ABSTRACT
Experimental elucidation of the decoupling of electron and proton transfer at a molecular level is essential for thoroughly understanding the kinetics of heterogeneous (photo)electrochemical proton-coupled electron transfer water oxidation. Here we illustrate the electron-transfer intermediates of positively charged surface oxygenated species on Au (Au-OH+) and their correlations with the rate of water oxidation by in situ microphotoelectrochemical surface-enhanced Raman spectroscopy (SERS) and ambient-pressure X-ray photoelectron spectroscopy. At the intermediate stage of water oxidation, a characteristic blue shift of the vibration of Au-OH species in laser-power-density-dependent measurements was assigned to the light-induced production of Au-OH+ in water oxidation. The photothermal effect was excluded according to the vibrational frequencies of Au-OH species as the temperature was increased in a variable-temperature SERS measurement. Density functional theory calculations evidenced that the frequency blue shift is from the positively charged Au-OH species. The photocurrent-dependent frequency blue shift indicated that Au-OH+ is the key electron-transfer intermediate in water oxidation by decoupled electron and proton transfer.
ABSTRACT
Molecules based on benzimidazolone-dioxazine are known as blue/violet pigments and have been commercialized for decades. However, unfavorable solubility limits the application of these structures as building blocks of conjugated polymers despite their low band gaps. Herein, a series of donor-acceptor conjugated polymers containing soluble benzimidazolone-dioxazine structures as the acceptors and oligothiophene as donors are synthesized and investigated. With increasing numbers of thiophene rings, the steric hindrance diminishes and high molecular weight polymers can be achieved, leading to an improved performance in organic field effect transistor devices. The hole mobility of polymers with three to six thiophene units is in the order of 10-1 cm2 V-1 s -1 . Among all the polymers, polymer P3 with three thiophene units between benzimidazolone-dioxazine structures shows the best hole mobility of 0.4 cm2 V-1 s -1 . Grazing-incidence wide-angle X-ray scattering results reveal that the high mobility of organic field-effect transistors (OFETs) can be accredited by matched donor-acceptor packing in the solid thin films.
Subject(s)
Bandages , Benzimidazoles , Polymers , ThiophenesABSTRACT
To understand the roles of Au(III) (hydro-)oxides in promoting plasmon-mediated photoelectrochemical (PMPEC) water-oxidation, we employed in situ microphotoelectrochemical surface-enhanced Raman spectroscopy and ambient-pressure x-ray photoelectron spectroscopy to elucidate the correlations between the amount of surface Au(III) (hydro-)oxides and the photocurrent of PMPEC water-oxidation on Au. By applying preoxidation potentials, we made surface Au(III) (hydro-)oxides on a plasmonic Au photoanode. According to the charge of reductively stripping surface oxygenated species before and after PMPEC water-oxidation, we found that a negative shift of an onset potential, increase in photocurrent, and much less growth of surface (hydro-)oxides were correlated with each other as a result of the increase in the coverage of Au (III) (hydro-)oxides. These results suggest that the surface Au(III) (hydro-)oxides kinetically promoted water-oxidation by restricting the growth of surface (hydro-)oxides.
ABSTRACT
Temperature variation at the nanoscale is pivotal for the thermodynamics and kinetics of small entities. Surface-enhanced Raman spectroscopy (SERS) is a promising technique for monitoring temperature variations at the nanoscale. A key but ambiguous topic is methods to design a sensitive SERS thermometer. Here, we elucidate that the type of chemical bond of molecular probes and the surface chemical bonding effect are crucial for maximizing the sensitivity of the SERS thermometer, as illustrated by the variable-temperature SERS measurements and quantum chemistry calculations for the frequency-temperature functions of a series of molecules. The sensitivity of the frequency-temperature function follows the sequence of triple bond > double bond > single bond, which is available for both aliphatic and aromatic molecules. The surface chemical bonding effect between the SERS substrate and molecular probe substantially increases the sensitivity of the frequency-temperature function. These results provide universally available guidelines for the rational design of a sensitive SERS thermometer by examining the functional groups of molecular probes.
Subject(s)
Spectrum Analysis, Raman , Thermometers , Molecular Probes , Spectrum Analysis, Raman/methodsABSTRACT
OBJECTIVES: Adipokine resistin is highly expressed in the serum and synovial uid (SF) of patients with knee osteoarthritis (KOA) but its pathogenic role in KOA remains unclear. We aimed to explore the mechanism of resistin/CAP1 in human KOA chondrocytes. METHODS: We enrolled 103 patients with radiographic KOA and 86 healthy participants as controls. Resistin levels in serum and SF were determined by enzyme-linked immunosorbent assay (ELISA). CAP1 expression was measured in cartilage tissues using immunohistochemistry, quantitative real-time polymerase chain reaction (qRT-PCR), and western blot. Effects of resistin on chondrocytes and CAP1 were evaluated via qRT-PCR and co-immunoprecipitation. The roles of CAP1, p38-MAPK, and NF-κB signalling pathways in KOA development were evaluated using adenovirus-mediated CAP1 short hairpin RNA, qRT-PCR, western blot, and ELISA. RESULTS: Resistin expression in serum and SF was elevated in severe radiographic KOA. CAP1 levels were higher in KOA cartilage and were positively correlated with resistin expression. Resistin promoted CCL3, CCL4, MMP13, and ADAMTS-4 expression through the CAP1 receptor. Resistin also directly bound to CAP1, as confirmed by co-immunoprecipitation. CAP1 knockdown in chondrocytes attenuated resistin-induced expression of CCL3, CCL4, MMP13, and ADAMTS-4 and activated p38-MAPK and NF-κB signalling pathways. CONCLUSIONS: Resistin binds CAP1 and upregulates the expression of proinflammatory cytokines and matrix-degrading enzymes via p38-MAPK and NF-κB signalling in human chondrocytes.
Subject(s)
Chondrocytes , NF-kappa B , Cell Cycle Proteins/metabolism , Cell Cycle Proteins/pharmacology , Cells, Cultured , Chemokines , Chondrocytes/metabolism , Cytoskeletal Proteins/metabolism , Humans , Matrix Metalloproteinases/metabolism , Matrix Metalloproteinases/pharmacology , NF-kappa B/metabolism , Oligopeptides , Resistin , p38 Mitogen-Activated Protein Kinases/metabolismABSTRACT
Eliminating the latent HIV reservoir remains a difficult problem for creating an HIV functional cure or achieving remission. The "block-and-lock" strategy aims to steadily suppress transcription of the viral reservoir and lock the HIV promoter in deep latency using latency-promoting agents (LPAs). However, to date, most of the investigated LPA candidates are not available for clinical trials, and some of them exhibit immune-related adverse reactions. The discovery and development of new, active, and safe LPA candidates for an HIV cure are necessary to eliminate residual HIV-1 viremia through the block-and-lock strategy. In this study, we demonstrated that a new small-molecule compound, Q308, silenced the HIV-1 provirus by inhibiting Tat-mediated gene transcription and selectively downregulating the expression levels of the facilitated chromatin transcription (FACT) complex. Strikingly, Q308 induced the preferential apoptosis in HIV-1 latently infected cells, indicating that Q308 may reduce the size of the viral reservoir and thus further prevent viral rebound. These findings highlight that Q308 is a novel and safe anti-HIV-1 inhibitor candidate for a functional cure.
Subject(s)
HIV Infections , HIV-1 , CD4-Positive T-Lymphocytes , Chromatin , HIV Infections/drug therapy , HIV-1/genetics , Humans , Proviruses/genetics , Virus LatencyABSTRACT
In spinal cord ischemia-reperfusion (I/R) injury, large amounts of reactive oxygen species can cause mitochondrial damage. Therefore, mitophagy acts as the main mechanism for removing damaged mitochondria and protects nerve cells. This study aimed to illustrate the important role of GPCR kinase 2-interacting protein-1 (GIT1) in mitophagy in vivo and in vitro. The level of mitophagy in the neurons of Git1 knockout mice was significantly reduced after ischemia-reperfusion. However, the overexpression of adeno-associated virus with Git1 promoted mitophagy and inhibited the apoptosis of neurons. GIT1 regulated the phosphorylation of Beclin-1 in Thr119, which could promote the translocation of Parkin to the mitochondrial outer membrane. This process was independent of PTEN-induced kinase 1 (PINK1), but it could not rescue the role in the absence of PINK1. Overall, GIT1 enhanced mitophagy and protected neurons against ischemia-reperfusion injury and, hence, might serve as a new research site for the protection of ischemia-reperfusion injury.
Subject(s)
Beclin-1/metabolism , Cell Cycle Proteins/metabolism , GTPase-Activating Proteins/metabolism , Mitophagy , Reperfusion Injury , Spinal Cord Diseases , Ubiquitin-Protein Ligases/metabolism , Animals , Beclin-1/genetics , Cell Cycle Proteins/genetics , GTPase-Activating Proteins/genetics , Mice , Mice, Knockout , Protein Kinases/genetics , Protein Kinases/metabolism , Reperfusion Injury/genetics , Reperfusion Injury/metabolism , Reperfusion Injury/pathology , Reperfusion Injury/prevention & control , Spinal Cord Diseases/genetics , Spinal Cord Diseases/metabolism , Spinal Cord Diseases/pathology , Spinal Cord Diseases/prevention & control , Ubiquitin-Protein Ligases/geneticsABSTRACT
The rational design and applications of plasmon-mediated chemical reactions (PMCRs) are fundamentally determined by an understanding of photon-electron-molecule interactions. However, the current understanding of the PMCR of plasmon-decayed hot electron-mediated reactions remains implicit, since there has not been a single measurement of both hot-electron transfer and molecular transformation following photon excitation. Therefore, we invented a method called microphotoelectrochemical surface-enhanced Raman spectroscopy (µPEC-SERS) that uses an ultramicroelectrode (UME) whose dimensions match those of the focused laser spot. This system can simultaneously record the photocurrent (â¼picoamps) of hot-electron transfer with a high signal-to-noise ratio and the SERS spectra of a molecular reaction in the same electrode area. The responses of the photocurrent and SERS spectra to laser illumination can correlate the surface reaction activated by hot electrons with the SERS spectral changes. A typical PMCR of p-aminothiophenol (PATP) on a Ag UME was used to illustrate that the correlation of the photocurrent with the spectral changes is capable of revealing the reaction mechanism in terms of the formation of activated oxygenated species. The laser power-, laser wavelength-, and surface roughness-dependent photocurrents link the formation of activated oxygenated species to the hot-electron transfer. Further comparisons of the photocurrent with the conventional electrochemical current of the oxygen reduction reaction indicate that the activated oxygenated species are oxidative in transforming PATP to p,p'-dimercaptoazobenzene, which is supported by a density functional theory (DFT) calculation. Therefore, µPEC-SERS could be a powerful tool for investigating PMCRs and other systems involving photon-electron-molecule interactions.
ABSTRACT
Surface plasmons (SPs) originating from the collective oscillation of conduction electrons in nanostructured metals (Au, Ag, Cu, etc.) can redistribute not only the electromagnetic fields but also the excited carriers (electrons and holes) and heat energy in time and space. Therefore, SPs can engage in a variety of processes, such as molecular spectroscopy and chemical reaction. Recently, plenty of demonstrations have made plasmon-mediated chemical reactions (PMCRs) a very active research field and make it as a promising approach to facilitate light-driven chemical reactions under mild conditions. Concurrently, making use of the same SPs, surface-enhanced Raman spectroscopy (SERS) with a high surface sensitivity and energy resolution becomes a powerful and commonly used technique for the in situ study of PMCRs. Typically, various effects induced by SPs, including the enhanced electromagnetic field, local heating, excited electrons, and excited holes, can mediate chemical reactions. Herein, we use the para-aminothiophenol (PATP) transformation as an example to elaborate how SERS can be used to study the mechanism of PMCR system combined with theoretical calculations. First, we distinguish the chemical transformation of PATP to 4,4'-dimercaptoazobenzene (DMAB) from the chemical enhancement mechanism of SERS through a series of theoretical and in situ SERS studies. Then, we focus on disentangling the photothermal, hot electrons, and "hot holes" effects in the SPs-induced PATP-to-DMAB conversion. Through varying the key reaction parameters, such as the wavelength and intensity of the incident light, using various core-shell plasmonic nanostructures with different charge transfer properties, we extract the key factors that influence the efficiency and mechanism of this reaction. We confidently prove that the transformation of PATP can occur on account of the oxygen activation induced by the hot electrons or because of the action of hot holes in the absence of oxygen and confirm the critical effect of the interface between the plasmonic nanostructure and reactants. The products of these two process are different. Furthermore, we compare the correlation between PMCRs and SERS, discuss different scenario of PMCRs in situ studied by SERS, and provide some suggestions for the SERS investigation on the PMCRs. Finally, we comment on the mechanism studies on how to distinguish the multieffects of SPs and their influence on the PMCRs, as well as on how to power the chemical reaction and regulate the product selectivity in higher efficiencies.
ABSTRACT
To turn on the fluorescence of the native green fluorescence protein (GFP) chromophore, 4-hydroxybenzylidene-dimethylimidazolinone (HBDI), in an artificial supramolecular system has been a challenging task, because it requires high local environmental rigidity. This work shows that the formation of H-aggregates of an HBDI-containing organogelator results in two orders of magnitude fluorescence enhancement (Φf =2.9 vs. 0.02 %), in which the inter-HBDI OHâ â â OH H-bonds play a crucial role. The aggregation-induced fluorescence enhancement of HBDI has important implications on the origin of the high fluorescence quantum efficiency of HBDI in the GFP ß-barrel and on the supramolecular strategy for a full fluorescence recovery of HBDI. These results reveal a new approach to designing rigid chromophore aggregates for high-performance optoelectronic properties.
Subject(s)
Green Fluorescent Proteins/chemistry , Fluorescence , Hydrogen Bonding , Molecular StructureABSTRACT
ß1,4-GalT1 is a type II membrane glycosyltransferase. It catalyzes the production of lactose in the lactating mammary gland and is supposedly also involved in the galactosylation of terminal GlcNAc of complex-type N-glycans. In-vitro studies of the bovine ß4Gal-T1 homolog showed that replacing a single residue of tyrosine with leucine at position 289 alters the donor substrate specificity from UDP-Gal to UDP-N-acetyl-galactosamine (UDP-GalNAc). The effect of this peculiar change in ß1,4GalT1 specificity was investigated in-vivo, by generating biallelic Tyr286Leu ß1,4GalT1 mice using CRISPR/Cas9 and crossbreeding. Mice bearing this mutation showed no appreciable defects when compared to wild-type mice, with the exception of biallelic female B4GALT1 mutant mice, which were unable to produce milk. The detailed comparison of wild-type and mutant mice derived from liver, kidney, spleen, and intestinal tissues showed only small differences in their N-glycan pattern. Comparable N-glycosylation was also observed in HEK 293 wild-type and knock-out B4GALT1 cells. Remarkably and in contrast to the other analyzed tissue samples, sialylation and galactosylation of serum N-glycans of biallelic Tyr286Leu GalT1 mice almost disappeared completely. These results suggest that ß1,4GalT1 plays a special role in the synthesis of serum N-glycans. The herein described Tyr286Leu ß1,4GalT1 mutant mouse model may, therefore, prove useful in the investigation of the mechanism which regulates tissue-dependent galactosylation.
Subject(s)
Galactose/metabolism , Galactosyltransferases/genetics , Polysaccharides/blood , Animals , Cattle , Female , Galactosyltransferases/metabolism , Glycosylation , HEK293 Cells , Humans , Lactation/genetics , Mice , Polymorphism, Single Nucleotide/genetics , Polysaccharides/genetics , Substrate SpecificityABSTRACT
BACKGROUND: The incidence of patient dissatisfaction due to anterior knee pain (AKP) and patellar crepitus after total knee arthroplasty (TKA) remains a concern. However, it has been shown that improvements in the femoral component of traditional prostheses could reduce these instances of pain in the case of TKA performed with patellar resurfacing. This study aims to investigate whether TKA without patellar resurfacing can also benefit from the aforementioned femoral component modification in reducing AKP and patellar crepitus post-TKA. METHODS: Sixty-two patients (85 knees) who underwent TKA using the modern prosthesis and 62 age- and sex-matched patients (90 knees) fitted with the traditional prosthesis were enrolled in this study. The occurrence of AKP and patellar crepitus as well as the Knee Society Score (KSS) were consequently recorded, and the data was analyzed in order to determine whether there was a statistically significant difference between the two groups. RESULTS: The incidence of AKP was significantly lower in the study group compared with the control group at the 3-month and 1-year follow-ups (4.7% vs. 13.3% [p = 0.048] and 3.5% vs. 13.3% [p = 0.021], respectively). In addition, the incidence of patellar crepitus was also significantly lower in the study group compared with the control group at the 3-month and 1-year follow-ups (15.3% vs. 34.4% [p = 0.004] and 10.6% vs. 28.9% [p = 0.002], respectively). There was no significant difference in the KSS between the two groups. CONCLUSIONS: These results revealed that TKA without patellar resurfacing will indeed benefit from the modified femoral implant design in reducing AKP and patellar crepitus, a finding that may be beneficial to surgeons who select implants for their patients when patellar resurfacing is not planned or not possible due to other reasons.
Subject(s)
Arthroplasty, Replacement, Knee/adverse effects , Knee Prosthesis/adverse effects , Postoperative Complications/prevention & control , Prosthesis Design , Aged , Arthroplasty, Replacement, Knee/instrumentation , Case-Control Studies , China , Female , Femur/surgery , Humans , Knee Joint/surgery , Male , Middle Aged , Pain/prevention & control , Patella/surgery , Postoperative Complications/epidemiology , Postoperative Complications/etiology , Prospective Studies , Range of Motion, Articular , Treatment OutcomeABSTRACT
Recombinant therapeutic proteins are becoming very important pharmaceutical agents for treating intractable diseases. Most biopharmaceutical proteins are produced in mammalian cells because this ensures correct folding and glycosylation for protein stability and function. However, protein production in mammalian cells has several drawbacks, including heterogeneity of glycans attached to the produced protein. In this study, we established cell lines with high-mannose-type N-linked, low-complexity glycans. We first knocked out two genes encoding Golgi mannosidases (MAN1A1 and MAN1A2) in HEK293 cells. Single knockout (KO) cells did not exhibit changes in N-glycan structures, whereas double KO cells displayed increased high-mannose-type and decreased complex-type glycans. In our effort to eliminate the remaining complex-type glycans, we found that knocking out a gene encoding the endoplasmic reticulum mannosidase I (MAN1B1) in the double KO cells reduced most of the complex-type glycans. In triple KO (MAN1A1, MAN1A2, and MAN1B1) cells, Man9GlcNAc2 and Man8GlcNAc2 were the major N-glycan structures. Therefore, we expressed two lysosomal enzymes, α-galactosidase-A and lysosomal acid lipase, in the triple KO cells and found that the glycans on these enzymes were sensitive to endoglycosidase H treatment. The N-glycan structures on recombinant proteins expressed in triple KO cells were simplified and changed from complex types to high-mannose types at the protein level. Our results indicate that the triple KO HEK293 cells are suitable for producing recombinant proteins, including lysosomal enzymes with high-mannose-type N-glycans.
Subject(s)
Gene Expression , Gene Knockdown Techniques , Golgi Apparatus/enzymology , Mannosidases , Glycosylation , Golgi Apparatus/genetics , HEK293 Cells , Humans , Mannosidases/genetics , Mannosidases/metabolism , Recombinant Proteins/biosynthesis , Recombinant Proteins/geneticsABSTRACT
BACKGROUND: The diversity of avian eggshell colour plays important biological roles in ensuring successful reproduction. Eggshell colour is also an important trait in poultry, but the mechanisms underlying it are poorly understood in ducks. This study aimed to provide insights into the mechanism of blue-green eggshell colour generation. RESULTS: Here, white-shelled ducks (HBR) and blue-green-shelled ducks (HQR) were selected from Putian black ducks, and white-shelled ducks (BBR) were selected from Putian white ducks. Transcriptional changes in the shell gland were analysed using RNA-sequencing on the Illumina HiSeq 2500. Twenty-seven individual cDNA libraries were sequenced and generated an average of 7.35 million reads per library; 70.6% were mapped to the duck reference genome, yielding an average of 13,794 genes detected, which accounted for approximately 86.39% of all 15,967 annotated duck genes. A total of 899 differentially expressed genes (DEGs) were detected between the HQR and BBR groups, and 373 DEGs were detected between the HQR and HBR groups. We analysed the DEGs in the HQR-vs-BBR and HQR-vs-HBR comparisons. None of these DEGs were directly involved in the eggshell pigmentation process in HQR-vs-HBR, while UDP-glucuronosyltransferase 2A2 (UGT2A2) and UDP-glucuronosyltransferase 1-1-like (UGT1-1-like), which participate in biliverdin breakdown, were two of the DEGs in HQR-vs-BBR. In the RT-qPCR results, delta-aminolevulinic acid synthase 1 (ALAS1) and EPRS glutamyl-prolyl-tRNA synthetase were significantly upregulated in the HBR group compared with the HQR and BBR groups (P < 0.05). Haem oxygenase (HMOX1) was significantly downregulated in BBR compared with HQR and HBR (P < 0.05). Biliverdin reductase A (BLVRA), GUSB glucuronidase beta, cytochrome c-type haem lyase, protohaem IX farnesyltransferase and UGT2A2 were significantly upregulated in HBR and BBR compared with HQR (P < 0.05). CONCLUSIONS: We conducted a comparative transcriptome analysis of the shell glands of Putian white ducks and Putian black ducks. None of the differentially regulated pathways were directly involved in the eggshell pigmentation process in the HQR-vs-HBR comparison, while 2 DEGs related to biliverdin breakdown were found in HQR-vs-BBR. Based on the RT-qPCR results, we can speculate that both HQR and HBR can produce biliverdin, but HBR cannot accumulate it. Compared with HQR, BBR produced less biliverdin and did not accumulate it.
Subject(s)
Avian Proteins/genetics , Ducks/genetics , Egg Shell/metabolism , Pigmentation/genetics , Sequence Analysis, RNA/methods , Animals , Color , Ducks/classification , Egg Shell/chemistry , Gene Expression Profiling/methods , Molecular Sequence Annotation , Phenotype , Signal Transduction/genetics , Transcriptome/geneticsABSTRACT
Surface plasmons (SPs) are able to promote chemical reactions through the participation of the energetic charge carriers produced following plasmons decay. Using p-aminothiophenol (PATP) as a probe molecule, we used surface-enhanced Raman spectroscopy to follow the progress of its transformation, in situ, to investigate systematically the role of hot electrons and holes. The energetic carrier mediated PATP oxidation was found to occur even in the absence of oxygen, and was greatly influenced by the interface region near the gold surface. The observed reaction, which occurred efficiently on Au@TiO2 nanostructures, did not happen on bare gold nanoparticles (NPs) or core-shell nanostructures when a silicon oxide layer blocked access to the gold. Moreover, the product of the PATP oxidation with oxygen on Au@TiO2 nanostructures differed from what was obtained without oxygen, suggesting that the mechanism through which "hot holes" mediated the oxidation reaction was different from that operating with oxygen activated by hot electrons.
ABSTRACT
Platinum plays a central role in a variety of electrochemical devices and its practical use depends on the prevention of electrode degradation. However, understanding the underlying atomic processes under conditions of repeated oxidation and reduction inducing irreversible surface structure changes has proved challenging. Here, we examine the correlation between the evolution of the electrochemical signal of Pt(111) and its surface roughening by simultaneously performing cyclic voltammetry and in situ electrochemical scanning tunnelling microscopy (EC-STM). We identify a 'nucleation and early growth' regime of nanoisland formation, and a 'late growth' regime after island coalescence, which continues up to at least 170 cycles. The correlation analysis shows that each step site that is created in the 'late growth' regime contributes equally strongly to both the electrochemical and the roughness evolution. In contrast, in the 'nucleation and early growth' regime, created step sites contribute to the roughness, but not to the electrochemical signal.
ABSTRACT
Objective: To evaluate the expression levels of adipokines in the synovium and infrapatellar fat pad (IPFP) in osteoarthritis (OA) patients with and without metabolic syndrome (MetS). Methods: 120 female patients with OA were enrolled, and 60 healthy women matched body mass index, age, and sex, served as controls. Adipokines levels were measured using a sandwich enzyme-linked immunosorbent assay of the serum of all participants and synovial fluid (SF) of OA patients. Local expression levels of adipokines in the synovium and IPFP were examined by immunohistochemical analysis. The amount of adipokine proteins was analyzed using Western blot, and adipokine mRNA expressions were determined via quantitative real-time polymerase chain reaction (qRT-PCR). Results: Serum leptin levels were significantly higher in the non-MetS-OA group than those in controls (7.97 vs. 4.24 ng/ml, p< 0.001), and even higher leptin levels were found in the MetS-OA group (19.05 ng/ml; p< 0.001 for both). Serum adiponectin levels were significantly lower in the MetS-OA group than those in controls (8.09 vs. 10.07 µg/ml, respectively; p= 0.001). The synovium and IPFP in the MetS-OA group secreted more leptin and less adiponectin than those in the non-MetS-OA group (Leptin: 5.32 vs. 1.28 in synovium, respectively; p= 0.028; 6.44 vs. 0.88 in IPFP, respectively; p= 0.017. Adiponectin: 1.12 vs. 0.12 in synovium, respectively; p= 0.042; 1.07 vs. 0.09 in IPFP, respectively; p= 0.027). Resistin expression levels in the serum, SF, and articular tissues were similar among the groups. Conclusions: Expressions of adipokines were different in the synovium and IPFP of OA patients with and without MetS.
Subject(s)
Adiponectin/biosynthesis , Adipose Tissue/metabolism , Gene Expression Regulation , Knee Joint/metabolism , Leptin/biosynthesis , Metabolic Syndrome/metabolism , Osteoarthritis, Knee/metabolism , Synovial Membrane/metabolism , Adipose Tissue/pathology , Aged , Female , Humans , Knee Joint/pathology , Male , Metabolic Syndrome/complications , Metabolic Syndrome/pathology , Middle Aged , Osteoarthritis, Knee/complications , Osteoarthritis, Knee/pathology , Synovial Membrane/pathologyABSTRACT
Five ferrocene alkymethylimidazolium cations 1aâ»1d and 2 with different alkyl spacer lengths were reinvestigated using voltammetry and density functional theory (DFT) calculations. The voltammetric responses of ligand 2 toward various anions are described in detail. An interesting and unprecedented finding from both experimental and theoretical studies is that coupled electron and intramolecular anion (F-) transfer may be present in these molecules. In addition, it was also observed that, in these studied molecules, the electrostatic attraction interaction toward F- would effectively vanish beyond 1 nm, which was previously reported only for cations.
Subject(s)
Ferrous Compounds/chemistry , Imidazoles/chemistry , Metallocenes/chemistry , Anions/chemistry , Crystallography, X-Ray , Density Functional Theory , Electrochemical Techniques , Molecular StructureABSTRACT
BACKGROUND/PURPOSE: To analyze the real-world clinical practice for the treatment of psoriatic arthritis (PsA) and to assess physicians' prescription, difficulties in diagnosis, therapeutic strategy, rationales for biologic therapies and unmet needs in Taiwan. METHODS: We conducted a nationwide cross-sectional observational study by face-to-face in depth interviews with 50 rheumatologists and 30 dermatologists who took care of patients with PsA. RESULTS: The major procedures for recognizing PsA included joint, skin and nail examinations, radiographic imaging, and medical history. More dermatologists established the diagnosis when psoriatic patients with arthritis didn't present with rheumatoid factors (p < 0.05). For milder arthritis, physicians tended to prescribe etanercept in combination with conventional disease-modifying antirheumatic drugs (DMARDs). The efficacy, safety, retention rate, and non-parenteral administration are the major concerns of physicians which are also the primary unmet needs in the current management of PsA. CONCLUSION: This survey showed the status quo in Taiwan of the clinical management for PsA including diagnostic difficulties, therapeutic consideration, rationales for biologic DMARDs selection and unmet needs in treatment. It has indicated that interdisciplinary collaboration may further improve the quality for PsA care. These results may help establish new strategy to develop next generation biologics.
Subject(s)
Arthritis, Psoriatic/drug therapy , Antirheumatic Agents/adverse effects , Antirheumatic Agents/therapeutic use , Arthritis, Psoriatic/diagnosis , Cross-Sectional Studies , Humans , PhysiciansABSTRACT
Nanoscience and nanotechnology shows immense interest in various areas of research and applications, including biotechnology, biomedical sciences, nanomedicine, and veterinary medicine. Studies and application of nanotechnology was explored very extensively in the human medical field and also studies undertaken in rodents extensively, still either studies or applications in veterinary medicine is not up to the level when compared to applications to human beings. The application in veterinary medicine and animal production is still relatively innovative. Recently, in the era of health care technologies, Veterinary Medicine also entered into a new phase and incredible transformations. Nanotechnology has tremendous and potential influence not only the way we live, but also on the way that we practice veterinary medicine and increase the safety of domestic animals, production, and income to the farmers through use of nanomaterials. The current status and advancements of nanotechnology is being used to enhance the animal growth promotion, and production. To achieve these, nanoparticles are used as alternative antimicrobial agents to overcome the usage alarming rate of antibiotics, detection of pathogenic bacteria, and also nanoparticles being used as drug delivery agents as new drug and vaccine candidates with improved characteristics and performance, diagnostic, therapeutic, feed additive, nutrient delivery, biocidal agents, reproductive aids, and finally to increase the quality of food using various kinds of functionalized nanoparticles, such as liposomes, polymeric nanoparticles, dendrimers, micellar nanoparticles, and metal nanoparticles. It seems that nanotechnology is ideal for veterinary applications in terms of cost and the availability of resources. The main focus of this review is describes some of the important current and future principal aspects of involvement of nanotechnology in Veterinary Medicine. However, we are not intended to cover the entire scenario of Veterinary Medicine, despite this review is to provide a glimpse at potential important targets of nanotechnology in the field of Veterinary Medicine. Considering the strong potential of the interaction between the nanotechnology and Veterinary Medicine, the aim of this review is to provide a concise description of the advances of nanotechnology in Veterinary Medicine, in terms of their potential application of various kinds of nanoparticles, secondly we discussed role of nanomaterials in animal health and production, and finally we discussed conclusion and future perspectives of nanotechnology in veterinary medicine.