aromatic amines) with high functional group compatibility. When allied with follow-up transformations, it provides a highly flexible platform to access synthetically useful enantioenriched amine building blocks.

15.
Biomark Res ; 11(1): 63, 2023 Jun 07.
Artículo en Inglés | MEDLINE | ID: mdl-37287049

RESUMEN

The ATP-adenosine pathway has emerged as a promising target for cancer therapy, but challenges remain in achieving effective tumor control. Early research focused on blocking the adenosine generating enzyme CD73 and the adenosine receptors A2AR or A2BR in cancer. However, recent studies have shown that targeting CD39, the rate-limiting ecto-enzyme of the ATP-adenosine pathway, can provide more profound anti-tumor efficacy by reducing immune-suppressive adenosine accumulation and increasing pro-inflammatory ATP levels. In addition, combining CD39 blocking antibody with PD-1 immune checkpoint therapy may have synergistic anti-tumor effects and improve patient survival. This review will discuss the immune components that respond to CD39 targeting in the tumor microenvironment. Targeting CD39 in cancer has been shown to not only decrease adenosine levels in the tumor microenvironment (TME), but also increase ATP levels. Additionally, targeting CD39 can limit the function of Treg cells, which are known to express high levels of CD39. With phase I clinical trials of CD39 targeting currently underway, further understanding and rational design of this approach for cancer therapy are expected.

16.
J Gastroenterol ; 58(9): 925-944, 2023 09.
Artículo en Inglés | MEDLINE | ID: mdl-37391589

RESUMEN

BACKGROUND: N6-methyladenine modification of RNA, a critical component of the regulatory role at the post-transcriptional level, has a crucial effect on tumor development and progression. vir-Like m6A methyltransferase associated (VIRMA) has been recently discovered as an N6-methyladenine methyltransferase; however, its specific role in intrahepatic cholangiocarcinoma (ICC) remains to be investigated in-depth. METHODS: VIRMA expression and its association with clinicopathological characteristics were evaluated using The Cancer Genome Atlas (TCGA) dataset and tissue microarrays. In vivo and in vitro assays were performed to determine the role of VIRMA in ICC proliferation and metastasis. The underlying mechanism by which VIRMA influences ICC was clarified by RNA sequencing (RNA-seq), methylated RNA immunoprecipitation sequencing (MeRIP-seq), SLAM sequencing (SLAM-seq), RNA immunoprecipitation, a luciferase reporter assay, and chromatin immunoprecipitation assay. RESULTS: VIRMA showed high expression in ICC tissues, and this finding predicted a dismal prognostic outcome. The high expression of VIRMA in ICC was due to the demethylation of H3K27me3 modification in the promoter region. Functionally, VIRMA is required for the endothelial-mesenchymal transition (EMT) process in ICC cells, as shown by multiple ICC models in in vitro and in vivo experiments. Mechanistically, multi-omics analysis using ICC cells demonstrated that TMED2 and PARD3B were the direct downstream target of VIRMA. The methylated TMED2 and PARD3B transcripts were directly recognized by HuR, which exerted stabilizing effects on its bound RNA. VIRMA-induced expression of TMED2 and PARD3B activated the Akt/GSK/ß-catenin and MEK/ERK/Slug signaling pathways, thereby promoting ICC proliferation and metastasis. CONCLUSIONS: The present study showed that VIRMA plays a critical role in ICC development by stabilizing TMED2 and PARD3B expression through the m6A-HuR-mediated mechanism. Thus, demonstrating VIRMA and its pathway as candidate therapeutic targets for ICC treatment.


Asunto(s)
Neoplasias de los Conductos Biliares , Colangiocarcinoma , Proteínas de Unión al ARN , Humanos , Neoplasias de los Conductos Biliares/genética , Neoplasias de los Conductos Biliares/patología , Conductos Biliares Intrahepáticos/metabolismo , Conductos Biliares Intrahepáticos/patología , Proteínas Portadoras/genética , Línea Celular Tumoral , Colangiocarcinoma/genética , Colangiocarcinoma/patología , Epigénesis Genética , Proteínas de la Membrana/genética , Metiltransferasas/genética , ARN Mensajero/genética , ARN Mensajero/metabolismo , Proteínas de Transporte Vesicular/genética , Proteínas de Transporte Vesicular/metabolismo , Proteínas de Unión al ARN/genética
17.
Angew Chem Int Ed Engl ; 62(27): e202302983, 2023 Jul 03.
Artículo en Inglés | MEDLINE | ID: mdl-37154671

RESUMEN

Transition-metal catalyzed enantioconvergent cross-coupling of tertiary alkyl halides with ammonia offers a rapid avenue to chiral unnatural α,α-disubstituted amino acids. However, the construction of chiral C-N bonds between tertiary-carbon electrophiles and nitrogen nucleophiles presented a great challenge owing to steric congestion. We report a copper-catalyzed enantioconvergent radical C-N cross-coupling of alkyl halides with sulfoximines (as ammonia surrogates) under mild conditions by employing a chiral anionic N,N,N-ligand with a long spreading side arm. An array of α,α-disubstituted amino acid derivatives were obtained with good efficiency and enantioselectivity. The synthetic utility of the strategy has been showcased by the elaboration of the coupling products into different chiral α-fully substituted amine building blocks.

18.
Neural Comput Appl ; 35(15): 10717-10731, 2023.
Artículo en Inglés | MEDLINE | ID: mdl-37155461

RESUMEN

The Coronavirus disease 2019 (COVID-19) has rapidly spread all over the world since its first report in December 2019, and thoracic computed tomography (CT) has become one of the main tools for its diagnosis. In recent years, deep learning-based approaches have shown impressive performance in myriad image recognition tasks. However, they usually require a large number of annotated data for training. Inspired by ground glass opacity, a common finding in COIVD-19 patient's CT scans, we proposed in this paper a novel self-supervised pretraining method based on pseudo-lesion generation and restoration for COVID-19 diagnosis. We used Perlin noise, a gradient noise based mathematical model, to generate lesion-like patterns, which were then randomly pasted to the lung regions of normal CT images to generate pseudo-COVID-19 images. The pairs of normal and pseudo-COVID-19 images were then used to train an encoder-decoder architecture-based U-Net for image restoration, which does not require any labeled data. The pretrained encoder was then fine-tuned using labeled data for COVID-19 diagnosis task. Two public COVID-19 diagnosis datasets made up of CT images were employed for evaluation. Comprehensive experimental results demonstrated that the proposed self-supervised learning approach could extract better feature representation for COVID-19 diagnosis, and the accuracy of the proposed method outperformed the supervised model pretrained on large-scale images by 6.57% and 3.03% on SARS-CoV-2 dataset and Jinan COVID-19 dataset, respectively.

19.
Life (Basel) ; 13(4)2023 Apr 10.
Artículo en Inglés | MEDLINE | ID: mdl-37109505

RESUMEN

Optical coherence tomography (OCT) provides unique advantages in ophthalmic examinations owing to its noncontact, high-resolution, and noninvasive features, which have evolved into one of the most crucial modalities for identifying and evaluating retinal abnormalities. Segmentation of laminar structures and lesion tissues in retinal OCT images can provide quantitative information on retinal morphology and reliable guidance for clinical diagnosis and treatment. Convolutional neural networks (CNNs) have achieved success in various medical image segmentation tasks. However, the receptive field of convolution has inherent locality constraints, resulting in limitations of mainstream frameworks based on CNNs, which is still evident in recognizing the morphological changes of retina OCT. In this study, we proposed an end-to-end network, TranSegNet, which incorporates a hybrid encoder that combines the advantages of a lightweight vision transformer (ViT) and the U-shaped network. The CNN features under multiscale resolution are extracted based on the improved U-net backbone, and a ViT with the multi-head convolutional attention is introduced to capture the feature information in a global view, realizing accurate localization and segmentation of retinal layers and lesion tissues. The experimental results illustrate that hybrid CNN-ViT is a strong encoder for retinal OCT image segmentation tasks and the lightweight design reduces its parameter size and computational complexity while maintaining its outstanding performance. By applying TranSegNet to healthy and diseased retinal OCT datasets separately, TranSegNet demonstrated superior efficiency, accuracy, and robustness in the segmentation results of retinal layers and accumulated fluid than the four advanced segmentation methods, such as FCN, SegNet, Unet and TransUnet.

20.
J Am Chem Soc ; 145(11): 6535-6545, 2023 Mar 22.
Artículo en Inglés | MEDLINE | ID: mdl-36912664

RESUMEN

Transition-metal-catalyzed enantioselective functionalization of acyl radicals has so far not been realized, probably due to their relatively high reactivity, which renders the chemo- and stereocontrol challenging. Herein, we describe Cu(I)-catalyzed enantioselective desymmetrizing C-O bond coupling of acyl radicals. This reaction is compatible with (hetero)aryl and alkyl aldehydes and, more importantly, displays a very broad scope of challenging alcohol substrates, such as 2,2-disubstituted 1,3-diols, 2-substituted-2-chloro-1,3-diols, 2-substituted 1,2,3-triols, 2-substituted serinols, and meso primary 1,4-diols, providing enantioenriched esters characterized by challenging acyclic tetrasubstituted carbon stereocenters. Partnered by one- or two-step follow-up transformations, this reaction provides a convenient and practical strategy for the rapid preparation of chiral C3 building blocks from readily available alcohols, particularly the industrially relevant glycerol. Mechanistic studies supported the proposed C-O bond coupling of acyl radicals.

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