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1.
Molecules ; 28(8)2023 Apr 19.
Artigo em Inglês | MEDLINE | ID: mdl-37110812

RESUMO

A convenient silver-promoted radical cascade aryldifluoromethylation/cyclization of 2-allyloxybenzaldehydes has been developed. Experimental studies disclosed that the addition of aryldifluoromethyl radicals in situ produced from easily accessible gem-difluoroarylacetic acids to unactivated double bonds in 2-allyloxybenzaldehyde was an effective route to access a series of 3-aryldifluoromethyl-containing chroman-4-one derivatives in moderate to good yields under mild reaction conditions.

2.
Angew Chem Int Ed Engl ; 62(14): e202300238, 2023 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-36752412

RESUMO

Cyclic ether, such as 1,3-dioxolane (DOL), are promising solvent for low-temperature electrolytes because of the low freezing point. Their use in electrolytes, however, is severely limited since it easily polymerizes in the presence of lithium inorganic salts. The trace water plays a key role via providing the source (proton) for chain initiation, which has, unfortunately, been neglected in most cases. In this work, we present an electrophile, trimethylsilyl isocyanate (Si-NCO), as the water scavenger, which eliminates moisture by a nucleophilic addition reaction. Si-NCO allows DOL to maintain liquid over a wide temperature range even in high-concentration electrolyte. Electrolyte with Si-NCO additive shows promising low-temperature performance. Our finding expands the use of cyclic ether solvents in the presence of inorganic salts and highlights a large space for unexplored design of water scavenger with electrophilic feature for low-temperature electrolytes.

3.
Chem Asian J ; 17(15): e202200448, 2022 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-35661611

RESUMO

An efficient silver-promoted decarboxylative gem-difluoromethylenation of aryl- or alkyl-substituted α,ß-unsaturated carboxylic acids with readily available benzo-1,3-diazolic difluoromethyl bromides has been developed. This convenient transformation demonstrated good functional-group tolerability and broad substrate scope, and afforded the allylic difluorides in good to excellent yields with exclusive E-stereoselectivity under mild reaction conditions.


Assuntos
Ácidos Carboxílicos , Prata , Brometos , Catálise , Descarboxilação
4.
Front Vet Sci ; 9: 814562, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35478603

RESUMO

The circadian clock system is based on interlocked positive and negative transcriptional and translational feedback loops of core clock genes and their encoded proteins. The mammalian circadian clock system has been extensively investigated using mouse models, but has been poorly investigated in diurnal ruminants. In this study, goat embryonic fibroblasts (GEFs) were isolated and used as a cell model to elucidate the caprine circadian clock system. Real-time quantitative PCR analysis showed that several clock genes and clock-controlled genes were rhythmically expressed in GEFs over a 24 h period after dexamethasone stimulation. Immunofluorescence revealed that gBMAL1 and gNR1D1 proteins were expressed in GEFs, and western blotting analysis further verified that the proteins were expressed with circadian rhythmic changes. Diurnal changes in clock and clock-controlled gene expression at the mRNA and protein levels were also observed in goat liver and kidney tissues at two representative time points in vivo. Amino acid sequences and tertiary structures of goat BMAL1 and CLOCK proteins were found to be highly homologous to those in mice and humans. In addition, a set of goat representative clock gene orthologs and the promoter regions of two clock genes of goats and mice were cloned. Dual-luciferase reporter assays showed that gRORα could activate the promoter activity of the goat BMAL1, while gNR1D1 repressed it. The elevated pGL4.10-gNR1D1-Promoter-driven luciferase activity induced by mBMAL1/mCLOCK was much higher than that induced by gBMAL1/gCLOCK, and the addition of gCRY2 or mPER2 repressed it. Real-time bioluminescence assays revealed that the transcriptional activity of BMAL1 and NR1D1 in goats and mice exhibited rhythmic changes over a period of approximately 24 h in NIH3T3 cells or GEFs. Notably, the amplitudes of gBMAL1 and gNR1D1 promoter-driven luciferase oscillations in NIH3T3 cells were higher than those in GEFs, while mBMAL1 and mNR1D1 promoter-driven luciferase oscillations in NIH3T3 cells had the highest amplitude. In sum, transcriptional and translational loops of the mammalian circadian clock system were found to be broadly conserved in goats and not as robust as those found in mice, at least in the current experimental models. Further studies are warranted to elucidate the specific molecular mechanisms involved.

5.
Chem Asian J ; 17(10): e202200088, 2022 May 16.
Artigo em Inglês | MEDLINE | ID: mdl-35319154

RESUMO

An efficient method for silver-catalyzed radical cascade arylthiodifluoromethylation/cyclization of isonitriles is disclosed. The transformation comprised addition of an arylthiodifluoromethyl radical generated in situ by the oxidative decarboxylation of arylthiodifluoroacetic salts to the isonitrile functionality to construct an ArSCF2 -C bond, followed by intramolecular cyclization to eventually afford 6-phenanthridinyldifluoromethyl aryl thioethers. The protocol provided a variety of 6-phenanthridinyldifluoromethyl aryl thioethers in medium to excellent yields with a good functional group tolerance under mild reaction conditions.


Assuntos
Prata , Sulfetos , Catálise , Ciclização , Oxirredução , Sulfetos/química
6.
J Pept Sci ; 28(3): e3371, 2022 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-34608710

RESUMO

A cathepsin B (Cat B)-responsive optical nanoprobe is designed and prepared for report of HL60 differentiation into macrophage. A peptide sequence FRFK is linked to fluorescein (FITC) via the distant amino group of its lysine and N-terminated with acrylic acid (AA) to yield a molecular fluorescent probe AA-FRFK (FITC). The molecular probe is further embedded in poly(lactic-co-glycolic acid) (PLGA) to form a fluorescent nanoprobe AA-FRFK (FITC)@PLGA. The resultant optical nanoprobe is degradable by lysosomal Cat B, which is expressed in macrophages with a level of 5-10 times of that in HL60 cells. As a result, a significant decrease in fluorescence intensity is associated with the differentiation process of HL60 to macrophage and can be used as an indication of the differentiation process. The findings may pave a way toward the development of a universal in vitro labeling strategy of exogenous stem cells for report of in vivo cell differentiation by a dual-mode imaging modality involving optical imaging and magnetic resonance imaging.


Assuntos
Catepsina B , Macrófagos , Diferenciação Celular , Fluoresceína-5-Isotiocianato/química , Células HL-60 , Humanos
7.
Am J Physiol Cell Physiol ; 322(2): C231-C245, 2022 02 01.
Artigo em Inglês | MEDLINE | ID: mdl-34936504

RESUMO

Autophagy of granulosa cells (GCs) is involved in follicular atresia, which occurs repeatedly during the ovarian development cycle. Several circadian clock genes are rhythmically expressed in both rodent ovarian tissues and GCs. Nuclear receptor subfamily 1 group D member 1 (NR1D1), an important component of the circadian clock system, is involved in the autophagy process through the regulation of autophagy-related genes. However, there are no reports illustrating the role of the circadian clock system in mouse GC autophagy. In the present study, we found that core circadian clock genes (Bmal1, Per2, Nr1d1, and Dbp) and an autophagy-related gene (Atg5) exhibited rhythmic expression patterns across 24 h in mouse ovaries and primary GCs. Treatment with SR9009, an agonist of NR1D1, significantly reduced the expression of Bmal1, Per2, and Dbp in mouse GCs. ATG5 expression was significantly attenuated by SR9009 treatment in mouse GCs. Conversely, Nr1d1 knockdown increased ATG5 expression in mouse GCs. Decreased NR1D1 expression at both the mRNA and protein levels was detected in the ovaries of Bmal1-/- mice, along with elevated expression of ATG5. Dual-luciferase reporter assay and electrophoretic mobility shift assay showed that NR1D1 inhibited Atg5 transcription by binding to two putative retinoic acid-related orphan receptor response elements within the promoter. In addition, rapamycin-induced autophagy and ATG5 expression were partially reversed by SR9009 treatment in mouse GCs. Taken together, our current data demonstrated that the circadian clock regulates GC autophagy through NR1D1-mediated inhibition of ATG5 expression, and thus, plays a role in maintaining autophagy homeostasis in GCs.


Assuntos
Proteína 5 Relacionada à Autofagia/biossíntese , Autofagia/fisiologia , Relógios Circadianos/fisiologia , Ritmo Circadiano/fisiologia , Células da Granulosa/metabolismo , Membro 1 do Grupo D da Subfamília 1 de Receptores Nucleares/biossíntese , Animais , Proteína 5 Relacionada à Autofagia/antagonistas & inibidores , Proteína 5 Relacionada à Autofagia/genética , Células Cultivadas , Peptídeos e Proteínas de Sinalização do Ritmo Circadiano/biossíntese , Peptídeos e Proteínas de Sinalização do Ritmo Circadiano/genética , Feminino , Células da Granulosa/patologia , Células HEK293 , Humanos , Camundongos , Camundongos Endogâmicos C57BL , Camundongos Transgênicos , Membro 1 do Grupo D da Subfamília 1 de Receptores Nucleares/genética
8.
Theriogenology ; 174: 9-19, 2021 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-34416563

RESUMO

The circadian clock system plays an important role in regulating testosterone synthesis in mammals. Male Bmal1-/- mice are infertile with low serum testosterone levels and decreased expression of testicular steroidogenic genes, suggesting that circadian clock genes regulate testosterone biosynthesis by activating steroidogenic gene transcription. However, whether the circadian clock regulates testosterone production via other genes remains unknown. Using Bmal1-/- mice and their wild-type (WT) siblings, we aimed to identify additional genes by which the circadian clock regulates testosterone synthesis. WT and Bmal1-/- mouse testes sections had similar normal morphologies, although there was a decrease in testicular spermatozoa in the Bmal1-/- mice. Low serum testosterone levels were detected in the Bmal1-/- mice. RNA sequencing identified 37 and 48 genes that were differentially expressed between WT and Bmal1-/- mouse testes at circadian time (CT2 and CT14), respectively. The cholesterol metabolism pathway was significantly enriched in the KEGG pathway analysis, and there was lower expression of three apolipoprotein genes (Apoa1, Apoa2, and Apoc3) at CT2 in the testes of Bmal1-/- mice than in those of WT mice. These decreases in Apoa1, Apoa2, and Apoc3 expression were verified by quantitative polymerase chain reaction analysis, which also revealed downregulation of the expression of the circadian clock (Per2, Dbp, and Nr1d1) and steroidogenic (StAR, Cyp11a1, and Hsd17b3) genes. The expression of circadian clock genes was relatively stable in WT mice over a 20-h period, whereas there was clear circadian rhythmic expression of Apoa1, Apoa2, Apoc3, StAR, Cyp11a1, Hsd3b2, and Hsd17b3. Bmal1-/- mice showed severely reduced expression of testicular circadian clock genes at three time points (CT4, CT12, and CT20), and a reduction in mRNA expression levels of Apo (Apoa1, Apoa2, and Apoc3) and steroidogenic (StAR, Cyp11a1, Hsd3b2, and Hsd17b3) genes. Oil Red O staining showed decreased lipid aggregation in the Leydig cells of Bmal1-/- mouse testes. Considering the vital role of Apo genes in high-density lipoprotein formation and cholesterol transport, the present data suggest that the circadian clock system regulates testosterone production by orchestrating the rhythmic expression of Apo genes. These data extend our understanding of the role of the circadian clock in regulating testosterone production in mammals.


Assuntos
Relógios Circadianos , Testosterona , Animais , Apolipoproteínas , Proteínas CLOCK/genética , Ritmo Circadiano , Expressão Gênica , Regulação da Expressão Gênica , Masculino , Camundongos , Testículo
9.
Sci Total Environ ; 785: 147323, 2021 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-33957581

RESUMO

Glyphosate is a broad-spectrum herbicide that impairs testosterone synthesis in mammals. Leydig cells (LCs), the primary producers of testosterone, demonstrate rhythmic expression of circadian clock genes both in vivo and in vitro. The nuclear receptor NR1D1 is an important clock component that constitutes the subsidiary transcriptional/translational loop in the circadian clock system. Nr1d1 deficiency resulted in diminished fertility in both male and female mice. However, whether NR1D1 is involved in the glyphosate-mediated inhibition of testosterone synthesis in LCs remains unclear. Here, the involvement of NR1D1 in glyphosate-mediated inhibition of testosterone synthesis was investigated both in vitro and in vivo. Glyphosate exposure of TM3 cells significantly increased Nr1d1 mRNA levels, but decreased Bmal1, Per2, StAR, Cyp11a1, and Cyp17a1 mRNA levels. Western blotting confirmed elevated NR1D1 and reduced StAR protein levels following glyphosate exposure. Glyphosate exposure also reduced testosterone production in TM3 cells. In primary LCs, glyphosate exposure also upregulated Nr1d1 mRNA levels and downregulated the mRNA levels of other clock genes (Bmal1 and Per2) and steroidogenic genes (StAR, Cyp17a1, Cyp11a1, and Hsd3b2), and inhibited testosterone synthesis. Moreover, glyphosate exposure significantly reduced the amplitude and shortened the period of PER2::LUCIFERASE oscillations in primary LCs isolated from mPer2Luciferase knock-in mice. Four weeks of oral glyphosate upregulated NR1D1 at both the mRNA and protein levels in mouse testes, and this was accompanied by a reduction in StAR expression. Notably, serum testosterone levels were also drastically reduced in mice treated with glyphosate. Moreover, dual-luciferase reporter and EMSA assays revealed that in TM3 cells NR1D1 inhibits the expression of StAR by binding to a canonical RORE element present within its promoter. Together, these data demonstrate that glyphosate perturbs testosterone synthesis via NR1D1 mediated inhibition of StAR expression in mouse LCs. These findings extend our understanding of how glyphosate impairs male fertility.


Assuntos
Relógios Circadianos , Células Intersticiais do Testículo , Animais , Feminino , Glicina/análogos & derivados , Glicina/toxicidade , Masculino , Camundongos , Membro 1 do Grupo D da Subfamília 1 de Receptores Nucleares , Testosterona , Glifosato
10.
J Cell Physiol ; 236(9): 6706-6725, 2021 09.
Artigo em Inglês | MEDLINE | ID: mdl-33598947

RESUMO

Testosterone is produced by Leydig cells (LCs) and undergoes diurnal changes in serum levels in rats, mice, and humans, but little is known in goats. The present study revealed that goat serum testosterone levels displayed diurnal rhythmic changes (peak time at ZT11.2). Immunohistochemical staining showed that BMAL1, a circadian clock protein, is highly expressed in goat LCs. ELISA revealed that both hCG (0-5 IU/ml) and 22R-OH-cholesterol (0-30 µM) addition stimulated testosterone synthesis in primary goat LCs in a dose-dependent manner. Treating goat LCs with hCG (5 IU/ml) significantly increased intracellular cAMP levels. Additionally, real-time quantitative polymerase chain reaction (PCR) analysis revealed that the circadian clock (BMAL1, PER1, PER2, DBP, and NR1D1) and steroidogenesis-related genes (SF1, NUR77, StAR, HSD3B2, CYP17A1, CYP11A1, and HSD17B3) showed rhythmic expression patterns in goat LCs following dexamethasone synchronization. Several Bmal1-Luc circadian oscillations were clearly observed in dexamethasone-treated goat LCs transfected with the pLV6-Bmal1-Luc plasmid. BMAL1 knockdown significantly downregulated mRNA levels of PER2, NR1D1, DBP, StAR, HSD3B2, SF1, NUR77, and GATA4, and dramatically decreased StAR and HSD3B2 protein levels and testosterone production. In contrast, BMAL1 overexpression significantly increased the mRNA and protein expression levels of StAR and HSD17B3 and enhanced testosterone production. Reporter assays revealed that goat BMAL1, or in combination with mouse CLOCK, activated goat HSD17B3 transcription in vitro. These data indicate that BMAL1 contributes to testosterone production by regulating transcription of steroidogenesis-related genes in goat LCs, providing a basis for further exploring the underlying mechanism by which the circadian clock regulates ruminant reproductive capability.


Assuntos
Fatores de Transcrição ARNTL/genética , Relógios Circadianos/genética , Regulação da Expressão Gênica , Cabras/genética , Células Intersticiais do Testículo/metabolismo , Fosfoproteínas/genética , Testosterona/biossíntese , Transcrição Gênica , 17-Hidroxiesteroide Desidrogenases/metabolismo , Fatores de Transcrição ARNTL/metabolismo , Animais , Apoptose/efeitos dos fármacos , Apoptose/genética , Relógios Circadianos/efeitos dos fármacos , Dexametasona/farmacologia , Perfilação da Expressão Gênica , Regulação da Expressão Gênica/efeitos dos fármacos , Técnicas de Silenciamento de Genes , Cabras/sangue , Humanos , Hidroxicolesteróis/metabolismo , Células Intersticiais do Testículo/efeitos dos fármacos , Masculino , Modelos Biológicos , Testosterona/sangue , Transcrição Gênica/efeitos dos fármacos
11.
Org Biomol Chem ; 19(9): 2023-2029, 2021 03 11.
Artigo em Inglês | MEDLINE | ID: mdl-33594399

RESUMO

An efficient silver-catalyzed method of decarboxylative radical allylation of α,α-difluoroarylacetic acids to build CF2-allyl bonds has been developed. Using allylsulfone as an allyl donor, α,α-difluorine substituted arylacetic acids bearing various functional groups are successfully allylated to access a series of 3-(α,α-difluorobenzyl)-1-propylene compounds in moderate to excellent yields in aqueous CH3CN solution under the mild conditions. Experimental studies disclosed that the α-fluorine substitution of arylacetic acid has a great influence on free radical activity and reactivity.

12.
Am J Physiol Endocrinol Metab ; 320(4): E747-E759, 2021 04 01.
Artigo em Inglês | MEDLINE | ID: mdl-33554778

RESUMO

Prostaglandin G/H synthase 2 (PTGS2) is a rate-limiting enzyme in prostaglandin synthesis. The present study assessed the role of the uterine circadian clock on Ptgs2 transcription in response to steroid hormones during early pregnancy. We demonstrated that the core clock genes (Bmal1, Per2, Nr1d1, and Dbp), Vegf, and Ptgs2, and their encoded proteins, have rhythmic expression in the mouse uterus from days 3.5 to 4.5 (D3.5-4.5) of pregnancy. Progesterone (P4) treatment of cultured uterus endometrial stromal cells (UESCs) isolated from mPer2Luciferase reporter gene knock-in mice on D4 induced a phase shift in PER2::LUCIFERASE oscillations. This P4-induced phase shift of PER2::LUCIFERASE oscillations was significantly attenuated by the P4 antagonist RU486. Additionally, the amplitude of PER2::LUCIFERASE oscillations was increased by estradiol (E2) treatment in the presence of P4. Consistently, the mRNA levels of clock genes (Bmal1 and Per2), Vegf, and Ptgs2 were markedly increased by E2 treatment of UESCs in the presence of P4. Treatment with E2 also promoted prostaglandin E2 (PGE2) synthesis by UESCs. Depletion of Bmal1 in UESCs by small-interfering RNA (siRNA) decreased the transcript levels of clock genes (Nr1d1 and Dbp), Vegf, and Ptgs2 compared with nonsilencing siRNA treatment. Bmal1 knockdown also inhibited PGE2 synthesis. Moreover, the mRNA expression levels of clock genes (Nr1d1 and Dbp), Vegf, and Ptgs2, and their respective proteins were significantly decreased in the uterus of Bmal1-/- mice. Thus, these data suggest that Bmal1 in mice promotes PGE2 synthesis by upregulating Ptgs2 in response to increases in E2 on D4 of pregnancy.NEW & NOTEWORTHY Rhythmic expression of Bmal1 and Ptgs2 was observed in the uterus isolated from D3.5-4.5 of pregnant mice. E2 increased the expression of Bmal1 and Ptg2 in UESCs isolated from mice on D4. The expression of Ptgs2 was significantly decreased in Bmal1-siRNA treated UESCs. Bmal1 knockdown also inhibited PGE2 synthesis. Thus, these data suggest that Bmal1 in mice promotes PGE2 synthesis by upregulating Ptgs2 in response to increases in E2 on D4 of pregnancy.


Assuntos
Fatores de Transcrição ARNTL/fisiologia , Ciclo-Oxigenase 2/genética , Dinoprostona/biossíntese , Estradiol/sangue , Fatores de Transcrição ARNTL/genética , Animais , Células Cultivadas , Ciclo-Oxigenase 2/metabolismo , Estradiol/farmacologia , Feminino , Idade Gestacional , Masculino , Camundongos , Camundongos da Linhagem 129 , Camundongos Endogâmicos C57BL , Camundongos Knockout , Gravidez , Progesterona/farmacologia , Ativação Transcricional/efeitos dos fármacos , Útero/efeitos dos fármacos , Útero/metabolismo
13.
J Toxicol Environ Health A ; 84(3): 112-124, 2021 02 01.
Artigo em Inglês | MEDLINE | ID: mdl-33148124

RESUMO

Zearalenone (ZEA), a mycotoxin, is known to impair reproductive capability by disrupting the synthesis and secretion of testosterone by Leydig cells (LCs), although the mechanism is unknown. Robust rhythmicity of circadian clock and steroidogenic genes were identified in LCs. The aim of this study was to examine whether ZEA significantly attenuated the transcription of core clock genes (Bmal1, Dbp, Per2, and Nr1d1) as well as steroidogenic genes (StAR, Hsd3b2, and Cyp11a1) in mouse testis Leydig cell line (TM3). Western blotting confirmed declines in BMAL1, NR1D1, and StAR protein levels. ZEA also suppressed secreted testosterone levels. In primary LCs, isolated from PER2::LUCIFERASE reporter gene knock in mice, ZEA diminished the amplitude of PER2::LUC expression, and induced a phase shift and period extension. In primary LCs, ZEA also suppressed the expression levels of core clock and steroidogenic genes, reduced protein levels of BMAL1, and decreased testosterone secretion. In vivo expression of core clock and steroidogenic genes were reduced in testes of mice exposed to ZEA for 1 week leading to decreased serum testosterone levels. In summary, data suggest that ZEA may impair testosterone synthesis through attenuation of the circadian clock in LCs culminating in reproductive dysfunction in male mammals .


Assuntos
Relógios Circadianos/efeitos dos fármacos , Estrogênios não Esteroides/farmacologia , Células Intersticiais do Testículo/efeitos dos fármacos , Testosterona/metabolismo , Zearalenona/farmacologia , Animais , Células Intersticiais do Testículo/metabolismo , Masculino , Camundongos
14.
Chem Asian J ; 14(16): 2780-2784, 2019 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-31207187

RESUMO

The Acinetobacter sp. strain M isolated from a contaminated soil sample in Jiangsu Province of China was found to be able to degrade perfluorooctane sulfonamide (PFOSA) effectively. Fluoride anion (F- ) released from PFOSA degradation was detected by ion chromatography, and showed positive correlation to the growth curve of Acinetobacter sp. strain M. The PFOSA degradation efficiency of strain M was approximately 27 %, as assessed by GC analysis. It was shown that enzymes localized outside of cells of Acinetobacter sp. strain M catalyzed the degradation of PFOSA. This further indicates a possibly new (multi-step/pathway) mechanism for PFOSA degradation. It revealed that the extracellular enzyme of the Acinetobacter strain M preferentially cleaves carbon-carbon and carbon-fluorine bonds instead of destroying the carbon-sulfur bond. The growth condition for Acinetobacter sp. strain M was optimized at 30 °C and pH 7.0 in the presence of 2000 mg L-1 of PFOSA and 0.5 % (v/v) of Tween-20. The optimal PFOSA degradation time was found to be 12 h, with a degradation efficiency of 76 % by extracellular enzymes in strain M as determined by GC analysis. The result may provide potential applications for biodegradition of perfluoro organic compounds, such as derivatives of perfluorooctane (C8).


Assuntos
Acinetobacter/metabolismo , Enzimas/metabolismo , Fluorocarbonos/metabolismo , Sulfonamidas/metabolismo , Acinetobacter/enzimologia , Acinetobacter/crescimento & desenvolvimento , Cromatografia Gasosa-Espectrometria de Massas , Microbiologia do Solo
15.
Langmuir ; 35(21): 6981-6992, 2019 May 28.
Artigo em Inglês | MEDLINE | ID: mdl-31066284

RESUMO

Mechanical operation could be seriously affected by friction and controlling it by oil lubrication has been considered as an effective way. Good lubricant additives are very necessary to avoid the friction damages, and to find or design new additives is always a challenge. In this study, a systematic investigation of using cholesteryl liquid crystals (LCs) as lubricant additives to obtain exceptional tribological behaviors was performed. In total, four cholesteryl LC compounds were synthesized targetedly and their thermal and mesogenic properties were studied to see the inherent relationship between the mesogenic phases and antifriction and antiwear performance. Through a series of tribological and related tests, including the UMT TriboLab test, three-dimensional optical microscopy, oil film thickness and viscosity tests, etc., the effect of the mesogenic phases and structures of the synthesized cholesteryl LCs on their tribological properties as lubricant additives was investigated and a related mechanism was analyzed. The result showed that within and close to the mesogenic phase temperature ranges, which we called as effective temperature ranges of LC additives ( TEF), the LCs presented better tribological behaviors, meaning they could be used in special lubrication applications that need to be confined in certain temperature scopes; however, the ester groups with long alky tails could help dissolve in base oils and adsorb onto the friction pairs. Among the four LCs, LC-D with a long perfluoroalkyl tail brought widest mesogenic phase with considerably enhanced lubrication performance and increased oil film thickness, viscosity, and thermal stability, indicating that the perfluoroalkyl group could be well used in the structural modification of LC additives to give unexpected tribological performance. This study, in conjunction with our experimental data, suggested that the liquid crystals may be evaluated as potential friction modifiers for temperature-controllable lubrication and also shed a fresh light on the development of novel liquid crystal lubrication materials.

16.
Mol Med Rep ; 16(4): 4068-4074, 2017 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-28765924

RESUMO

A small molecule tetraazacyclododecane-1,4,7,10-tetraacetic acid (Gd­DOTA)4­TPP agent is used to label human mesenchymal stem cells (hMSCs) via electroporation (EP). The present study assessed the cytotoxicity of cell labeling, in addition to its effect on cell differentiation potential. There were no significant adverse effects on cell viability or differentiation induced by either EP or cellular uptake of (Gd­DOTA)4­TPP. Labeled live and dead hMSCs were transplanted into mouse forelimb muscles. T2­weighted magnetic resonance imaging (MRI) was used to track the in vivo fate of the cell transplants. The labeling and imaging strategy allowed long term tracking of the cell transplants and unambiguous distinguishing of the cell transplants from their surrounding tissues. Cell migration was observed for live hMSCs injected into subcutaneous tissues, however not for either live or dead hMSCS injected into limb muscles. A slow clearance process occurred of the dead cell transplants in the limb muscular tissue. The MRI results therefore reveal that the fate and physiological activities of cell transplants depend on the nature of their host tissue.


Assuntos
Morte Celular , Membro Anterior , Imageamento por Ressonância Magnética , Transplante de Células-Tronco Mesenquimais , Células-Tronco Mesenquimais/patologia , Músculo Esquelético/diagnóstico por imagem , Músculo Esquelético/patologia , Animais , Apoptose , Diferenciação Celular , Sobrevivência Celular , Humanos , Imageamento por Ressonância Magnética/métodos , Camundongos , Coloração e Rotulagem
17.
Org Biomol Chem ; 15(25): 5308-5317, 2017 Jun 27.
Artigo em Inglês | MEDLINE | ID: mdl-28613344

RESUMO

A silver-catalyzed oxidative decarboxylative gem-difluoromethylenation of difluoroacetates with activated alkenes under mild reaction conditions has been developed. This radical cascade reaction provides a new method for the construction of a variety of gem-difluoromethylenated oxindoles.

18.
Org Lett ; 19(9): 2406-2409, 2017 05 05.
Artigo em Inglês | MEDLINE | ID: mdl-28430453

RESUMO

An efficient method for the synthesis of the thermally stable and pharmaceutically important gem-difluoromethylene azo compounds is developed. This protocol achieved gem-difluoromethylenation of the nitrogen center of arenediazonium salts through in situ generated benzo-1,3-diazolic difluoromethylene radical addition to arenediazonium salts under mild Ag-initiated conditions.

19.
Chem Commun (Camb) ; 52(8): 1598-601, 2016 Jan 28.
Artigo em Inglês | MEDLINE | ID: mdl-26662493

RESUMO

A mild, versatile and efficient method for the silver(I)-catalyzed oxidative decarboxylative gem-difluoromethylenation has been developed. The radical cascade reaction comprises the addition of an oxidatively generated difluoromethylene radical to the isonitrile functionality and subsequent homolytic aromatic substitution. It provides a novel and efficient access to the C-CF2 bond formation.

20.
Chem Commun (Camb) ; 51(87): 15756-9, 2015 Nov 11.
Artigo em Inglês | MEDLINE | ID: mdl-26313464

RESUMO

Efficient direct gem-difluoromethylenation of an sp(3)-hybridized carbon center in benzyl bromides using benzo-1,3-azolic (oxa-, thia- or aza-) difluoromethyl bromides for construction of a CH2-CF2 linkage has been developed through radical/radical C-C cross-coupling via two separate single electron transfer processes (SET) under the promotion of different copper sources.


Assuntos
Compostos de Benzil/química , Radicais Livres/química , Hidrocarbonetos Fluorados/síntese química , Alquilação , Benzimidazóis/síntese química , Benzotiazóis/síntese química , Benzoxazóis/síntese química , Brometos/química , Catálise , Cobre/química , Óxidos N-Cíclicos/química , Oxirredução
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