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1.
Appl Microbiol Biotechnol ; 108(1): 328, 2024 May 08.
Artigo em Inglês | MEDLINE | ID: mdl-38717672

RESUMO

Pseudogenes are defined as "non-functional" copies of corresponding parent genes. The cognition of pseudogenes continues to be refreshed through accumulating and updating research findings. Previous studies have predominantly focused on mammals, but pseudogenes have received relatively less attention in the field of microbiology. Given the increasing recognition on the importance of pseudogenes, in this review, we focus on several aspects of microorganism pseudogenes, including their classification and characteristics, their generation and fate, their identification, their abundance and distribution, their impact on virulence, their ability to recombine with functional genes, the extent to which some pseudogenes are transcribed and translated, and the relationship between pseudogenes and viruses. By summarizing and organizing the latest research progress, this review will provide a comprehensive perspective and improved understanding on pseudogenes in microorganisms. KEY POINTS: • Concept, classification and characteristics, identification and databases, content, and distribution of microbial pseudogenes are presented. • How pseudogenization contribute to pathogen virulence is highlighted. • Pseudogenes with potential functions in microorganisms are discussed.


Assuntos
Bactérias , Pseudogenes , Pseudogenes/genética , Bactérias/genética , Bactérias/classificação , Virulência/genética , Vírus/genética , Vírus/classificação
2.
Nat Commun ; 14(1): 7179, 2023 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-37935714

RESUMO

Circularly polarized light (CPL) adds a unique dimension to optical information processing and communication. Integrating CPL sensitivity with light learning and memory in a photonic artificial synapse (PAS) device holds significant value for advanced neuromorphic vision systems. However, the development of such systems has been impeded by the scarcity of suitable CPL active optoelectronic materials. In this work, we employ a helical chiral perovskite hybrid combined with single-wall carbon nanotubes to achieve circularly polarized ultraviolet neuromorphic vision sensing and imaging. The heterostructure demonstrates long-term charge storage as evidenced by multiple-pulsed transient absorption measurements and highly sensitive circular polarization-dependent photodetection, thereby enabling efficient CPL-resolved synaptic and neuromorphic behaviors. Significantly, our PAS sensor arrays adeptly visualize, discriminate, and memorize distinct circularly polarized images with up to 93% recognition accuracy in spiking neural network simulations. These findings underscore the pivotal role of chiral perovskites in advancing PAS technology and circular polarization-enhanced ultraviolet neuromorphic vision systems.

3.
Nano Lett ; 23(12): 5705-5712, 2023 Jun 28.
Artigo em Inglês | MEDLINE | ID: mdl-37285458

RESUMO

Color-tunable electroluminescence (EL) from a single emitting material can be used to develop single-pixel multicolor displays. However, finding materials capable of broad EL color tuning remains challenging. Herein, we report the observation of broad voltage-tunable EL in colloidal type-II InP/ZnS quantum-dot-seeded CdS tetrapod (TP) LEDs. The EL color can be tuned from red to bluish white by varying the red and blue emission intensities from type-II interfaces and arms, respectively. The capacitor device proves that an external electric field can enhance the color tuning in type-II TPs. COMSOL simulations, numerical calculations, and transient absorption measurements are performed to understand the underlying photophysical mechanism. Our results indicate that the reduced hole relaxation rate from the arm to the quantum dot core can enhance the emission from the CdS arms, which is favorable for EL color tuning. This study provides a novel method to realize voltage-tunable EL colors with potential in display and micro-optoelectronic applications.

4.
Front Cell Infect Microbiol ; 13: 1146394, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-36936761

RESUMO

Pestiviruses are a class of viruses that in some cases can cause persistent infection of the host, thus posing a threat to the livestock industry. Interferons (IFNs) are a group of secreted proteins that play a crucial role in antiviral defense. In this review, on the one hand, we elaborate on how pestiviruses are recognized by the host retinoic acid-inducible gene-I (RIG-I), melanoma-differentiation-associated protein 5 (MDA5), and Toll-like receptor 3 (TLR3) proteins to induce the synthesis of IFNs. On the other hand, we focus on reviewing how pestiviruses antagonize the production of IFNs utilizing various strategies mediated by self-encoded proteins, such as the structural envelope protein (Erns) and non-structural protein (Npro). Hence, the IFN signal transduction pathway induced by pestiviruses infection and the process of pestiviruses blockade on the production of IFNs intertwines into an intricate regulatory network. By reviewing the interaction between IFN and pestiviruses (based on studies on BVDV and CSFV), we expect to provide a theoretical basis and reference for a better understanding of the mechanisms of induction and evasion of the innate immune response during infection with these viruses.


Assuntos
Pestivirus , Vírus , Interferons , Imunidade Inata , Antivirais , Pestivirus/metabolismo
5.
Molecules ; 28(3)2023 Jan 30.
Artigo em Inglês | MEDLINE | ID: mdl-36770988

RESUMO

The photosynthetic tetrapyrroles share a common structural feature comprised of a ß-ketoester motif embedded in an exocyclic ring (ring E). As part of a total synthesis program aimed at preparing native structures and analogues, 3-(3-methoxy-1,3-dioxopropyl)pyrrole was sought. The pyrrole is a precursor to analogues of ring C and the external framework of ring E. Four routes were developed. Routes 1-3 entail a Pd-mediated coupling process of a 3-iodopyrrole with potassium methyl malonate, whereas route 4 relies on electrophilic substitution of TIPS-pyrrole with methyl malonyl chloride. Together, the four routes afford considerable latitude. A long-term objective is to gain the capacity to create chlorophylls and bacteriochlorophylls and analogues thereof by facile de novo means for diverse studies across the photosynthetic sciences.


Assuntos
Pirróis , Tetrapirróis , Pirróis/química , Clorofila/química , Bacterioclorofilas/química , Fotossíntese
6.
Adv Synth Catal ; 365(14): 2361-2366, 2023 Jul 18.
Artigo em Inglês | MEDLINE | ID: mdl-38464363

RESUMO

A mild photocatalyzed approach to achieve the α-alkylation of esters via formation of an α -radical is disclosed here. Cesium enolates of esters were generated in situ using Cs2CO3 as a base. A subsequent photocatalyzed oxidation at the α-carbon of these enolates produced an α-radical that was added into activated alkenes. This is the first example accessing the α-carbon radical of esters in photoredox catalyed transformations.

7.
IEEE Trans Image Process ; 31: 5989-6001, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36099213

RESUMO

Recent deep learning based salient object detection methods with attention mechanisms have made great success. However, existing attention mechanisms can be generally separated into two categories. One part chooses to calculate weights indiscriminately, which yields computational redundancy. While one part focuses randomly on a small part of the images, such as hard attention, resulting in incorrectness owing to insufficiently targeted selection of a subset of tokens. To alleviate these problems, we design a Curiosity-driven Network (CNet) and a Curiosity-driven Learning Algorithm (CLA) based on fragment attention (FA) mechanism newly defined in this paper. FA imitates the process of cognition perception driven by human curiosity, and divides the degree of curiosity into three levels, i.e. curious, a little curious and not curious. These three levels correspond to five saliency degrees, including salient and non-salient, likewise salient and likewise non-salient, completely uncertain. With more knowledge gained by the network, CLA transforms the curiosity degree of each pixel to yield enhanced detail-enriched saliency maps. In order to extract more context-aware information of potential salient objects and make a better foundation for CLA, a high-level feature extraction module (HFEM) is further proposed. Based on the much better high-level features extracted by HFEM, FA can classify the curiosity degree for each pixel more reasonably and accurately. Extensive experiments on five popular datasets clearly demonstrate that our method outperforms the state-of-the-art approaches without any pre-processing operations or post-processing operations.


Assuntos
Algoritmos , Comportamento Exploratório , Cognição , Humanos
8.
Inorg Chem ; 61(31): 12308-12317, 2022 Aug 08.
Artigo em Inglês | MEDLINE | ID: mdl-35892197

RESUMO

The monoanionic tetrapyrrolic macrocycle B,C-tetradehydrocorrin (TDC) resides chemically between corroles and corrins. This chemical space remains largely unexplored due to a lack of reliable synthetic strategies. We now report the preparation and characterization of Co(II)- and Ni(II)-metalated TDC derivatives ([Co-TDC]+ and [Ni-TDC]+, respectively) with a combination of crystallographic, electrochemical, computational, and spectroscopic techniques. [Ni-TDC]+ was found to undergo primarily ligand-centered electrochemical reduction, leading to hydrogenation of the macrocycle under cathodic electrolysis in the presence of acid. Transient absorption (TA) spectroscopy reveals that [Ni-TDC]+ and the two-electron-reduced [Ni-TDC]- possess long-lived excited states, whereas the excited state of singly reduced [Ni-TDC] exhibits picosecond dynamics. The Co(I) compound [Co-TDC] is air stable, highlighting the notable property of the TDC ligand to stabilize low-valent metal centers in contradistinction to other tetrapyrroles such as corroles, which typically stabilize metals in higher oxidation states.

9.
Adv Synth Catal ; 364(3): 518-524, 2022 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-35431717

RESUMO

N-heterocyclic carbenes (NHCs) have emerged as catalysts for the construction of C-C bonds in the synthesis of substituted ketones under single-electron processes. Despite these recent reports, there still remains a need to increase the utility and practicality of these reactions by exploring new radical coupling partners. Herein, we report the synthesis of γ-aryloxyketones via combined NHC/photoredox catalysis. In this reaction, an α-aryloxymethyl radical is generated via oxidation of an aryloxymethyl potassium trifluoroborate salt, which is then added into styrene derivatives to provide a stabilized benzylic radical. Subsequent radical-radical coupling reaction with an azolium radical affords the γ-aryloxy ketone products.

10.
ACS Appl Mater Interfaces ; 13(48): 57822-57830, 2021 Dec 08.
Artigo em Inglês | MEDLINE | ID: mdl-34797636

RESUMO

Interlayer charge transfer (CT) between PtSe2 and WS2 is studied experimentally. Layer-selective pump-probe and photoluminescence quenching measurements reveal ultrafast interlayer CT in the heterostructure formed by bilayer PtSe2 and monolayer WS2, confirming its type-II band alignment. The CT facilitates the formation of the interlayer excitons with a lifetime of several hundred ps to 1 ns, a diffusion coefficient of 0.9 cm2 s-1, and a diffusion length reaching 200 nm. These results demonstrate the integration of PtSe2 with other materials in van der Waals heterostructures with novel charge-transfer properties and help develop fundamental understanding on the performance of various optoelectronic devices based on heterostructures involving PtSe2.

11.
J Org Chem ; 86(17): 11794-11811, 2021 09 03.
Artigo em Inglês | MEDLINE | ID: mdl-34347485

RESUMO

Native chlorophylls and bacteriochlorophylls share a common trans-substituted pyrroline ring D (17-propionic acid, 18-methyl), whereas diversity occurs in ring A particularly at the 3-position. Two dihydrodipyrrins equipped with native-like D-ring substituents and tailorable A-ring substituents have been synthesized. The synthesis relies on a Schreiber-modified Nicholas reaction to construct the stereochemically defined precursor to ring D, a dialkyl-substituted pent-4-ynoic acid. The carboxylic acid group of the intact propionic acid proved unworkable, whereupon protected propionate (-CO2tBu) and several latent propyl ethers were examined. The tert-butyldiphenylsilyl-protected propanol substituent proved satisfactory for reaction of the chiral N-acylated oxazolidinone, affording (2S,3S)-2-(3-((tert-butyldiphenylsilyl)oxy)propyl)-3-methylpent-4-ynoic acid in ∼30% yield over 8 steps. Two variants for ring A, 2-tert-butoxycarbonyl-3-Br/H-5-iodo-4-methylpyrrole, were prepared via the Barton-Zard route. Dihydrodipyrrin formation from the pyrrole and pentynoic acid entailed Jacobi Pd-mediated lactone formation, Petasis methenylation, and Paal-Knorr-type pyrroline formation. The two AD-dihydrodipyrrins bear the D-ring methyl and protected propanol groups with a stereochemical configuration identical to that of native (bacterio)chlorophylls, and a bromine or no substitution in ring A corresponding to the 3-position of (bacterio)chlorophylls. The analogous ß-position of a lactone-pyrrole intermediate on the path to the dihydrodipyrrin also was successfully brominated, opening opportunities for late-stage diversification in the synthesis of (bacterio)chlorophylls.


Assuntos
Bacterioclorofilas , Porfirinas
12.
Sichuan Da Xue Xue Bao Yi Xue Ban ; 52(3): 452-457, 2021 05.
Artigo em Chinês | MEDLINE | ID: mdl-34018364

RESUMO

Objective: To investigate the difference in the expression of Ras-associated protein 1 (Rap1) in necrotic and healthy areas of non-traumatic osteonecrosis of femoral head (NONFH) patients. Methods: Femoral head tissue samples from 30 cases of NONFH and 30 cases of traumatic osteonecrosis of the femoral head (TONFH) were collected after hip replacement surgery, respectively. No significant difference of Association Research Circulation Osseous (ARCO) staging was found between the NONFH and the TONFH groups ( Z=-0.769, P=0.442). In the NONFH group, 8 patients were ARCO stage IIIb, 10 were stage IV, and 12 were stage V, while in the TONFH ground, 11 patients were ARCO stage IIIb, 9 were stage IV, and 10 were stage V. There were 19 males and 11 females in the NONFH group, with an average age of 49.6 yr. (26-69 yr.), and 16 males and 14 females in the TONFH group, with an average age of 54.2 yr. (37-68 yr.). There was no significant difference in gender or age between the two groups ( P>0.05). Specimens were collected from different bone areas, including those from the necrotic areas (area A) and the healthy areas (area B) of the NONFH group, and those from the healthy areas (area B') of the TONFH group, i.e., the control group. Western blot and quantitative real-time reverse transcription PCR (qRT-PCR) were used to analyze the different expression of Rap1, vascular endothelial growth factor (VEGF) protein, phosphoinositide 3-kinase (PI3K), and Akt protein and their corresponding mRNA in the three areas of bone tissue. HE staining and immunohistochemisty staining were done in order to observe the morphological changes of each area. Results: Western blot results indicated that there was no statistical difference in the relative expression of Rap1, VEGF, PI3K, and Akt proteins ( P>0.05). The relative expressions of Rap1, VEGF, PI3K, and Akt proteins in the area A were lower than those in the area B and the difference was statistically significant ( P<0.05). qRT-PCR results showed that the relative expressions of Rap1, VEGF, PI3 K and Akt mRNA in area A were lower than those of area B, and a statistical difference was found ( P<0.05). The relative expression of the mRNA of Rap1, VEGF , PI3 K and Akt in area B and area B' were not significantly different ( P>0.05). HE staining and immunohistochemisty staining showed that chondrocytes decreased in the necrotic area (area A) of NONFH, chondrocytes nucleus disappeared, subchondral bone trabeculae were broken, bone trabeculae thickened, and empty bone lacunae appeared. Granulation tissues composed of new capillaries and fibrous cells have proliferated and crawled around the necrotic area. Positive expressions of the Rap1, VEGF, PI3K and Akt proteins in area A were weaker than those of the normal area. In addition, there were positive expressions of Rap1, PI3K and Akt on the trabecular bone of both area A and area B at similar intensity of expression. There were strong positive expressions of Rap1, VEGF, PI3K and Akt on the intima of arterioles and venules, and on the peripheral stromal cell membrane, but the positive expression in area A was significantly lower than that in area B. However, the positive expression positions and intensity of all indicators were similar in area B and area B'. Conclusion: The necrosis in NONFH may be related to vascular endothelial damages caused by the inhibition of the Rap1-PI3K/Akt signaling pathways and the subsequent decline in the protein expression.


Assuntos
Necrose da Cabeça do Fêmur , Cabeça do Fêmur , Adulto , Idoso , Endotélio Vascular , Feminino , Necrose da Cabeça do Fêmur/genética , Humanos , Masculino , Pessoa de Meia-Idade , Fosfatidilinositol 3-Quinases , Complexo Shelterina , Proteínas de Ligação a Telômeros , Fator A de Crescimento do Endotélio Vascular/genética
13.
Front Immunol ; 12: 603563, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-33603759

RESUMO

The high infection rate and rapid spread of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) make it a world-wide pandemic. Individuals infected by the virus exhibited different degrees of symptoms, and most convalescent individuals have been shown to develop both cellular and humoral immune responses. However, virus-specific adaptive immune responses in severe patients during acute phase have not been thoroughly studied. Here, we found that in a group of COVID-19 patients with acute respiratory distress syndrome (ARDS) during hospitalization, most of them mounted SARS-CoV-2-specific antibody responses, including neutralizing antibodies. However, compared to healthy controls, the percentages and absolute numbers of both NK cells and CD8+ T cells were significantly reduced, with decreased IFNγ expression in CD4+ T cells in peripheral blood from severe patients. Most notably, their peripheral blood lymphocytes failed in producing IFNγ against viral proteins. Thus, severe COVID-19 patients at acute infection stage developed SARS-CoV-2-specific antibody responses but were impaired in cellular immunity, which emphasizes on the role of cellular immunity in COVID-19.


Assuntos
Linfócitos T CD4-Positivos/imunologia , Linfócitos T CD8-Positivos/imunologia , COVID-19/imunologia , Células Matadoras Naturais/imunologia , Síndrome do Desconforto Respiratório/imunologia , SARS-CoV-2/imunologia , Anticorpos Neutralizantes/sangue , Anticorpos Antivirais/sangue , Contagem de Células , Células Cultivadas , Progressão da Doença , Feminino , Humanos , Imunidade Celular , Interferon gama/metabolismo , Masculino , Pessoa de Meia-Idade
14.
Appl Microbiol Biotechnol ; 105(3): 923-935, 2021 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-33427935

RESUMO

It is of great significance to establish sensitive and accurate pathogen detection methods, considering the continuous emergence or re-emergence of infectious diseases seriously influences the safety of human and animals. Proximity ligation assay (PLA) is developed for the sensitive protein detection and also can be used for the detection of pathogens. PLA employs aptamer or monoclonal/polyclonal antibody-nucleic acid complexes as proximity probes. When the paired proximity probes bind to the same target protein or protein complex, they will be adjacent to each other and form an amplifiable DNA sequence through ligation. Combining the specificity of enzyme-linked immunosorbent assay (ELISA) and sensitivity of polymerase chain reaction (PCR), PLA transforms the detection of protein into the detection of DNA nucleic acid sequence. Therefore, as an ultrasensitive protein assay, PLA has great potential for quantification, localization of protein, and clinical diagnostics. In this review, we summarize the basic principles of PLA and its applications in pathogen detection. KEY POINTS: • Different forms of proximity ligation assay are introduced. • Applications of proximity ligation assay in pathogen detection are summarized. • Proximity ligation assay is an ultrasensitive method to quantify protein and pathogen.


Assuntos
DNA , Oligonucleotídeos , Animais , Bioensaio , Ensaio de Imunoadsorção Enzimática , Humanos , Reação em Cadeia da Polimerase
15.
Appl Microbiol Biotechnol ; 104(22): 9719-9732, 2020 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-33009938

RESUMO

Salmonella spp. can cause animal and human salmonellosis. In this study, we established a simple method to detect all Salmonella species by amplifying a specific region within the flgE gene encoding the flagellar hook protein. Our preliminary sequence analysis among flagella-associated genes of Salmonella revealed that although Salmonella Gallinarum and Salmonella Pullorum are lacking flagella, they did have flagella-associated genes, including flgE. To investigate in detail, a comparative flgE sequence analysis was conducted using different bacterial strains including flagellated and non-flagellated Salmonella as well as non-Salmonella strains. Two unique regions (481-529 bp and 721-775 bp of the reference sequence) within the flgE open reading frame were found to be highly conserved and specific to all Salmonella species. Next, we designed a pair of PCR primers (flgE-UP and flgE-LO) targeting the above two regions, and performed a flgE-tailored PCR using as template DNA prepared from a total of 76 bacterial strains (31 flagellated Salmonella strains, 26 non-flagellated Salmonella strains, and 19 other non-Salmonella bacteria strains). Results showed that specific positive bands with expected size were obtained from all Salmonella (including flagellated and non-flagellated Salmonella) strains, while no specific product was generated from non-Salmonella bacterial strains. PCR products from the positive bands were confirmed by DNA sequencing. The minimum detection amount for genomic DNA and bacteria cells reached 18.3 pg/µL and 100 colony-forming unit (CFU) per PCR reaction, respectively. Using the flgE-PCR method to detect Salmonella in artificially contaminated milk samples, as low as 1 CFU/mL Salmonella was detectable after an 8-h pre-culture. Meanwhile, the flgE-tailored PCR method was applied to evaluate 247 clinical samples infected with Salmonella from different chicken breeding farms. The detection results indicated that flgE-PCR could be used to specifically detect Salmonella in concordance with the traditional bacterial culture-based detection method. It is worthwhile noticed that identification results using flgE-tailored PCR should be completed within less than 1 day, expanding the result of much faster than the standard method, which took more than 5 days. Overall, the flgE-tailored PCR method can specifically detect flagellated and non-flagellated Salmonella and can serve as a powerful tool for rapid, simple, and sensitive detection of Salmonella species. KEY POINTS : • Targeting flgE gene for all Salmonella spp. found. • The established PCR assay is used to specifically detect all Salmonella spp. • The PCR method is applied to detect clinical Salmonella spp. samples within less than 1 day.


Assuntos
Proteínas de Bactérias , Salmonella , Animais , Proteínas de Bactérias/genética , Galinhas , Flagelos/genética , Humanos , Reação em Cadeia da Polimerase , Salmonella/genética , Sensibilidade e Especificidade
16.
Immunity ; 52(6): 971-977.e3, 2020 06 16.
Artigo em Inglês | MEDLINE | ID: mdl-32413330

RESUMO

The World Health Organization has declared SARS-CoV-2 virus outbreak a worldwide pandemic. However, there is very limited understanding on the immune responses, especially adaptive immune responses to SARS-CoV-2 infection. Here, we collected blood from COVID-19 patients who have recently become virus-free, and therefore were discharged, and detected SARS-CoV-2-specific humoral and cellular immunity in eight newly discharged patients. Follow-up analysis on another cohort of six patients 2 weeks post discharge also revealed high titers of immunoglobulin G (IgG) antibodies. In all 14 patients tested, 13 displayed serum-neutralizing activities in a pseudotype entry assay. Notably, there was a strong correlation between neutralization antibody titers and the numbers of virus-specific T cells. Our work provides a basis for further analysis of protective immunity to SARS-CoV-2, and understanding the pathogenesis of COVID-19, especially in the severe cases. It also has implications in developing an effective vaccine to SARS-CoV-2 infection.


Assuntos
Betacoronavirus/fisiologia , Infecções por Coronavirus/imunologia , Imunidade Celular , Imunidade Humoral , Pneumonia Viral/imunologia , Adulto , Anticorpos Neutralizantes/imunologia , Anticorpos Antivirais/sangue , Anticorpos Antivirais/imunologia , COVID-19 , Convalescença , Infecções por Coronavirus/sangue , Infecções por Coronavirus/patologia , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Pandemias , Pneumonia Viral/sangue , Pneumonia Viral/patologia , SARS-CoV-2 , Glicoproteína da Espícula de Coronavírus/imunologia
17.
J Org Chem ; 85(10): 6605-6619, 2020 05 15.
Artigo em Inglês | MEDLINE | ID: mdl-32364381

RESUMO

Challenges to the de novo synthesis of bacteriochlorophyll a (BChl a), the chief pigment for anoxygenic bacterial photosynthesis, include creating the macrocycle along with the trans-dialkyl substituents in both pyrroline rings (B and D). A known route to a model bacteriochlorophyll with a gem-dimethyl group in each pyrroline ring has been probed for utility in the synthesis of BChl a by preparation of a hybrid macrocycle (BC-1), which contains a trans-dialkyl group in ring D and a gem-dimethyl group in ring B. Stereochemical definition began with the synthesis of (2S,3S)-2-ethyl-3-methylpent-4-ynoic acid, a precursor to the trans-dialkyl-substituted AD dihydrodipyrrin. Knoevenagel condensation of the latter and a gem-dimethyl, ß-ketoester-substituted BC dihydrodipyrrin afforded the enone (E, 70%; Z, 3%); subsequent double-ring cyclization of the E-enone (via Nazarov, electrophilic aromatic substitution, and elimination reactions) gave BC-1 (53% yield) along with a trace of chlorin byproduct (1.4% relative to BC-1 upon fluorescence assay). BC-1 exhibited the desired trans-dialkyl stereochemistry in ring D and was obtained as a 7:1 mixture of (expected) epimers owing to the configuration of the 132-carbomethoxy substituent. The strategy wherein trans-dialkyl substituents are installed very early and carried through to completion, as validated herein, potentially opens a synthetic path to native photosynthetic pigments.


Assuntos
Bacterioclorofila A , Bacterioclorofilas , Bacterioclorofila A/química , Bacterioclorofilas/química , Fluorescência
18.
Molecules ; 25(8)2020 Apr 17.
Artigo em Inglês | MEDLINE | ID: mdl-32316663

RESUMO

Riley oxidation of advanced heterocyclic intermediates (dihydrodipyrrins and tetrahydrodipyrrins) is pivotal in routes to synthetic hydroporphyrins including chlorins, bacteriochlorins, and model (bacterio)chlorophylls. Such macrocycles find wide use in studies ranging from energy sciences to photomedicine. The key transformation (-CH3 → -CHO) is often inefficient, however, thereby crimping the synthesis of hydroporphyrins. The first part of the review summarizes 12 representative conditions for Riley oxidation across diverse (non-hydrodipyrrin) substrates. An interlude summarizes the proposed mechanisms and provides context concerning the nature of various selenium species other than SeO2. The second part of the review comprehensively reports the conditions and results upon Riley oxidation of 45 1-methyltetrahydrodipyrrins and 1-methyldihydrodipyrrins. A comparison of the results provides insights into the tolerable structural features for Riley oxidation of hydrodipyrrins. In general, Riley oxidation of dihydrodipyrrins has a broad scope toward substituents, but proceeds in only modest yield. Too few tetrahydrodipyrrins have been examined to draw conclusions concerning scope. New reaction conditions or approaches will be required to achieve high yields for this critical transformation in the synthesis of hydroporphyrins.


Assuntos
Compostos Heterocíclicos/química , Oxirredução , Porfirinas/química , Estrutura Molecular
19.
J Immunol ; 204(10): 2754-2761, 2020 05 15.
Artigo em Inglês | MEDLINE | ID: mdl-32269096

RESUMO

Citrobacter rodentium colonizes at the colon and causes mucosal inflammation in mice. Previous studies have revealed the importance of the innate and adaptive immune response for controlling C. rodentium infection. In the present study, we examined the role of T follicular helper (Tfh) cells in intestinal C. rodentium infection using mice with Bcl6 deficiency in T cells. Tfh cells were absolutely required at the late, but not the early, phase to control infection. Compared with control mice, we observed systemic pathogen dissemination and more severe colitis in Tfh-deficient mice. Furthermore, the susceptibility of Tfh-deficient mice correlated with an impaired serum IgG1 response to infection, and serum Abs from infected wild-type mice protected Tfh-deficient mice from infection. The transfer of wild-type Tfh cells also restored the levels of IgG1 and led to effective clearance of the pathogens in Tfh-deficient mice. Moreover, during C. rodentium infection, IL-21- and IL-4-producing Tfh cells were increased obviously in wild-type mice, correlating with IgG1 as the major isotype in germinal center B cells. Taken together, our work highlights the requirement and the function of Tfh cells in regulating humoral response for the host protection against C. rodentium infection.


Assuntos
Linfócitos B/imunologia , Citrobacter rodentium/fisiologia , Colite/imunologia , Colo/metabolismo , Infecções por Enterobacteriaceae/imunologia , Centro Germinativo/imunologia , Linfócitos T Auxiliares-Indutores/imunologia , Animais , Anticorpos Antibacterianos/sangue , Colo/patologia , Resistência à Doença , Humanos , Imunidade Humoral , Imunoglobulina G/sangue , Interleucina-4/metabolismo , Interleucinas/metabolismo , Camundongos , Camundongos Endogâmicos C57BL , Proteínas Proto-Oncogênicas c-bcl-6/genética
20.
J Phys Chem A ; 124(5): 1047-1052, 2020 Feb 06.
Artigo em Inglês | MEDLINE | ID: mdl-31961157

RESUMO

We introduce getchellite as a new layered material for fabrication of two-dimensional van der Waals materials and heterostructures. Nanofilms of AsSbS3 were fabricated by mechanical exfoliation. Transient absorption spectroscopy measurements identified a direct bandgap at about 710 nm, which is close to the ideal single-junction photovoltaic bandgap. Transient absorption microscopy measurements with high spatial and temporal resolution were performed to reveal the spatiotemporal dynamics of photocarriers in AsSbS3. We obtained a photocarrier lifetime of about 200 ps, a diffusion coefficient of about 5 cm2 s-1, a diffusion length of about 320 nm, and a carrier mobility of about 200 cm2 V-1 s-1. These results establish AsSbS3 as a promising two-dimensional semiconductor for optoelectronic applications as an individual material or in heterostructures.

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