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1.
Skeletal Radiol ; 2024 Feb 08.
Artigo em Inglês | MEDLINE | ID: mdl-38329533

RESUMO

Senescent cells play a vital role in the pathogenesis of musculoskeletal (MSK) diseases, such as chronic inflammatory joint disorders, rheumatoid arthritis (RA), and osteoarthritis (OA). Cellular senescence in articular joints represents a response of local cells to persistent stress that leads to cell-cycle arrest and enhanced production of inflammatory cytokines, which in turn perpetuates joint damage and leads to significant morbidities in afflicted patients. It has been recently discovered that clearance of senescent cells by novel "senolytic" therapies can attenuate the chronic inflammatory microenvironment of RA and OA, preventing further disease progression and supporting healing processes. To identify patients who might benefit from these new senolytic therapies and monitor therapy response, there is an unmet need to identify and map senescent cells in articular joints and related musculoskeletal tissues. To fill this gap, new imaging biomarkers are being developed to detect and characterize senescent cells in human joints and musculoskeletal tissues. This review article will provide an overview of these efforts. New imaging biomarkers for senescence cells are expected to significantly improve the specificity of state-of-the-art imaging technologies for diagnosing musculoskeletal disorders.

2.
Anim Genet ; 55(2): 277-281, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38282540

RESUMO

Polydactyly is a genetic abnormality that affects both pig welfare and industry profits. Despite efforts to explore the genetic basis of pig polydactyly, progress remains limited. In this study, we analyzed a group of Large White pigs with postaxial polydactyly, including 29 cases and 79 controls from 24 families. High-depth sequencing was performed on 20 pigs, while low-depth sequencing was improved through imputation for the remaining pigs. A genome-wide association study (GWAS) and genetic differentiation were conducted using the resequencing dataset, resulting in the identification of 48 significantly associated SNPs and 27 candidate regions. The genetic differentiation regions on chromosomes 5 and 18, which harbored GWAS-identified SNPs, were delineated as confidence regions. The confidence region at Chr18: 1.850-1.925 Mb covers the fifth intron of LMBR1, a gene that contains an important regulatory element for SHH, known as ZRS. Mutations in this ZRS have been found to cause polydactyly in animals and humans. Therefore, we propose LMBR1 as a prospective candidate gene for postaxial polydactyly. These findings emphasize the importance of exploring the role of ZRS within LMBR1 in the pathogenesis of polydactyly in pigs.


Assuntos
Dedos/anormalidades , Polidactilia , Doenças dos Suínos , Dedos do Pé/anormalidades , Humanos , Animais , Suínos/genética , Estudo de Associação Genômica Ampla/veterinária , Polidactilia/genética , Polidactilia/veterinária , Polidactilia/patologia , Dedos/patologia , Mutação , Doenças dos Suínos/genética
3.
Molecules ; 29(2)2024 Jan 22.
Artigo em Inglês | MEDLINE | ID: mdl-38276618

RESUMO

Sinomenine, an isoquinoline alkaloid extracted from the roots and stems of Sinomenium acutum, has been extensively studied for its derivatives as bioactive agents. This review concentrates on the research advancements in the biological activities and action mechanisms of sinomenine-related compounds until November 2023. The findings indicate a broad spectrum of pharmacological effects, including antitumor, anti-inflammation, neuroprotection, and immunosuppressive properties. These compounds are notably effective against breast, lung, liver, and prostate cancers, exhibiting IC50 values of approximately 121.4 nM against PC-3 and DU-145 cells, primarily through the PI3K/Akt/mTOR, NF-κB, MAPK, and JAK/STAT signaling pathways. Additionally, they manifest anti-inflammatory and analgesic effects predominantly via the NF-κB, MAPK, and Nrf2 signaling pathways. Utilized in treating rheumatic arthritis, these alkaloids also play a significant role in cardiovascular and cerebrovascular protection, as well as organ protection through the NF-κB, Nrf2, MAPK, and PI3K/Akt/mTOR signaling pathways. This review concludes with perspectives and insights on this topic, highlighting the potential of sinomenine-related compounds in clinical applications and the development of medications derived from natural products.


Assuntos
Alcaloides , Morfinanos , Masculino , Humanos , NF-kappa B/metabolismo , Proteínas Proto-Oncogênicas c-akt , Fator 2 Relacionado a NF-E2 , Fosfatidilinositol 3-Quinases , Anti-Inflamatórios/farmacologia , Anti-Inflamatórios/uso terapêutico , Morfinanos/farmacologia , Serina-Treonina Quinases TOR , Alcaloides/farmacologia
4.
Aging Dis ; 14(4): 1171-1183, 2023 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-37163434

RESUMO

Disorders of consciousness (DOC) is a state in which consciousness is affected by brain injuries, leading to dysfunction in vigilance, awareness, and behavior. DOC encompasses coma, vegetative state, and minimally conscious state based on neurobehavioral function. Currently, DOC is one of the most common neurological disorders with a rapidly increasing incidence worldwide. Therefore, DOC not only impacts the lives of individuals and their families but is also becoming a serious public health threat. Repetitive transcranial magnetic stimulation (rTMS) can stimulate electrical activity using a pulsed magnetic field in the brain, with great value in the treatment of chronic pain, neurological diseases, and mental illnesses. However, the clinical application of rTMS in patients with DOC is debatable. Herein, we report the recent main findings of the clinical therapeutics of rTMS for DOC, including its efficacy and possible mechanisms. In addition, we discuss the potential key parameters (timing, location, frequency, strength, and secession of rTMS applications) that affect the therapeutic efficiency of rTMS in patients with DOC. This review may help develop clinical guidelines for the therapeutic application of rTMS in DOC.

5.
Front Neurol ; 14: 1124871, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37006496

RESUMO

Objective: Recently, short-term spinal cord stimulation (st-SCS) has been used in neurorehabilitation and consciousness recovery. However, little is known about its effects on primary brainstem hemorrhage (PBSH)-induced disorders of consciousness (DOC). In this study, we examined the therapeutic effects of st-SCS in patients with PBSH-induced DOC. Methods: Fourteen patients received a 2-week st-SCS therapy. Each patient's state of consciousness was evaluated using the Coma Recovery Scale-Revised (CRS-R). CRS-R evaluation scores were recorded at the baseline (before SCS implantation) and 14 days later. Results: Over 70% (10/14) of the patients (CRS-R score increased to ≥2 points) responded to the SCS stimulation after 14 days of st-SCS treatment. All items included in the CRS-R exhibited a significant increase post-treatment compared with pretreatment. After 2 weeks of st-SCS treatment, seven patients showed diagnostic improvement, resulting in a 50% (7/14) overall effective rate. Approximately 75% (3/4) of patients with minimally conscious state plus (MCS+) improved to emergence from MCS (eMCS), and 50% (1/2) of patients with vegetative state or unresponsive wakefulness syndrome (VS/UWS) improved to MCS+. Conclusion: In PBSH-induced DOC, st-SCS is a safe and effective treatment. The clinical behavior of the patients improved significantly following the st-SCS intervention, and their CRS-R scores markedly increased. This was most effective for MCS+.

6.
J Am Chem Soc ; 145(18): 10045-10050, 2023 05 10.
Artigo em Inglês | MEDLINE | ID: mdl-37116079

RESUMO

Real-time detection of bio-event in whole animals provides essential information for understanding biological and therapeutic processes. Magnetic resonance (MR) imaging represents a non-invasive approach to generating three-dimensional anatomic images with high spatial-temporal resolution and unlimited depth penetration. We have developed several self-immolative enzyme-activatable agents that provide excellent in vivo contrast and function as gene expression reporters. Here, we describe a vast improvement in image contrast over our previous generations of these bioresponsive agents based on a new pyridyl-carbamate Gd(III) complex. The pyridyl-carbamate-based agent has a very low MR relaxivity in the "off-state" (r1 = 1.8 mM-1 s-1 at 1.41 T). However, upon enzymatic processing, it generates a significantly higher relaxivity with a Δr1 = 106% versus Δr1 ∼ 20% reported previously. Single X-ray crystal and nuclear magnetic relaxation dispersion analyses offer mechanistic insights regarding MR signal enhancement at the molecular scale. This work demonstrates a pyridyl-carbamate-based self-immolative molecular platform for the construction of enzymatic bio-responsive MR agents, which can be adapted to a wide range of other targets for exploring stimuli-responsive materials and biomedical applications.


Assuntos
Imageamento por Ressonância Magnética , Magnetismo , Animais , Imageamento por Ressonância Magnética/métodos , Meios de Contraste/química
7.
Phytother Res ; 37(7): 2979-2994, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-36866539

RESUMO

Aloe-emodin (AE) has been shown to inhibit the proliferation of several cancer cell lines, including human nasopharyngeal carcinoma (NPC) cell lines. In this study, we confirmed that AE inhibited malignant biological behaviors, including cell viability, abnormal proliferation, apoptosis, and migration of NPC cells. Western blotting analysis revealed that AE upregulated the expression of DUSP1, an endogenous inhibitor of multiple cancer-associated signaling pathways, resulting in blockage of the extracellular signal-regulated kinase (ERK)-1/2, protein kinase B (AKT), and p38-mitogen activated protein kinase(p38-MAPK) signaling pathways in NPC cell lines. Moreover, the selective inhibitor of DUSP1, BCI-hydrochloride, partially reversed the AE-induced cytotoxicity and blocked the aforementioned signaling pathways in NPC cells. In addition, the binding between AE and DUSP1 was predicted via molecular docking analysis using AutoDock-Vina software and further verified via a microscale thermophoresis assay. The binding amino acid residues were adjacent to the predicted ubiquitination site (Lys192) of DUSP1. Immunoprecipitation with the ubiquitin antibody, ubiquitinated DUSP1 was shown to be upregulated by AE. Our findings revealed that AE can stabilize DUSP1 by blocking its ubiquitin-proteasome-mediated degradation and proposed an underlying mechanism by which AE-upregulated DUSP1 may potentially target multiple pathways in NPC cells.


Assuntos
Aloe , Emodina , Neoplasias Nasofaríngeas , Humanos , Emodina/farmacologia , Carcinoma Nasofaríngeo , Ubiquitina , Simulação de Acoplamento Molecular , Transdução de Sinais , Apoptose , Proteínas Quinases p38 Ativadas por Mitógeno/metabolismo , Neoplasias Nasofaríngeas/tratamento farmacológico , Linhagem Celular Tumoral , Proliferação de Células , Fosfatase 1 de Especificidade Dupla/metabolismo
8.
Hereditas ; 159(1): 37, 2022 Sep 27.
Artigo em Inglês | MEDLINE | ID: mdl-36167571

RESUMO

BACKGROUND: C-C chemokine receptor 5 (CCR5) has recently been recognized as an underlying therapeutic target for various malignancies. However, the association of CCR5 with prognosis in the head and neck squamous cell carcinoma (HNSC) patients and tumor-infiltrating lymphocytes (TILs) is unclear. METHODS: In the current experiment, methods such as the Tumor Immune Estimation Resource Analysis (TIMER), Gene Expression Profiling Interactive Analysis (GEPIA), UALCAN, and Kaplan-Meier plotter Analysis were used to comprehensively evaluate the expression of CCR5 in human various malignancies and the clinical prognosis in HNSC patients. Subsequently, we used the TIMER database and the TISIDB platform to investigate the correlation between CCR5 expression levels and immune cell infiltration in the HNSC tumor microenvironment. Furthermore, immunomodulatory and chemokine profiling were performed using the TISIDB platform to analyse the correlation between CCR5 expression levels and immunomodulation in HNSC patients. RESULTS: We found that CCR5 expression in HNSC tumor tissues was significantly upregulated than in normal tissues. In HNSC, patients with high CCR5 expression levels had worse overall survival (OS, HR = 0.59, p = 0.00015) and worse recurrence-free survival (RFS, HR = 3.27, p = 0.00098). Upregulation of CCR5 expression is closely associated with immunomodulators, chemokines, and infiltrating levels of CD4+ T cells, neutrophils, macrophages, and myeloid dendritic cells. Furthermore, upregulated CCR5 was significantly associated with different immune markers in the immune cell subsets of HNSC. CONCLUSIONS: High expression of CCR5 plays an important prognostic role in HNSC patients and may serve as a prognostic biomarker correlated with immune infiltration, and further studies are still needed to investigate therapeutic targeting HNSC patients in the future.


Assuntos
Biologia Computacional , Neoplasias de Cabeça e Pescoço , Biologia Computacional/métodos , Neoplasias de Cabeça e Pescoço/genética , Humanos , Fatores Imunológicos , Prognóstico , Receptores CCR5/genética , Receptores de Quimiocinas , Carcinoma de Células Escamosas de Cabeça e Pescoço/genética , Microambiente Tumoral
9.
J Anim Sci ; 100(10)2022 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-35998083

RESUMO

Chinese goats are an important group of goats worldwide. However, there are few studies on the conservation priority, genetic relationship, and potential gene flow between Chinese and global goat breeds. Here, we genotyped 239 goats from conservation populations of the Chinese Guangfeng and Ganxi breeds using the GoatSNP50 BeadChip. The conservation priority, population structure, selection signatures and introgression of these goats were analyzed in the context of 36 global goat breeds. First, we showed that Guangfeng and Ganxi goats had the largest effective population sizes across the global breeds 13 generations ago. Nevertheless, Ganxi goats have recently experienced a high degree of inbreeding, resulting in their conservation priority based on total gene and allelic diversities being lower than that of most other Chinese breeds (including Guangfeng goats). Population structure and admixture analyses showed that an average of 18% of Guangfeng genomic components were introgressed from Boer goats approximately 18-yr ago. Next, we reconstructed the subfamily structure of the core populations of Guangfeng and Ganxi goats, and proposed reasonable conservation strategies for inbreeding management. Moreover, a list of candidate genes under selection for fertility, immunity, growth, and meat quality were detected in Guangfeng and Ganxi goats. Finally, we identified some genes related to body development and reproduction, which were introgressed from Boer goats and may be beneficial for improving performance and productivity of Guangfeng goats. In conclusion, this study not only provides new insights into the conservation and utilization of Guangfeng and Ganxi goats but also enriches our understanding of artificial introgression from exotic goats into Chinese local goats.


Guangfeng and Ganxi goats are the only two indigenous goat breeds in Jiangxi Province, China. Their genetic diversity, population structure, selective sweep, and potential introgression are largely unknown. We analyzed 50K genotype data to clarify these issues from a global perspective. The results showed that Ganxi goats had a low level of genetic diversity, and Guangfeng goats had an introgression from Boer goats that led to increased genetic diversity. We reconstructed the subfamily structure of Jiangxi goats based on neighbor-joining trees, and proposed a reasonable conservation strategy to maintain the genetic variability of these breeds. Then, we detected a list of candidate genes under selection for fecundity, growth, immunity, and meat quality in Jiangxi goats. Finally, we identified some body development and reproduction-related genes that were introgressed from Boer into Guangfeng goats. Our study will provide guidelines for conservation and breeding programs for Jiangxi goats and highlights the potential effect of human-mediated introgression on economic traits in Chinese indigenous goats.


Assuntos
Cabras , Polimorfismo de Nucleotídeo Único , Animais , Cabras/genética , Genética Populacional , Genômica , China , Variação Genética
10.
Front Genet ; 13: 774196, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35559012

RESUMO

Runs of homozygosity (ROH) and heterozygosity (ROHet) are windows into population demographic history and adaptive evolution. Numerous studies have shown that deleterious mutations are enriched in the ROH of humans, pigs, cattle, and chickens. However, the relationship of deleterious variants to ROH and the pattern of ROHet in goats have been largely understudied. Here, 240 Guangfeng and Ganxi goats from Jiangxi Province, China, were genotyped using the Illumina GoatSNP50 BeadChip and genome-wide ROH, ROHet, and genetic load analyses were performed in the context of 32 global goat breeds. The classes with the highest percentage of ROH and ROHet were 0.5-2 Mb and 0.5-1 Mb, respectively. The results of inbreeding coefficients (based on SNP and ROH) and ROHet measurements showed that Guangfeng goats had higher genetic variability than most Chinese goats, while Ganxi goats had a high degree of inbreeding, even exceeding that of commercial goat breeds. Next, the predicted damaging homozygotes were more enriched in long ROHs, especially in Guangfeng goats. Therefore, we suggest that information on damaging alleles should also be incorporated into the design of breeding and conservation programs. A list of genes related to fecundity, growth, and environmental adaptation were identified in the ROH hotspots of two Jiangxi goats. A sense-related ROH hotspot (chromosome 12: 50.55-50.81 Mb) was shared across global goat breeds and may have undergone selection prior to goat domestication. Furthermore, an identical ROHet hotspot (chromosome 1: 132.21-132.54 Mb) containing two genes associated with embryonic development (STAG1 and PCCB) was detected in domestic goat breeds worldwide. Tajima's D and BetaScan2 statistics indicated that this region may be caused by long-term balancing selection. These findings not only provide guidance for the design of conservation strategies for Jiangxi goat breeds but also enrich our understanding of the adaptive evolution of goats.

11.
Front Genet ; 13: 828884, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35419032

RESUMO

Age at first egg (AFE) and egg number (EN) are economically important traits related to egg production, as they directly influence the benefits of the poultry industry, but the molecular genetic research that affects those traits in laying ducks is still sparse. Our objective was to identify the genomic regions and candidate genes associated with AFE, egg production at 43 weeks (EP43w), and egg production at 66 weeks (EP66w) in a Shaoxing duck population using genome-wide association studies (GWASs) and haplotype-sharing analysis. Single-nucleotide polymorphism (SNP)-based genetic parameter estimates showed that the heritability was 0.15, 0.20, and 0.22 for AFE, EP43w, and EP66w, respectively. Subsequently, three univariate GWASs for AFE, EP43w, and EP66w were carried out independently. Twenty-four SNPs located on chromosome 25 within a 0.01-Mb region that spans from 4.511 to 4.521 Mb were associated with AFE. There are two CIs that affect EP43w, i.e., twenty-five SNPs were in strong linkage disequilibrium region spanning from 3.186 to 3.247 Mb on chromosome 25, a region spanning from 4.442 to 4.446 Mb on chromosome 25, and two interesting genes, ACAD8 and THYN1, that may affect EP43w in laying ducks. There are also two CIs that affect EP66w, i.e., a 2.412-Mb region that spans from 127.497 to 129.910 Mb on chromosome 2 and a 0.355-Mb region that spans from 4.481 to 4.837 Mb on chromosome 29, and CA2 and GAMT may be the putative candidate genes. Our study also found some haplotypes significantly associated with these three traits based on haplotype-sharing analysis. Overall, this study was the first publication of GWAS on egg production in laying ducks, and our findings will be helpful to provide some candidate genes and haplotypes to improve egg production performance based on breeding in laying duck. Additionally, we learned from a method called bootstrap test to verify the reliability of a GWAS with small experimental samples that users can access at https://github.com/xuwenwu24/Bootstrap-test.

12.
iScience ; 25(4): 104064, 2022 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-35355522

RESUMO

Photocatalysis under UV/visible light irradiation has emerged as one of the green methodologies for solar energy utilization and organic synthesis. These photocatalytic processes are typically initiated by one-photon-absorbing metal complexes or organic dyes. Nevertheless, the intrinsic restrictions of UV/visible light irradiation, such as shallow penetration in reaction solutions, competing absorption by substrates, and limited coverage of the solar spectrum, call for the development of innovative photocatalysts functioning under longer wavelength irradiation. Herein, we report a ruthenium complex containing a metal-organic framework, MOF-Ru1, which can drive diverse organic reactions under 740 nm light irradiation following the two-photon absorption (TPA) process. Various organic transformations such as energy transfer, reductive, oxidative, and redox neutral reactions were realized using this heterogeneous hybrid photocatalyst. Overall, MOF-Ru1 represents an intriguing TPA photocatalyst active under near-infrared light irradiation, paving a way for the efficient utilization of low-energy light and convenient photocatalyst recycling because of phase separation.

13.
Inorg Chem ; 60(19): 14810-14819, 2021 Oct 04.
Artigo em Inglês | MEDLINE | ID: mdl-34546744

RESUMO

Three tris-heteroleptic mononuclear Ru(II) complexes with dual fluorescence and phosphorescence-[Ru(dpma)(bpy)(phen)]2+ (12+), [Ru(dpma)(bpy)(dppz)]2+ (22+), and [Ru(dpma)(phen)(dppz)]2+ (32+)-have been designed and used as ratiometric light-response probes for DNA, where dpma is di(pyrid-2-yl)(methyl)-amine, bpy is 2,2'-bipyridine, phen is 1,10-phenanthroline, and dppz is dipyridophenazine, respectively. Single crystals of complex 2(PF6)2 have been obtained and studied by X-ray analysis. The interactions of these complexes with different DNAs are investigated by means of spectroscopic methods, viscosity measurements, and molecular modeling. In the presence of calf thymus DNA, complexes 2(PF6)2 and 3(PF6)2 show the emergence of a new lower-energy phosphorescence emission band; meanwhile, the higher-energy fluorescence emission band is essentially unchanged, functioning as an intrinsic internal reference. These two complexes exhibit stronger preference for calf thymus DNA over single-strand DNA (d(A)16 and d(C)16). In contrast, no binding interaction between 1(PF6)2 and calf thymus DNA is observed. The intrinsic binding constants (Kb) of 2(PF6)2 and 3(PF6)2 with calf thymus DNA are determined to be (1.4 ± 0.4) × 105 and (9.5 ± 0.15) × 104 M-1, respectively. In addition, these spectroscopic results are compared with those of the prototype complex [Ru(bpy)2(dppz)]2+ (42+), and density functional theory and time-dependent density functional theory calculations are employed to elucidate these experimental findings.


Assuntos
Complexos de Coordenação/química , DNA/química , Rutênio/química , Animais , Bovinos , Estrutura Molecular
14.
Evol Appl ; 14(2): 383-398, 2021 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-33664783

RESUMO

Laiwu pigs are a Chinese indigenous breed that is renowned for its exceptionally high intramuscular fat content (average greater than 6%), providing an excellent genetic resource for the genetic improvement of meat quality of modern commercial pigs. To uncover genetic diversity, population structure, signature of selection, and potential exotic introgression in this breed, we sampled 238 Laiwu pigs from a state-supported conservation population and genotyped these individuals using GeneSeek 80K SNP BeadChip. We then conducted in-depth population genetics analyses for the Laiwu pig in a context of 1,116 pigs from 42 Eurasian diverse breeds. First, we show that the current Laiwu population has more abundant genetic diversity than the population of 18 years ago likely due to gene flow from European commercial breeds. Both neighbor-joining (NJ) and principal component analyses indicate the introgression of European haplotypes into Laiwu pigs. The admixture analysis reveals that an average 26.66% of Laiwu genetic components are of European origin. Then, we assigned the tested individuals to different families according to their clustering patterns in the NJ tree and proposed a family-based conservation strategy to reduce the risk of inbreeding depression in Laiwu pigs. Next, we explored three statistics (ROH and iHS and EigenGWAS) to identify a list of candidate genes for fat deposition, reproduction, and growth in Laiwu pigs. Last, we detected a strong signature of introgression from European pigs into Laiwu pigs at the GPC6 locus that regulates the growth of developing long bones. Further association analyses indicate that the introgressed GPC6 haplotype likely contributed to the improvement of growth performance in Laiwu pigs. Altogether, this study not only benefits the better conservation of the Laiwu pig, but also advances our knowledge of the poorly understood effect of human-mediated introgression on phenotypic traits in Chinese indigenous pigs.

15.
J Am Chem Soc ; 143(7): 2908-2919, 2021 02 24.
Artigo em Inglês | MEDLINE | ID: mdl-33576621

RESUMO

Two trigonal prismatic metallacages 1 and 2 bearing triphenylamine and anthracene moieties are designed and synthesized to fabricate artificial light-harvesting systems (LHSs). These two cages are prepared via the coordination-driven self-assembly of two anthracene-triphenylamine-based tripyridyl ligand 3, three dicarboxylates, and six 90° Pt(II) acceptors. The design of the anthracene-triphenylamine chromophore makes possible the tunable excited-state property (like the emissive transition energy and lifetime) as a function of the solvent polarity, temperature, and concentration. The synergistic photophysical footprint of these metallacages, defined by their high absorptivity and emission quantum yield (QY) relative to the free ligand 3, signifies them as a superior light sensitizer component in an LHS. In the presence of the fluorescent dye Nile Red (NR) as an energy acceptor, the metallacages display efficient (>93%) excited energy transfer to NR through an apparent static quenching mechanism in viscous dimethyl sulfoxide solvent.

16.
J Am Chem Soc ; 142(5): 2601-2608, 2020 02 05.
Artigo em Inglês | MEDLINE | ID: mdl-31939661

RESUMO

Singlet oxygen (1O2), as an important active reagent, has found wide applications in photodynamic therapy (PDT), synthetic chemistry, and materials science. Organic conjugated aromatics serving as hosts to capture and release singlet oxygen have been systematically investigated over the last decades. Herein, we present a [6 + 6] organoplatinum(II) metallacycle by using ∼180° dipyridylanthracene donor and ∼120° Pt(II) acceptor as the building blocks, which enables the capture and release of singlet oxygen with relatively high photooxygenation and thermolysis rate constants. The photooxygenation of the metallacycle to the corresponding endoperoxide was performed by sensitized irradiation, and the resulting endoperoxide is stable at room temperature and can be stored under ambient condition over months. Upon simple heating of the neat endoperoxide under inert atmosphere at 120 °C for 4 h, the resulting endoperoxide can be reconverted to the corresponding parent form and singlet oxygen. The photooxygenation and thermolysis products were characterized by NMR spectroscopy and electrospray ionization time-of-flight mass spectrometric analysis. Density functional theory calculations were conducted in order to reveal the frontier molecular orbital interactions and reactivity. This work provides a new material platform for singlet oxygen related promising applications.


Assuntos
Compostos Organometálicos/química , Compostos de Platina/química , Oxigênio Singlete/química , Hidrocarbonetos Policíclicos Aromáticos/química , Análise Espectral/métodos
17.
Artigo em Inglês | MEDLINE | ID: mdl-31766298

RESUMO

In order to solve the problems of high energy consumption, complex process and low nitrogen removal efficiency in the currently available low carbon source wastewater treatment processes, a novel coagulation sedimentation/post-solid-phase denitrification biofilter process (CS-BAF-SPDB) was proposed. The effect of temperature on the nitrogen removal performance of BAF-SPDB was intensively studied, and the mechanism of the effect of temperature on nitrogen removal performance was analyzed from the perspective of microbial community structure by using the polymerase chain reaction denaturing gradient gel electrophoresis (PCR-DGGE). The results showed that, to realize favorable nitrifying and denitrifying performance simultaneously in the BAF-SPDB unit, the operation temperature should be set above 18 °C. In addition, the influence of the macro operation parameters on the performance of the BAF and SPDB has a direct relationship with the dynamic changes of the micro microbial community. The influence of temperature on nitrification performance in BAF was mainly embodied in the change of composition, amount and activity of ammonia oxidizing bacteria Candidatus Nitrospira defluvii and nitrite oxidizing bacteria Nitrosomonas sp. Nm47, while that on denitrification performance in SPDB is mainly embodied in the change of composition and amount of solid carbon substrate degrading denitrifying bacteria Pseudomonas sp., Myxobacterium AT3-03 and heterotrophic denitrifying bacteria Dechloromonas agitate, Thauera aminoaromatica, Comamonas granuli and Rubrivivax gelatinosus.


Assuntos
Microbiota , Nitrogênio/metabolismo , Temperatura , Eliminação de Resíduos Líquidos/métodos , Bactérias/metabolismo , Reatores Biológicos , Desnitrificação , Filtração , Floculação , Águas Residuárias
18.
Nat Commun ; 10(1): 4599, 2019 10 10.
Artigo em Inglês | MEDLINE | ID: mdl-31601813

RESUMO

Host-guest interactions are of central importance in many biological and chemical processes. However, the investigation of the formation and decomplexation of host-guest systems at the single-molecule level has been a challenging task. Here we show that the single-molecule conductance of organoplatinum(II) metallocycle hosts can be enhanced by an order of magnitude by the incorporation of a C60 guest molecule. Mechanically stretching the metallocycle-C60 junction with a scanning tunneling microscopy break junction technique causes the release of the C60 guest from the metallocycle, and consequently the conductance switches back to the free-host level. Metallocycle hosts with different shapes and cavity sizes show different degrees of flexibility to accommodate the C60 guest in response to mechanical stretching. DFT calculations provide further insights into the electronic structures and charge transport properties of the molecular junctions based on metallocycles and the metallocycle-C60 complexes.


Assuntos
Fulerenos/química , Compostos Organoplatínicos/química , Teoria da Densidade Funcional , Eletrodos , Ouro , Espectroscopia de Ressonância Magnética , Microscopia de Força Atômica , Microscopia de Tunelamento , Espectrofotometria Ultravioleta
19.
Inorg Chem ; 58(19): 13376-13381, 2019 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-31532649

RESUMO

In this work, we present the formation of two open-ended hexagonal-prism tubular macrocycles by the [6 + 12] self-assembly of the symmetric ∼120° organic ligand donor with ∼90° Pt(II) acceptor in a 1:2 ratio. The assembled structures were characterized by multinuclear NMR (1H NMR, 31P{1H} NMR, and 1H-1H COSY NMR), electrospray ionization mass spectrometry (ESI-TOF-MS), traveling wave ion mobility-mass spectrometry (TWIM-MS), and transmission electron microscopy. Molecular modeling was further conducted to get insight into their structured characteristics. We also examined their photophysical properties.

20.
Chem Asian J ; 14(18): 3119-3126, 2019 Sep 16.
Artigo em Inglês | MEDLINE | ID: mdl-31389657

RESUMO

The bottom-up functionalization of solid surfaces shows increasing importance for a wide range of interdisciplinary applications. Multidentate anchors with more than two contact points can bind to solid surfaces with strong chemisorption, well-defined upright configuration, and tailored functionality. The surface functionalization using multidentate anchors with three (tripodal), four (quadripodal), or more binding points is summarized herein, with a focus on those beyond classical tripodal anchors. In particular, the molecular design on how to achieve multisite interaction between anchor and substrate and the introduction of functional groups to thin films are discussed.

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