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1.
J Org Chem ; 2024 May 16.
Artigo em Inglês | MEDLINE | ID: mdl-38753315

RESUMO

Herein we have pioneered an innovative synthetic strategy for the efficient assembly of various heteroarene-condensed benzofuran derivatives, utilizing benzofuran-derived azadienes (BDAs) and quinolines as the starting materials. This method functions with transition-metal catalysis and uses cost-effective formic acid as the reducing agent. Mechanistic investigations indicate that this transformation would involve a [4 + 2] annulation cascade process. This approach demonstrates a high tolerance to various functional groups and yields excellent results.

2.
Appl Opt ; 63(9): 2352-2361, 2024 Mar 20.
Artigo em Inglês | MEDLINE | ID: mdl-38568591

RESUMO

Improving the spectrum efficiency (SE) is an effective method to further enhance the data rate of bandwidth-limited underwater wireless optical communication (UWOC) systems. Non-orthogonal frequency-division multiplexing (NOFDM) with a compression factor of 0.5 can save half of the bandwidth without introducing any inter-carrier-interference (ICI) only if the total number of subcarriers is large enough, and we termed it as half-spectrum OFDM (HS-OFDM). To the best of our knowledge, this is the first reported work on a closed-form HS-OFDM signal in the discrete domain from the perspective of a correlation matrix. Due to the special mathematical property, no extra complex decoding algorithm is required at the HS-OFDM receiver, making it as simple as the conventional OFDM receiver. Compared with traditional OFDM, HS-OFDM can realize the same data rate, but with a larger signal-to-noise ratio (SNR) margin. To fully use the SNR resource of the communication system, we further propose a digital power division multiplexed HS-OFDM (DPDM-HS-OFDM) scheme to quadruple the SE of conventional OFDM for the bandwidth-starved UWOCs. The experimental results show that HS-OFDM can improve the receiver sensitivity by around 4 dB as opposed to conventional 4QAM-OFDM with the same data rate and SE. With the help of the DPDM-HS-OFDM scheme, the data rate of multi-user UWOC can reach up to 4.5 Gbps under the hard-decision forward error correction (HD-FEC) limit of a bit error rate (BER) of 3.8×10-3. Although there is some performance degradation in comparison with single-user HS-OFDM, the BER performance of multi-user DPDM-HS-OFDM is still superior to that of conventional single-user 4QAM-OFDM. Both single-user HS-OFDM and multi-user DPDM-HS-OFDM successfully achieve 2 Gbps/75 m data transmission, indicating that the DPDM-HS-OFDM scheme is of great importance in bandwidth-limited UWOC systems and has guiding significance to underwater wireless optical multiple access.

3.
Artigo em Inglês | MEDLINE | ID: mdl-38662115

RESUMO

OBJECTIVE: This purpose of this study is to investigate the effectiveness and safety of utilizing the arterial spin-labeling (ASL) combined with diffusion-weighted imaging (DWI) and fluid-attenuated inversion recovery (FLAIR) combined with DWI double mismatch in the endovascular treatment of patients diagnosed with wake-up stroke (WUS). METHODS: In this single-center trial, patients diagnosed with WUS underwent thrombectomy if acute ischemic lesions were observed on DWI indicating large precerebral circulation occlusion. Patients with no significant parenchymal hypersignal on FLAIR and ASL imaging showing a hypoperfusion tissue to infarct core volume ratio of at least 1.2 were included. The participants were divided into groups receiving endovascular thrombectomy plus medical therapy or medical therapy alone, based on their subjective preference. Functional outcomes were assessed using the ordinal score on the modified Rankin scale (mRs) at 90 days, along with the rate of functional independence. RESULTS: In this study, a total of 77 patients were included, comprising 38 patients in the endovascular therapy group and 39 patients in the medical therapy group. The endovascular therapy group exhibited more favorable changes in the distribution of functional prognosis measured by mRs at 90 days, compared to the medical therapy group (adjusted common odds ratio, 3.25; 95% CI, 1.03 to 10.26; P < 0.01). Additionally, the endovascular therapy group had a higher proportion of patients achieving functional independence (odds ratio, 4.0; 95% CI, 1.36 to 11.81; P < 0.01). Importantly, there were no significant differences observed in the incidence of intracranial hemorrhage or mortality rates between the two groups. CONCLUSION: Guided by the ASL-DWI and FLAIR-DWI double mismatch, endovascular thrombectomy combined with standard medical treatment appears to yield superior functional outcomes in patients with WUS and large vessel occlusion compared to standard medical treatment alone.

4.
Opt Express ; 31(20): 33435-33448, 2023 Sep 25.
Artigo em Inglês | MEDLINE | ID: mdl-37859126

RESUMO

Due to a great many superior features of infrared light communication (ILC), like high capacity and strong privacy, ILC is considered a potential candidate for serving the high demands of beyond fifth-generation/sixth-generation (B5G/6 G) communication systems. However, the terminal's limited field-of-view (FOV) induces great difficulty in establishing line-of-sight (LoS) link between the transceiver and the terminal. In this paper, we propose a wide-FOV auto-coupling optical antenna system that utilizes a wide-FOV telecentric lens to collect incident infrared beams and automatically couple them into a specific single-mode-fiber (SMF) channel of fiber array and optical switch. The performance of this optical antenna system is assessed through simulation and manual alignment operation, and validated by automatic alignment results. A coupling loss of less than 10.6 dB within a FOV of 100° for both downstream and upstream beams in C band is demonstrated by the designed system. Furthermore, we establish a bidirectional optical wireless communications (OWC) system employing this antenna and a fiber-type modulating retro-reflector (MRR) system in the terminal. Both 10-Gbps on-off keying (OOK) downstream and upstream transmissions are successfully realized with the FOV of up to 100° in C band where the measured bit-error-rate (BER) is lower than 3.8 × 10-3. To the best of our knowledge, this is a brand-new auto-coupling optical antenna system with the largest FOV in ILC automatic alignment works in terminals that have ever been reported.

5.
Org Biomol Chem ; 21(20): 4191-4194, 2023 May 24.
Artigo em Inglês | MEDLINE | ID: mdl-37132390

RESUMO

Fused furans are commonly found units in natural products and medicinal molecules, and methods for their introduction are of fundamental importance. Here we report one-pot cycloadditions of ethynyl indoloxazolidones with 1,3-cyclohexanediones enabled by copper catalysis, leading to a series of functionalized furan derivatives in good yields. This method features mild reaction conditions, high efficiency, and wide substrate scope.

6.
Chem Commun (Camb) ; 59(23): 3463-3466, 2023 Mar 16.
Artigo em Inglês | MEDLINE | ID: mdl-36872868

RESUMO

Heterocyclic Quaternary Phosphonium Salts (HQPS) have emerged as promising chemicals for organic synthesis and medicinal chemistry. However, the present synthetic methodology of this type of compound is still limited. Here, we report a deconstructive reorganization strategy based on Brønsted acid-mediated tandem 1,4 addition/intramolecular cyclization of triphenylphosphine derivatives and in situ generated o-AQMs for the first time. This protocol provides a novel approach to heterocyclic quaternary phosphonium salts. The method also features a non-metal catalyst, mild reaction conditions, high efficiency and wide substrate scope. Moreover, a series of obtained heterocyclic phosphonium salts can be converted to isotopically labelled 2-benzofuran compounds directly by simple deuteration reactions.

7.
Appl Opt ; 62(3): 541-551, 2023 Jan 20.
Artigo em Inglês | MEDLINE | ID: mdl-36821256

RESUMO

Underwater wireless optical communication (UWOC) has broad prospects in underwater real-time applications. We design and experimentally demonstrate a real-time discrete Fourier transform spread discrete multi-tone (DFT-S DMT) signal transmission based on a field programmable gate array for a blue-LED-based UWOC system with a data rate of up to 30 Mbps over a 15-m underwater channel. The architecture and usage of an on-chip resource as well as power consumption are analyzed and discussed. To reduce the impacts of multipath fading and received intensity fluctuation, spatial diversity reception is also introduced. Furthermore, the receiver sensitivity at a specified bit error rate (BER) threshold and the quality of the images are evaluated using three types of Reed-Solomon (RS) codes. At the BER threshold of 10-4, over 2.8-dB receiver sensitivity improvement is obtained by the DFT-S DMT scheme with the RS (64, 56) code as compared to the uncoded one at the data rate of 30 Mbps. The performance of BER, color difference, and structural similarity in the image transmission of DFT-S DMT is superior to that of the conventional hard clipping quadrature amplitude modulation DMT in a high-data-rate region because of the low peak-to-average-power ratio and ability to mitigate high-frequency fading in a band-limited UWOC system. With schemes of the RS code, DFT-S, and diversity reception, error-free transmission of images is achieved over a 15-m water channel. The proposed UWOC system has the advantages of low power consumption and portability, which foresees a bright future in underwater applications over short to moderate distances.

8.
J Diabetes Investig ; 14(2): 263-288, 2023 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-36514864

RESUMO

AIMS/INTRODUCTION: Diet therapy is a vital approach to manage type 2 diabetes and prediabetes. However, the comparative efficacy of different eating patterns is not clear enough. We aimed to compare the efficacy of various eating patterns for glycemic control, anthropometrics, and serum lipid profiles in the management of type 2 diabetes and prediabetes. MATERIALS AND METHODS: We conducted a network meta-analysis using arm-based Bayesian methods and random effect models, and drew the conclusions using the partially contextualized framework. We searched twelve databases and yielded 9,534 related references, where 107 studies were eligible, comprising 8,909 participants. RESULTS: Eleven diets were evaluated for 14 outcomes. Caloric restriction was ranked as the best pattern for weight loss (SUCRA 86.8%) and waist circumference (82.2%), low-carbohydrate diets for body mass index (81.6%), and high-density lipoprotein (84.0%), and low-glycemic-index diets for total cholesterol (87.5%) and low-density lipoprotein (86.6%). Other interventions showed some superiorities, but were imprecise due to insufficient participants and needed further investigation. The attrition rates of interventions were similar. Meta-regression suggested that macronutrients, energy intake, and weight may modify outcomes differently. The evidence was of moderate-to-low quality, and 38.2% of the evidence items met the minimal clinically important differences. CONCLUSIONS: The selection and development of dietary strategies for diabetic/prediabetic patients should depend on their holistic conditions, i.e., serum lipid profiles, glucometabolic patterns, weight, and blood pressure. It is recommended to identify the most critical and urgent metabolic indicator to control for one specific patient, and then choose the most appropriate eating pattern accordingly.


Assuntos
Diabetes Mellitus Tipo 2 , Estado Pré-Diabético , Humanos , Teorema de Bayes , Lipídeos , Metanálise em Rede
9.
J Am Chem Soc ; 145(1): 171-178, 2023 01 11.
Artigo em Inglês | MEDLINE | ID: mdl-36571763

RESUMO

Controlling absolute stereochemistry in catalytic photochemical reactions is generally challenging owing to high rates of background reactivity. Successful strategies broadly rely on selective excitation of the reaction substrate when associated with a chiral catalyst. Recent studies have demonstrated that chiral Lewis acid complexes can enable selective energy transfer from a photosensitizer to facilitate enantioselective triplet state reactions. Here, we apply this approach to the enantioselective catalysis of a 6π photocyclization through the design of an iridium photosensitizer optimized to undergo energy transfer to a reaction substrate only in the presence of a chiral Lewis acid complex. Among a group of iridium(III) sensitizers, enantioselectivity and yield closely correlate with photocatalyst triplet energy within a narrow window enabled by a modest reduction in substrate triplet energy upon binding a scandium/ligand complex. These results demonstrate that photocatalyst tuning offers a means to suppress background reactivity and improve enantioselectivity in photochemical reactions.


Assuntos
Irídio , Ácidos de Lewis , Ácidos de Lewis/química , Irídio/química , Estereoisomerismo , Fármacos Fotossensibilizantes , Catálise
10.
Appl Intell (Dordr) ; 53(9): 10053-10067, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-35991679

RESUMO

Most existing action quality assessment (AQA) methods provide only an overall quality score for the input video and lack an evaluation of each substage of the movement process; thus, these methods cannot provide detailed feedback for users. Moreover, the existing datasets do not provide labels for substage quality assessment. To address these problems, in this work, a new label-reconstruction-based pseudo-subscore learning (PSL) method is proposed for AQA in sporting events. In the proposed method, the overall score of an action is not only regarded as a quality label but also used as a feature of the training set. A label-reconstruction-based learning algorithm is built to generate pseudo-subscore labels for the training set. Moreover, based on the pseudo-subscore labels and overall score labels, a multi-substage AQA model is fine-tuned from the PSL model to predict the action quality score of each substage and the overall score for an athlete. Several ablation experiments are performed to verify the effectiveness of each module. The experimental results show that our approach achieves state-of-the-art performance.

11.
BMJ Open ; 12(11): e063100, 2022 11 25.
Artigo em Inglês | MEDLINE | ID: mdl-36428023

RESUMO

OBJECTIVES: The administration of nursing assistants (NAs) is closely associated with patient outcomes, but studies evaluating intrahospital administration of NAs are limited. This study aimed to identify existing literature on intrahospital NAs' administration approaches. DESIGN: Scoping review. DATA SOURCES: PubMed, Embase, CINAHL, Scopus, ProQuest, CNKI, APA PsycInfo, Wanfang Med, SinoMed, Ovid Emcare, NICE, AHRQ, CADTH, JBI EBP and Cochrane DSR were searched for articles published between January 2011 and March 2022. ELIGIBILITY CRITERIA FOR SELECTING STUDIES: Qualitative, quantitative or mixed-method studies and evidence syntheses that evaluate administration approaches, models and appraisal tools of intrahospital NAs were included. DATA EXTRACTION AND SYNTHESIS: Two independent reviewers conducted search, data selection and data extraction according to Joanna Briggs Institute guidance and methodology for scoping review. The quality of included studies was assessed using Mixed Methods Appraisal Tool or AMSTAR V.2. Data were synthesised using narrative methods and frequency effect size analysis. RESULTS: Thirty-six studies were eligible, with acceptable quality. We identified 1 administration model, 9 administration methods, 15 educational programmes and 7 appraisal tools from the included studies. The frequency effect size analysis yielded 15 topics of the main focus at four levels, suggesting that included articles were mainly (33%) focused on the competency of NAs, and the lectures were the most (80%) used strategy in quality improvement projects. Evidence from the studies was of low-to-moderate quality, indicating huge gaps between evidence-based research and management practice. CONCLUSIONS: Practical intrahospital administration approaches were revealed, and fifteen primarily focused topics were identified. We should explore this area more thoroughly using structured frameworks and standardised methodology. This scoping review will help managers find more effective ways to improve the quality of care. Researchers may focus more on evidence-based practice in NA administration using the 15 topics as a breakthrough.


Assuntos
Hospitais , Assistentes de Enfermagem , Humanos , Prática Clínica Baseada em Evidências , Publicações , Projetos de Pesquisa
12.
Front Plant Sci ; 13: 1012186, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36325547

RESUMO

Common bean (Phaseolus vulgaris) is an important food crop; however, its production is affected by salt stress. Salt stress can inhibit seed germination, promote senescence, and modify cell wall biosynthesis, assembly, and architecture. Melatonin, an indole heterocycle, has been demonstrated to greatly impact cell wall structure, composition, and regulation in plants under stress. However, the molecular basis for such assumptions is still unclear. In this study, a common bean variety, "Naihua" was treated with water (W), 70 mmol/L NaCl solution (S), and 100 µmol/L melatonin supplemented with salt solution (M+S) to determine the response of common bean to exogenous melatonin and explore regulatory mechanism of melatonin against salt stress. The results showed that exogenous melatonin treatment alleviated salt stress-induced growth inhibition of the common bean by increasing the length, surface area, volume, and diameter of common bean sprouts. Moreover, RNA sequencing (RNA-seq) and real-time quantitative PCR (qRT-PCR) indicated that the cell wall regulation pathway was involved in the salt stress tolerance of the common bean enhanced by melatonin. Screening of 120 germplasm resources revealed that melatonin treatment improved the salt tolerance of more than 65% of the common bean germplasm materials. Melatonin also up-regulated cell wall pathway genes by at least 46%. Furthermore, we analyzed the response of the common bean germplasm materials to melatonin treatment under salt stress using the key genes associated with the synthesis of the common bean cell wall as the molecular markers. The results showed that two pairs of markers were significantly associated with melatonin, and these could be used as candidate markers to predict whether common bean respond to exogenous melatonin and then enhance salt tolerance at the sprouting stage. This study shows that cell wall can respond to exogenous melatonin and enhance the salt tolerance of common bean. The makers identified in this study can be used to select common bean varieties that can respond to melatonin under stress. Overall, the study found that cell wall could response melatonin and enhance the salt tolerance and developed the makers for predicting varieties fit for melatonin under stress in common bean, which may be applied in the selection or development of common bean varieties with abiotic stress tolerance.

13.
Appl Opt ; 61(22): 6534-6543, 2022 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-36255878

RESUMO

The nonlinearity of the light-emitting diode (LED) in underwater wireless optical communication (UWOC) systems is considered the one major limiting factor that degrades the system's performance. Volterra series-based nonlinear equalization is widely employed to mitigate such nonlinearity in communication systems. However, the conventional Volterra series-based model is of high complexity, especially for the nonlinearity of higher-order terms or longer memory lengths. In this paper, by pruning away some negligible beating terms and adaptively picking out some of the dominant terms while discarding the trivial ones, we propose and experimentally demonstrate a sparse pruned-term-based nonlinear decision-feedback equalization (SPT-NDFE) scheme for the LED-based UWOC system with an inappreciable performance degradation as compared to systems without the pruning strategy. Meanwhile, by replacing the self/cross beating terms with the terms formed by the absolute operation of a sum of two input samples instead of the product operation terms, a sparse pruned-term-based absolute operation nonlinear decision-feedback equalization (SPT-ANDFE) scheme is also introduced to further reduce complexity. The experimental results show that the SPT-NDFE scheme exhibits comparable performance as compared to the conventional NDFE (nonlinear decision-feedback equalization) scheme with lower complexity (the nonlinear coefficients are reduced by 63.63% as compared to the conventional NDFE scheme). While the SPT-ANDFE scheme yields suboptimal performance with further reduced complexity at the expense of a slight performance degradation, the robustness of the proposed schemes in different turbidity waters is experimentally verified. The proposed channel equalization schemes with low complexity and high performance are promising for power/energy-sensitive UWOC systems.

14.
J Org Chem ; 87(21): 14093-14102, 2022 Nov 04.
Artigo em Inglês | MEDLINE | ID: mdl-36281070

RESUMO

The visible-light-promoted difunctionalization of alkenyl ketones has been developed for easy access of various tetralones, cyclopropane, or alkenyl migration compounds. With fac-[Ir(ppy)3] as the photocatalyst, alkenyl ketones captured the α-carbonyl alkyl radical and evolved through intramolecular cyclization and the elimination of a proton to give the difunctionalized products. This strategy is characterized by good yields, mild reaction conditions, and outstanding functional group tolerance.

15.
Chem Res Toxicol ; 35(9): 1533-1540, 2022 09 19.
Artigo em Inglês | MEDLINE | ID: mdl-36074022

RESUMO

Nonylphenol (NP) is a widely used chemical, which has been considered a kind of endocrine-disrupting chemical and is involved in the occurrence and development of many types of cancers. Our recent studies demonstrated that NP exposure is related to colorectal cancer (CRC) progression. In this study, we also found epithelial-mesenchymal transition (EMT) promoted by NP treatment in CRC cells. However, the mechanism of NP on tumor metastasis is still unclear. In this study, we focused on the effect of the regulator of cell cycle (RGCC) induced by NP treatment. The cancer genome atlas (TCGA) analysis suggested that the expression of RGCC increased in CRC tissues, and our clinical samples showed that the expression of RGCC in tumor tissues is positively correlated with the serum level of NP in CRC patients. Further studies revealed that overexpression of RGCC could enhance the NP-induced EMT process in CRC cells and activate ERK signaling pathways. Inhibiting ERK signaling by ERK inhibitors or the knockdown of RGCC could attenuate the NP-induced EMT process. In addition, both RGCC overexpression and NP treatment could activate ERK pathways and attenuate the effect of ERK inhibitors on the EMT process in CRC cells. Altogether, this study demonstrated that NP could induce cell invasion and migration by increasing the expression of RGCC to enhance the EMT process, which might be through the activation of ERK signaling pathways. This finding supported a potential target for studying NP exposure-related colorectal cancers.


Assuntos
Neoplasias Colorretais , Transição Epitelial-Mesenquimal , Ciclo Celular , Linhagem Celular Tumoral , Movimento Celular , Proliferação de Células/genética , Neoplasias Colorretais/metabolismo , Regulação Neoplásica da Expressão Gênica , Humanos , Fenóis/farmacologia
16.
Front Nutr ; 9: 928805, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36105573

RESUMO

Flavonoids are important secondary metabolites, active biomolecules in germinating beans, and have prominent applications in food and medicine due to their antioxidant effects. Rutin is a plant flavonoid with a wide biological activity range. In this study, flavonoid (rutin) accumulation and its related molecular mechanisms in germinating common bean (Phaseolus vulgaris) were observed at different time points (0-120 h) under salt stress (NaCl). The rutin content increased from germination onset until 96 h, after which a reducing trend was observed. Metabolome analysis showed that salt stress alters flavonoid content by regulating phenylpropanoid (ko00940) and flavonoid (ko00941) biosynthesis pathways, as well as their enzyme activities, including cinnamyl-alcohol dehydrogenase (CAD), peroxidase (POD), chalcone isomerase (CHI), and flavonol synthase (FLS). The RNA-seq and quantitative real-time PCR (qRT-PCR) analyses also showed that these two pathways were linked to changes in flavonoid content following salt treatment. These results reveal that salt stress effectively enhanced rutin content accumulation in germinating beans, hence it could be employed to enhance the functional quality of germinating common beans.

17.
Front Endocrinol (Lausanne) ; 13: 893238, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36147561

RESUMO

Hypothalamus-pituitary-adrenal (HPA) axis plays critical roles in stress responses under challenging conditions such as hypoxia, via regulating gene expression and integrating activities of hypothalamus-pituitary-targets cells. However, the transcriptional regulatory mechanisms and signaling pathways of hypoxic stress in the pituitary remain to be defined. Here, we report that hypoxia induced dynamic changes in the transcription factors, hormones, and their receptors in the adult rat pituitary. Hypoxia-inducible factors (HIFs), oxidative phosphorylation, and cAMP signaling pathways were all differentially enriched in genes induced by hypoxic stress. In the pituitary gene network, hypoxia activated c-Fos and HIFs with specific pituitary transcription factors (Prop1), targeting the promoters of hormones and their receptors. HIF and its related signaling pathways can be a promising biomarker during acute or constant hypoxia. Hypoxia stimulated the transcription of marker genes for microglia, chemokines, and cytokine receptors of the inflammatory response. Corticotropin-releasing hormone receptor 1 (CRHR1) mediated the transcription of Pomc, Sstr2, and Hif2a, and regulated the function of HPA axis. Together with HIF, c-Fos initiated and modulated dynamic changes in the transcription of hormones and their receptors. The receptors were also implicated in the regulation of functions of target cells in the pituitary network under hypoxic stress. CRHR1 played an integrative role in the hypothalamus-pituitary-target axes. This study provides new evidence for CRHR1 involved changes of hormones, receptors, signaling molecules and pathways in the pituitary induced by hypoxia.


Assuntos
Sistema Hipotálamo-Hipofisário , Receptores de Hormônio Liberador da Corticotropina , Animais , Hormônios/metabolismo , Sistema Hipotálamo-Hipofisário/metabolismo , Hipóxia/genética , Hipóxia/metabolismo , Sistema Hipófise-Suprarrenal/metabolismo , Pró-Opiomelanocortina/genética , RNA Mensageiro/genética , Ratos , Receptores de Hormônio Liberador da Corticotropina/genética , Receptores de Hormônio Liberador da Corticotropina/metabolismo , Receptores de Citocinas/metabolismo , Fatores de Transcrição/metabolismo
18.
J Am Chem Soc ; 144(32): 14790-14797, 2022 08 17.
Artigo em Inglês | MEDLINE | ID: mdl-35921549

RESUMO

There are few enantioconvergent reactions in which racemic substrates bearing multiple stereochemical features are converted into products with high levels of diastereo- and enantiocontrol. Here, we disclose a process for the highly enantio- and diastereoselective syntheses of medium ring lactams via an intramolecular counterion-directed C-alkylation reaction. The treatment of racemic biaryl anilides that exist as a complex mixture of enantiomers and diastereoisomeric conformers by virtue of multiple axes of restricted rotation with a quinidine-derived ammonium salt under basic conditions affords medium ring lactams bearing elements of both axial and point chirality via an enolate-driven configurational relaxation process. Thermal equilibration of the syn- and anti-product diasteroisomers has demonstrated that the barriers to bowl inversion are >124 kJ mol-1. We propose that the chiral ammonium salt differentiates between a complex and rapidly equilibrating mixture of enolate and rotational isomers, ultimately leading to highly enantioselective alkylative ring closure. This dynamic and enantioconvergent process offers an operationally simple approach to the synthesis of valuable chiral medium ring lactams for which there are few catalytic and enantioselective approaches.


Assuntos
Compostos de Amônio , Lactamas , Alquilação , Ácidos Carboxílicos , Catálise , Estereoisomerismo
19.
Front Oncol ; 12: 853815, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35912262

RESUMO

Purpose: The aim of this study is to evaluate the utility of magnetization transfer (MT) imaging in the study of normal uterus and common uterine lesions. Methods: This prospective study enrolled 160 consecutive patients with suspected uterine lesions. MT ratio (MTR) map was obtained by pelvic MT imaging on a 3.0T MRI scanner. Patients confirmed by pathology were divided into microscopic lesion group and lesion group, according to whether the maximum diameter of the lesion was less than 5 mm. After evaluating and eliminating patients with poor image quality by a three-point Likert scale, MTR values of lesions and normal endometrium, myometrium, and cervix were independently measured on the MTR map by two radiologists. Inter-reader agreement was evaluated. MTR values were compared among different uterine lesions and normal uterine structures using the Mann-Whitney U test with Bonferroni correction. Receiver operating characteristic curve was performed. The correlations between age and MTR values were explored by Pearson correlation analyses. Results: A total of 96 patients with 121 uterine lesions in the lesion group and 41 patients in the microscopic lesion group were measured. The MTR values among normal endometrium, myometrium, and cervix were statistical significant differences (P < 0.05). There were significant differences between endometrial cancer and normal endometrium and between cervical cancer and normal cervix (both P ≤ 0.001). Area under the curve (AUC) for diagnosing endometrial and cervical cancer were 0.73 and 0.86. Myometrial lesions had significantly higher MTR values than endometrial lesions and cervical cancer (both P < 0.001), and the AUC for differentiating myometrial lesions from them were 0.89 and 0.94. MTR values of endometrial cancer were significantly higher than those of cervical cancer (P = 0.02). There was a critical correlation between age and MTR values in endometrial cancer (r = 0.81, P = 0.04). Conclusions: MTR values showed significant differences among normal uterine structures. It was valuable for diagnosing and differentiating uterine cancer. MTR values could differentiate myometrial lesions from endometrial or cervical lesions.

20.
Inorg Chem ; 61(23): 8662-8669, 2022 Jun 13.
Artigo em Inglês | MEDLINE | ID: mdl-35617168

RESUMO

Cluster-based framework metal iodides have diverse structures and excellent luminescence properties, and show promising applications in sensing and solid-state lighting. However, the design and synthesis of these materials remain great challenges because excess I- ions introduced into the synthesis systems decrease the condensation degree of M-I units. In this work, a new strategy is developed to control the condensation behavior of Ag-I units, and a new silver-rich cluster-based framework iodide [DabcoAg8I6(SPh)2]n (1) (Dabco = 1,4-diazabicyclo [2.2.2] octane) has been synthesized under solvothermal conditions in the presence of silver thiophenolate (AgSPh)n. Compound 1 features a three-dimensional (3-D) cluster-based framework with a pillared layer structure composed of cationic [Ag8I6]2+ clusters bridged by SPh- and Dabco, and displays low-temperature dual emission and luminescence thermochromism.

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