RESUMO
Electrocarboxylation of organic halides is one of the most investigated electrochemical approaches for converting thermodynamically inert carbon dioxide (CO2) into value-added carboxylic acids. By converting organic halides into their sulfone derivatives, we have developed a highly efficient electrochemical desulfonylative carboxylation protocol. Such a strategy takes advantage of CO2 as the abundant C1 building block for the facile preparation of multifunctionalized carboxylic acids, including the nonsteroidal anti-inflammatory drug ibuprofen, under mild reaction conditions.
Assuntos
Dióxido de Carbono , Ácidos CarboxílicosRESUMO
The in situ construction of the nanoassembly has been demonstrated to improve the performance of bioactive molecules, but the control of the morphology of nanomaterials in vivo still remains a tremendous challenge. Herein, a photothermal-promoted morphology transformation (PMT) strategy is developed to accelerate the formation of nanomaterials for improving the biological performance of drug molecules. Compared with the spontaneous process, the rate of transformation increases by â¼4 times in the PMT process. Owing to increased assembly rate, the tumor accumulation of drugs is â¼2-fold than that without photo irradiation, which inhibits tumor growth effectively. More importantly, the chemical reassembly process in vitro and in vivo is monitored by the advanced ratiometric photoacoustic image, confirming the photoinduced transformation acceleration. Through the noninvasively artificial control on assembly dynamics in vivo, the PMT strategy provides a new insight for developing the intelligent theranostics.
Assuntos
Antineoplásicos/farmacologia , Diagnóstico por Imagem/métodos , Neoplasias/tratamento farmacológico , Técnicas Fotoacústicas/métodos , Antineoplásicos/química , Linhagem Celular Tumoral , Humanos , Nanoestruturas/química , Fotoquimioterapia , Nanomedicina Teranóstica/tendênciasRESUMO
Self-assembly is an important strategy for constructing ordered structures and complex functions in nature. Based on this, people can imitate nature and artificially construct functional materials with novel structures through the supermolecular self-assembly pathway of biological interfaces. Among the many assembly units, peptide molecular self-assembly has received widespread attention in recent years. In this review, we introduce the interactions (hydrophobic interaction, hydrogen bond, and electrostatic interaction) between peptide nanomaterials and biological interfaces, summarizing the latest advancements in multifunctional self-assembling peptide materials. We systematically demonstrate the assembly mechanisms of peptides at biological interfaces, such as proteins and cell membranes, while highlighting their application potential and challenges in fields like drug delivery, antibacterial strategies, and cancer therapy.
Assuntos
Nanoestruturas , Peptídeos , Humanos , Peptídeos/química , Nanoestruturas/química , Sistemas de Liberação de MedicamentosRESUMO
OBJECTIVE: The objective of this study is to explore the patterns of alteration in left ventricular systolic function among patients with severe aortic stenosis (SAS) through the application of automatic myocardial motion quantification (aCMQ) techniques. Furthermore, we seek to ascertain dependable quantitative markers for the assessment of impaired left ventricular function in patients with SAS and an ejection fraction (EF) ≥ 60%. METHODS: Seventy patients who underwent echocardiography and received a diagnosis of severe aortic stenosis (SAS) in the hospital from November 2021 to August 2022 were selected for the SAS group and categorized into three subgroups based on ejection fraction (EF)-SAS group with EF ≥ 60%, SAS group with EF ranging from 50% to 59%, and SAS group with EF < 50%. Concurrently, 30 healthy individuals were recruited at the hospital during the same timeframe to serve as the control group. Participants from both groups underwent standard transthoracic echocardiography to assess conventional echocardiographic parameters. Dynamic images were examined using automatic myocardial motion quantification (aCMQ) software to derive longitudinal peak strain (LPS) parameters, which were then subjected to statistical analysis. RESULTS: In comparison to the control group participants, the measurements of ascending aorta diameter (AoD), left atrium diameter (LAD), interventricular septal end diastolic thickness (IVSd), left ventricular posterior wall end diastolic thickness (LVPWd), peak systolic velocity (Vmax), and mean pressure gradient (MPG) were significantly higher in the SAS groups (p < 0.05). When compared to participants in the SAS group with an EF ≥ 60%, the values of IVSd, LVPWd, Vmax, and MPG in the SAS group with EF ranging from 50% to 59% were significantly elevated (p < 0.05). Similarly, left ventricular end-diastolic diameter (LVEDD), the ratio of early diastolic mitral inflow velocity to early diastolic mitral annular velocity (E/e'), and the ratio of early to late diastolic mitral inflow velocities (E/A) in the SAS group with EF < 50% were significantly elevated (p < 0.05). The absolute values of longitudinal peak strain (LPS) in the SAS groups were significantly lower in comparison to those in the control group (p < 0.05). Furthermore, all measurements of left ventricular global longitudinal systolic peak strain (GLPS) showed a positive correlation with MPG, a moderate negative correlation with aortic valve area index (AVAI), and a moderate positive correlation with E/A. CONCLUSIONS: Patients with SAS and an EF < 50% exhibited the most profound impairment in left ventricular myocardial function. Utilizing the aCMQ technique enables the precise and quantitative evaluation of the severity of impaired left ventricular systolic function in patients within the SAS group with an EF ≥ 60%.
Assuntos
Estenose da Valva Aórtica , Ecocardiografia , Função Ventricular Esquerda , Humanos , Estenose da Valva Aórtica/diagnóstico por imagem , Estenose da Valva Aórtica/fisiopatologia , Masculino , Feminino , Idoso , Ecocardiografia/métodos , Pessoa de Meia-Idade , Função Ventricular Esquerda/fisiologia , Disfunção Ventricular Esquerda/diagnóstico por imagem , Disfunção Ventricular Esquerda/fisiopatologia , Índice de Gravidade de DoençaRESUMO
Background: Aortic arch atresia is a rare congenital cardiac defect that may occur after birth. Pregnant women with gestational diabetes mellitus may increase the risk of aortic arch atresia in newborns after birth. Case Description: A 16-day-old infant was referred to our hospital on the 15th postnatal day after an interrupted or atretic aortic arch was discovered. No obvious abnormality was detected in the infant during the prenatal ultrasound. Laboratory tests showed elevated inflammatory marker levels. Transthoracic echocardiography showed stenosis of the transverse arch of the aorta and a blind end at the distal end of the left subclavian artery. During surgery, it was found that the isthmus of the aorta was uninterrupted but completely occluded due to inflammation. Conclusion: This case demonstrates that type A interrupted aortic arch and coarctation of the aorta can be acquired after birth, and if coarctation of the aorta is complicated by inflammation or if the pregnant women have gestational diabetes mellitus, it can result in aortic arch atresia as the patient's condition worsens. It is advised to consider aortic arch atresia when imaging reveals type A interrupted aortic arch.
RESUMO
Mycotic pseudoaneurysm of the ascending aorta is extremely uncommon, particularly in children with no prior cardiac surgery or trauma. We report a rare case of a mycotic pseudoaneurysm of the ascending aorta in a 2-year-old girl with no history of cardiac surgery. Investigations revealed a methicillin-resistant Staphylococcus aureus infection and significant pericardial effusion in the child who presented with persistent fever and altered mental state. Cardiac ultrasound revealed a disruption in the aortic wall and a tumor-like structure. Contrast-enhanced computed tomography confirmed an ascending aortic pseudoaneurysm with thrombus. The child underwent successful surgical treatment without implants. This case emphasizes the diagnostic significance of imaging, particularly the advantages of ultrasound in pediatric settings, and the need for timely and accurate diagnosis using appropriate imaging modalities in children.
RESUMO
Over the last few years, an increasing number of protein mis-localization events have been reported under various conditions. It is important to understand these events and their relationship with complex disorders. Although many efforts had been made in establishing models with statistical or machine learning algorithms, a comprehensive database resource is still missing. Since the records of experimental-validated protein mis-localization events spread across many literatures, a collection of all these reports in a unique website is demanded. In this paper, we created the dbMisLoc database by manually curating conditional protein mis-localization events from various literatures. The dbMisLoc database records the protein localizations, mis-localizations, conditions for mis-localization, and the original reports. The dbMisLoc database allows the users to intuitively view, search, visualize and download protein mis-localization records. The dbMisLoc database integrates a BLAST search engine, which can search mis-localized proteins that are similar to user queries. The dbMisLoc database can be accessed directly through ( https://dbml.pufengdu.org ). The source code of dbMisLoc database is available from the GitHub repository ( https://github.com/quinlanW/dbMisLoc ) for free. Users can host their own mirrors of dbMisLoc database on their own servers. dbMisLoc is database for manually curated protein mis-localization events. It contains mis-localization events in 14 categories of conditions such as diseases, drug treatments and environmental stresses.
Assuntos
Proteínas , Software , Proteínas/metabolismo , Algoritmos , Bases de Dados Factuais , Aprendizado de MáquinaRESUMO
Chemodynamic therapy (CDT) is an emerging targeted treatment technique for tumors via the generation of highly cytotoxic hydroxyl radical (·OH) governed by tumor microenvironment-assisted Fenton reaction. Despite high effectiveness, it faces limitations like low reaction efficiency and limited endogenous H2 O2 , compromising its therapeutic efficacy. This study reports a novel platform with enhanced CDT performance by in situ sono-activated cascade Fenton reaction. A piezoelectric g-C3 N4 (Au-Fe-g-C3 N4 ) nanosheet is developed via sono-activated synergistic effect/H2 O2 self-supply mediated cascade Fenton reaction, realizing in situ ultrasound activated cascade Fenton reaction kinetics by synergistic modulation of electron-hole separation. The nanosheets consist of piezoelectric g-C3 N4 nanosheet oxidizing H2 O to highly reactive H2 O2 from the valence band, Fe3+ /Fe2+ cycling activated by conduction band to generate ·OH, and Au nanoparticles that lower the bandgap and further adopt electrons to generate more 1 O2 , resulting in improved CDT and sonodynamic therapy (SDT). Moreover, the Au-Fe-g-C3 N4 nanosheet is further modified by the targeted peptide to obtain P-Au-Fe-g-C3 N4 , which inhibits tumor growth in vivo effectively by generating reactive oxygen species (ROS). These results demonstrated that the sono-activated modulation translates into a high-efficiency CDT with a synergistic effect using SDT for improved anti-tumor therapy.
Assuntos
Nanopartículas Metálicas , Nanopartículas , Neoplasias , Humanos , Elétrons , Ouro/farmacologia , Cinética , Espécies Reativas de Oxigênio , Microambiente Tumoral , Linhagem Celular Tumoral , Neoplasias/tratamento farmacológico , Peróxido de HidrogênioRESUMO
In this paper, we reported the realization of 2nd-order random lasing in a half-opened fiber cavity, which is formed by a FBG with central wavelength at the 1st-order Raman Stokes wavelength and a single-mode fiber (SMF) performing as a random distributed feedback mirror. Using this proposed method, the threshold of 1st-order (2nd-order) random lasing is reduced to 0.7 (2.0) W, which is nearly 2 times lower than that observed in a completely-opened cavity.
Assuntos
Tecnologia de Fibra Óptica/instrumentação , Lasers , Lentes , Análise Espectral Raman/instrumentação , Desenho de Equipamento , Análise de Falha de EquipamentoRESUMO
Three new compounds, 4-hydroxyphenethyl-2'-hydroxypropanoate (1), 6-(1',2'-dimethyloxiran-1'-yl)-4-methoxy-3-methyl-2H-pyran-2-one (2), 6-(1-hydroxyethyl)-4-methoxy-3-methyl-2H-pyran-2-one (3), along with the two known compounds, nectriapyrone (4) and wermopyrone (5), have been isolated from the endophytic fungus of Cephalotaxus hainanensis. Their structures were determined on the basis of chemical and spectroscopic methods.
Assuntos
Fungos/química , Propionatos/isolamento & purificação , Pironas/isolamento & purificação , Cephalotaxus/microbiologia , China , Estrutura Molecular , Ressonância Magnética Nuclear Biomolecular , Propionatos/química , Pironas/químicaRESUMO
A couple of analogues of azobenzenyl beta-cyclodextrins 1 and 2 with self-locked and self-unlocked conformations have been synthesized via the Huisgen cycloaddition from the same reactants, but in distinct reaction conditions (i.e., the hydrothermal synthesis and the "click" reaction, respectively), their conformations were sufficiently proved by X-ray crystal structural analysis, molecular modeling study, and 2D NMR spectroscopy, and their self-assembly behaviors in aqueous solution were also investigated by NMR spectroscopy. Interestingly, the self-locked conformer 1, which could be regarded as a new type of [1]rotaxane, self-assembled to a novel bimolecular capsule, where its azobenzene substituent was included in both its own cavity and the counterpart's cavity, in aqueous solution and in the solid state. In contrast, by adjusting the conformation of 1 to a self-unlocked one, the resulting conformer 2 was found to self-assemble to a linear supramolecule. These studies have shown the stronger impact of the reaction condition changing in cyclodextrin's modification products and will provide a new access to control the structure of supramolecular assemblies by tuning the conformation of building blocks.
RESUMO
The inclusion complexation behavior and the solubilization effects of Bisphenol A (BPA, an endocrine-disrupting chemical) by cyclomaltohexaose, -heptaose, and -octaose (alpha-, beta-, and gamma-cyclodextrins) were investigated by (1)H NMR spectroscopy and by elemental analysis. The results showed that beta- and gamma-cyclodextrins gave the satisfactory solubilization ability to BPA up to 7.2 x 10(3) mg L(-1) and 9.0 x 10(3) mg L(-1), respectively. X-ray crystallographic diffraction and ROESY spectroscopy were also employed to investigate the structure of the beta-CD/BPA inclusion complex in both aqueous solution and the solid state. The result showed that this complex adopted a 2:2 stoichiometry in the solid state, that is, a head-to-head beta-CD dimer accommodated two BPA molecules. The inclusion of BPA led to the desolvation of the beta-CD cavity and the destruction of the circularly closed hydrogen-bond network in the secondary side of beta-CD, which made the complex more soluble.
Assuntos
Fenóis/química , beta-Ciclodextrinas/química , Compostos Benzidrílicos , Configuração de Carboidratos , Espectroscopia de Ressonância Magnética , Modelos Moleculares , Solubilidade , Água/químicaRESUMO
A series of beta-cyclodextrin (beta-CD) dimers with 4,4'-diselenobis(benzoyl) linkers, that is, 6,6'-[4,4'-diselenobis(benzoyloxyl)]-bridged bis(beta-CD) (1a), 6,6'-[4,4'-diselenobis[2-(benzoylamino)ethyleneamino]]-bridged bis(beta-CD) (2a), and 6,6'-[4,4'-diselenobis[2-(benzoylamino)-3,6-diazaoctylamino]]-bridged bis(beta-CD) (3a), were synthesized in moderate yields by the reaction of 4,4'-diselenobis(benzoic acid) with beta-CD or oligo(ethylenediamino)-6-deoxy-beta-CD. Their binding behaviors with some structure-related substrates, such as acridine red (AR), neutral red (NR), rhodamine B (RhB), ammonium 8-anilino-1-naphthalenesulfonate (ANS), and 6-p-toluidino-2-naphthalenesulfonic acid (TNS), were investigated in aqueous phosphate buffer solution (pH 7.20) at 298.15 K by means of fluorescence, NMR, as well as circular dichroism spectroscopy and compared with those of their 2,2'-diselenobis(benzoyl)-linked analogues, that is, 6,6'-[2,2'-diselenobis(benzoyloxyl)]-bridged bis(beta-CD) (1b), 6,6'-[2,3'-diselenobis[2-(benzoylamino)ethyleneamino]]-bridged bis(beta-CD) (2b), and 6,6'-[2,2'-diselenobis[2-(benzoylamino)-3,6-diazaoctylamino]]-bridged bis(beta-CD) (3b). The results showed that bis(beta-CD)s 1a-3a, whose Se-Se bonds were located at the para position of the carboxyl group, gave stronger binding abilities toward nonlinear guests (RhB and ANS) than their analogues 1b-3b, whose Se-Se bonds were located at the ortho position relative to the carboxyl group. The molecular binding ability and selectivity of model substrates by these ditopic hosts were sufficiently discussed to reveal not only the cooperative contributions of the linker group and CD cavities upon inclusion complexation with dye guest molecules but also the controlling factors for the molecular selective binding.
RESUMO
The preorganized bis(polypseudorotaxane) (approximately 20 nm long) formed by the multiple metallo-bridged poly(beta-cyclodextrin)s has been successfully converted to the lengthened bis(molecular tube) (approximately 200 nm long) through the intermolecular joining of approximately 10 discrete bis(polypseudorotaxane) units and the subsequent removal of the polymer templates. The obtained bis(molecular tube), which is quite soluble in water, dimethylformamide, and dimethyl sulfoxide, has been comprehensively characterized by NMR, gel permeation chromatography, static light scattering, X-ray powder diffraction, thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy, and scanning tunneling microscopy. Further investigations demonstrate that this bis(molecular tube) can capture C(60) through interaction with its many pi-electron-rich biquinolino groups.