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1.
Environ Sci Technol ; 58(20): 8889-8898, 2024 May 21.
Article in English | MEDLINE | ID: mdl-38685194

ABSTRACT

The slow reaction rates to chemical and photochemical degradation are well-known properties of plastics. However, large plastic surfaces exposed to environmental conditions release particles and compounds that affect ecosystems and human health. The aim of this work was to identify compounds associated with the degradation of polyethylene (PE), polystyrene (PS), and polyvinyl chloride (PVC) microplastics (markers) on silica and sand and evaluate their use to screen microplastics on natural sand. Products were identified by using targeted and untargeted LC-HRMS analysis. All polymers underwent chemical oxidation on silica. PE released dicarboxylic acids (HO2C-(CH2)n-CO2H (n = 4-30), while PS released cis/trans-chalcone, trans-dypnone, 3-phenylpropiophenone, and dibenzoylmethane. PVC released dicarboxylic acids and aromatic compounds. Upon irradiation, PE was stable while PS released the same compounds as under chemical oxidation but at lower yields. Under the above condition, PVC generated HO2C-[CH2-CHCl]n-CH2-CO2H and HO2C-[CH2-CHCl]n-CO2H (n = 2-19) dicarboxylic acids. The same products were detected on sand but at a lower concentration than on silica due to better retention within the pores. Detection of markers of PE and PS on natural sand allowed us to screen microplastics by following a targeted analysis. Markers of PVC were not detected before or after thermal/photo-oxidation due to the low release of compounds and limitations associated with surface exposure/penetration of radiation.


Subject(s)
Microplastics , Plastics , Polyethylene/chemistry , Environmental Monitoring , Environmental Biomarkers
2.
Ann Thorac Surg ; 117(2): 370-377, 2024 Feb.
Article in English | MEDLINE | ID: mdl-37774760

ABSTRACT

BACKGROUND: Studies that have assessed the Rastelli and Nikaidoh operations for transposition of the great arteries (TGA) with obstructed left ventricular outflow tract obstruction (LVOTO) have not fully evaluated the anatomic drivers that may contribute to surgical selection. We present our procedural selection process for optimizing outcomes of complex TGA in the modern era. METHODS: This is a single-center, retrospective study that included pediatric patients who underwent either a Nikaidoh or Rastelli operation for the treatment of TGA-LVOTO, congenitally corrected TGA-LVOTO, or double-outlet right ventricle TGA type-LVOTO from June 2004 to June 2021. RESULTS: There were 34 patients stratified by Nikaidoh (n = 16) or Rastelli (n = 18) operation. The incidence of all postoperative complications and mortality was low, and the incidence of complications between the groups was similar. Patients were more likely to have undergone a Nikaidoh than a Rastelli if they had a pulmonary annulus >5 mm (87.5% vs 11.1%), anteriorly/posteriorly oriented great vessels (88% vs 8%), remote (80% vs 11%) or restrictive (75% vs 6%) ventricular septal defect, and right ventricular hypoplasia (50% vs 0%; all, P < .05). The resulting rates of reoperation were similar between the groups (44.0% vs 37.5%; P = .24) and largely composed of conduit replacements in the Rastelli patients and valvular repairs or replacements in the Nikaidoh group. Rates of catheter-based interventions were also similar. CONCLUSIONS: These findings suggest that for the optimal treatment of conotruncal anomalies with discordant ventriculoarterial connections, procedural selection should be based on pathoanatomic criteria that can ensure patients undergo the operation most suited to their anatomy.


Subject(s)
Transposition of Great Vessels , Ventricular Outflow Obstruction, Left , Ventricular Outflow Obstruction , Child , Humans , Infant , Transposition of Great Vessels/complications , Transposition of Great Vessels/surgery , Retrospective Studies , Treatment Outcome , Ventricular Outflow Obstruction/complications
3.
Physiol Behav ; 272: 114378, 2023 Dec 01.
Article in English | MEDLINE | ID: mdl-37858914

ABSTRACT

Chemical cues provide potential mates with information about reproductive status and resource-holding potential. In the Mozambique tilapia (Oreochromis mossambicus), males can distinguish female reproductive status through chemical cues, and accessibility of males to females depends on their position in the hierarchy, determined in part by chemical cues. Here, we hypothesized that tilapia faecal cues are attractive to conspecifics once released into the water. C18 solid-phase extracts of faeces from dominant males and pre-ovulatory females evoked stronger olfactory epithelium electrical responses (EOG) than, respectively, subordinate males and post-spawning females. Mass spectrometry of the reverse-phase C18 high-performance liquid chromatography fractions of these extracts with highest EOG, identified by amino acids and bile acids. Faeces from pre-ovulatory females contain significantly higher concentrations of cholic acid (CA) and taurocholic acid (TCH) than both post-spawning females and males. A pool of amino acids had no effect on aggression or attraction in males. However, males were attracted to the scent of pre-ovulatory female faeces, as well as CA and TCH, when applied separately. This attraction was accompanied by increased digging behaviour compared to the odour of post-spawning females. CA and TCH exert their action through separate receptor mechanisms. These findings are consistent with a role for faeces - and bile acids therein - in chemical communication in this species, acting as an attractant for males to reproductive females.


Subject(s)
Tilapia , Animals , Male , Female , Tilapia/physiology , Bile Acids and Salts , Reproduction/physiology , Odorants , Amino Acids
4.
Mar Drugs ; 21(6)2023 May 25.
Article in English | MEDLINE | ID: mdl-37367645

ABSTRACT

Tetrodotoxin (TTX) and its analogues are naturally occurring toxins historically responsible for human poisoning fatalities in Eastern Asia. It is typically linked to the consumption of pufferfish and, to a lesser extent, marine gastropods and crabs. In the scope of a comprehensive project to understand the prevalence of emergent toxins in edible marine organisms, we report, for the first time, the detection of TTX analogues in the soft tissues of edible crabs, the European fiddler crab (Afruca tangeri) and green crab (Carcinus maenas), harvested in southern Portugal. No TTX was detected in the analyzed samples. However, three TTX analogues were detected-an unknown TTX epimer, deoxyTTX, and trideoxyTTX. These three analogues were found in the European fiddler crab while only trideoxyTTX was found in the green crab, suggesting that the accumulation of TTX analogues might be influenced by the crabs' different feeding ecology. These results highlight the need to widely monitor TTX and its analogues in edible marine species in order to provide adequate information to the European Food Safety Authority and to protect consumers.


Subject(s)
Brachyura , Gastropoda , Animals , Humans , Tetrodotoxin/analysis , Seafood , Food Safety
5.
Plants (Basel) ; 12(6)2023 Mar 21.
Article in English | MEDLINE | ID: mdl-36987082

ABSTRACT

Susceptibility to the severe Citrus tristeza virus (CTV), T36, is higher for Citrus macrophylla (CM) than for C. aurantium (CA). How host-virus interactions are reflected in host physiology is largely unknown. In this study, the profile of metabolites and the antioxidant activity in the phloem sap of healthy and infected CA and CM plants were evaluated. The phloem sap of quick decline (T36) and stem pitting (T318A) infected citrus, and control plants was collected by centrifugation, and the enzymes and metabolites analyzed. The activity of the antioxidant enzymes, superoxide dismutase (SOD) and catalase (CAT), in infected plants increased significantly in CM and decreased in CA, compared to the healthy controls. Using LC-HRMS2 a metabolic profile rich in secondary metabolites was assigned to healthy CA, compared to healthy CM. CTV infection of CA caused a drastic reduction in secondary metabolites, but not in CM. In conclusion, CA and CM have a different response to severe CTV isolates and we propose that the low susceptibility of CA to T36 may be related to the interaction of the virus with the host's metabolism, which reduces significantly the synthesis of flavonoids and antioxidant enzyme activity.

6.
Sensors (Basel) ; 23(4)2023 Feb 10.
Article in English | MEDLINE | ID: mdl-36850608

ABSTRACT

A refractive index sensor based on an on-chip silicon nitride (Si3N4) ridge waveguide long-range surface plasmon polariton (LRSPP) is theoretically designed. The waveguide sensor consists of a gold film to enable the plasmonic resonance on top of a Cytop polymer layer. A proper finite element method was used to design and optimize the geometric parameters at the optical wavelength of 633 nm. In addition, the spectral performance was evaluated using the transfer matrix method from 580 to 680 nm. The redshifted interference spectrum results from an increasing analyte refractive index. The sensitivities of 6313 dB/cm/RIU and 251.82 nm/RIU can be obtained with a 400 nm wide and 25 nm thick Au layer. The proposed sensor has the potential for point-of-care applications considering its compactness and simplicity of construction.

7.
Rheumatology (Oxford) ; 62(11): 3627-3635, 2023 11 02.
Article in English | MEDLINE | ID: mdl-36847423

ABSTRACT

OBJECTIVES: The treatment target in SLE should be maintained stable by preventing flares. The objectives were to identify predictors of flare in patients attaining lupus low disease activity state (LLDAS), and to assess whether remission with no glucocorticoids is associated with lower risk of flares. METHODS: This was a cohort study of SLE patients followed in a referral centre over 3 years. Baseline was the first visit where each patient attained LLDAS. Flares up to 36 months' follow-up were identified by three instruments: revised Safety of Estrogen in Lupus Erythematosus National Assessment (SELENA) Flare Index (r-SFI), SLEDAI-2000 (SLEDAI-2K) and SLE Disease Activity Score (SLE-DAS). Demographic, clinical and laboratory parameters at baseline were evaluated as predictors of flare, with distinct models for each flare instrument, using survival analysis with univariate followed by multivariate Cox regression. Hazard ratios (HR) were determined with 95% CI. RESULTS: A total of 292 patients fulfilling LLDAS were included. Over follow-up, 28.4%, 24.7% and 13.4% of the patients developed one or more flare, according to r-SFI, SLE-DAS and SLEDAI-2K definitions, respectively. After multivariate analysis, the predictors of SLE-DAS flares were presence of anti-U1-ribonucleoprotein (anti-U1RNP) (HR = 2.16, 95% CI 1.30, 3.59), SLE-DAS score at baseline (HR = 1.27, 95% CI 1.04, 1.54) and immunosuppressants (HR = 2.43, 95% CI 1.43, 4.09). These predictors were equally significant for r-SFI and SLEDAI-2K flares. Remitted patients with no glucocorticoids presented a lower risk of SLE-DAS flares (HR = 0.60, 95% CI 0.37, 0.98). CONCLUSION: In patients with LLDAS, anti-U1RNP, disease activity scored by SLE-DAS and SLE requiring maintenance immunosuppressants predict higher risk of flare. Remission with no glucocorticoids is associated with lower risk of flares.


Subject(s)
Lupus Erythematosus, Systemic , Humans , Cohort Studies , Lupus Erythematosus, Systemic/drug therapy , Lupus Erythematosus, Systemic/complications , Follow-Up Studies , Immunosuppressive Agents/therapeutic use , Glucocorticoids/therapeutic use , Severity of Illness Index
8.
Article in English | MEDLINE | ID: mdl-36441669

ABSTRACT

Tetrodotoxin (TTX) is a potent neurotoxin responsible for a human intoxication event in Spain associated with the consumption of trumpet shell Charonia lampas. In Europe, TTX is not regulated or monitored, and there is little knowledge about its presence in seafood. Here, we investigated the tissue distribution of TTX and analogues in three specimens of trumpet shell C. lampas bought in a market in southern Portugal. Toxin concentration was above the EFSA recommended limit in the non-edible tissues of all specimens and within the limit in the edible tissues of two specimens. 4,9-AnhydroTTX and 13 additional TTX analogues were detected in tissues, the most abundant being anhydrotrideoxyTTX and trideoxyTTX. These results suggest that although thorough evisceration may lower the amount of TTX consumed, it may not be sufficient to ensure consumer safety. Regular monitoring of TTX and analogues in trumpet shell and other edible gastropods is therefore recommended to avoid poisoning incidents.


Subject(s)
Gastropoda , Animals , Humans , Tetrodotoxin , Neurotoxins , Europe , Spain
9.
Mar Drugs ; 20(11)2022 Oct 28.
Article in English | MEDLINE | ID: mdl-36355003

ABSTRACT

Saxitoxin and its more than 50 analogues are a group of naturally occurring neurotoxins collectively designated as paralytic shellfish toxins (PSTs). PSTs are toxic to humans and maximum legal limits in seafood have been implemented by regulatory authorities worldwide. In the European Union, monitoring of PSTs is performed using the AOAC Official Method 2005.06, based on liquid chromatography coupled with fluorescence detection (LC- FLD). However, this method has been suggested to not effectively detect the emerging C-11 hydroxyl (M-toxins) and benzoate (GC-toxins) analogues, with these analogues currently not being surveyed in monitoring programs. In this study, a liquid chromatography-high resolution mass spectrometry (LC-HRMS) method was used to search for these emerging PSTs in mussels, Mytilus galloprovincialis, contaminated following an intense Gymnodinium catenatum bloom in the Tagus estuary (Lisbon, Portugal). Five M-toxins (M1, M2, M6, dcM6, and dcM10), but no GC-toxins, were detected in the mussels' whole-soft body tissue. Moreover, the classical PSTs (C1 to C4, GTX 4 to GTX6, dcGTX1 to dcGTX4, dcSTX, dcNEO, and STX) were also found and comprised the largest fraction of the PSTs' profile. The presence of unregulated PSTs in edible mussel samples suggests potential seafood safety risks and urges further research to determine the frequency of these analogues in seafood and their contribution to toxicity.


Subject(s)
Dinoflagellida , Mytilus , Shellfish Poisoning , Humans , Animals , Shellfish Poisoning/etiology , Marine Toxins/chemistry , Dinoflagellida/chemistry , Chromatography, Liquid , Saxitoxin , Tandem Mass Spectrometry , Shellfish/analysis
10.
J Org Chem ; 87(21): 14422-14432, 2022 11 04.
Article in English | MEDLINE | ID: mdl-36242558

ABSTRACT

Stimuli-responsive supramolecular receptors are important building blocks for the construction of self-assembled functional materials. We report the design and synthesis of a pH- and light-responsive 2-hydroxychalcone-ß-cyclodextrin conjugate (1-Ct) and its characterization by spectroscopic and computational methods. 1-Ct follows the typical reaction network of trans-chalcone-flavylium photoswitches. Upon light irradiation, 1-Ct can be photochemically converted into the cis-chalcone/hemiketal forms (1-Cc/1-B) under neutral pH conditions or to the flavylium cation (1-AH+) at acidic pH values. This stimuli-responsive ß-cyclodextrin host, 1-Ct, was found to form stronger intramolecular self-inclusion complexes (Kintra = 14) than 1-AH+ (Kintra = 3) and weaker than 1-Cc/1-B (overall Kintra = 179), allowing control over their stability and binding properties by combinations of pH and light stimuli.


Subject(s)
Chalcone , Chalcones , beta-Cyclodextrins , Chalcones/chemistry , beta-Cyclodextrins/chemistry , Chalcone/chemistry , Hydrogen-Ion Concentration
11.
Sensors (Basel) ; 22(9)2022 Apr 22.
Article in English | MEDLINE | ID: mdl-35590913

ABSTRACT

In this work a plasmonic sensor with a D-Shaped microstructured optical fiber (MOF) is proposed to detect a wide range of analyte refractive index (RI ;na) by doping the pure silica (SiO2) core with distinct concentrations of Germanium Dioxide (GeO2), causing the presentation of high spectral sensitivity. In this case, the fiber is shaped by polishing a coating of SiO2, on the region that will be doped with GeO2, in the polished area, a thin gold (Au) layer, which constitutes the plasmonic material, is introduced, followed by the analyte, in a way which the gold layer is deposited between the SiO2. and the analyte. The numerical results obtained in the study shows that the sensor can determine efficiently a range of 0.13 refractive index units (RIU), with a limit operation where na varies from 1.32 to 1.45. Within this application, the sensor has reached an average wavelength sensitivity (WS) of up to 11,650.63 nm/RIU. With this level of sensitivity, the D-Shaped format and wide range of na detection, the proposed fiber has great potential for sensing applications in several areas.


Subject(s)
Germanium , Optical Fibers , Surface Plasmon Resonance , Gold , Silicon Dioxide , Surface Plasmon Resonance/instrumentation
12.
Mar Drugs ; 20(2)2022 Feb 15.
Article in English | MEDLINE | ID: mdl-35200672

ABSTRACT

The analysis of marine lipophilic toxins in shellfish products still represents a challenging task due to the complexity and diversity of the sample matrix. Liquid chromatography coupled with mass spectrometry (LC-MS) is the technique of choice for accurate quantitative measurements in complex samples. By combining unambiguous identification with the high selectivity of tandem MS, it provides the required high sensitivity and specificity. However, LC-MS is prone to matrix effects (ME) that need to be evaluated during the development and validation of methods. Furthermore, the large sample-to-sample variability, even between samples of the same species and geographic origin, needs a procedure to evaluate and control ME continuously. Here, we analyzed the toxins okadaic acid (OA), dinophysistoxins (DTX-1 and DTX-2), pectenotoxin (PTX-2), yessotoxin (YTX) and azaspiracid-1 (AZA-1). Samples were mussels (Mytilus galloprovincialis), both fresh and processed, and a toxin-free mussel reference material. We developed an accurate mass-extracted ion chromatogram (AM-XIC) based quantitation method using an Orbitrap instrument, evaluated the ME for different types and extracts of mussel samples, characterized the main compounds co-eluting with the targeted molecules and quantified toxins in samples by following a standard addition method (SAM). An AM-XIC based quantitation of lipophilic toxins in mussel samples using high resolution and accuracy full scan profiles (LC-HR-MS) is a good alternative to multi reaction monitoring (MRM) for instruments with HR capabilities. ME depend on the starting sample matrix and the sample preparation. ME are particularly strong for OA and related toxins, showing values below 50% for fresh mussel samples. Results for other toxins (AZA-1, YTX and PTX-2) are between 75% and 110%. ME in unknown matrices can be evaluated by comparing their full scan LC-HR-MS profiles with those of known samples with known ME. ME can be corrected by following SAM with AM-XIC quantitation if necessary.


Subject(s)
Chromatography, Liquid/methods , Marine Toxins/isolation & purification , Mass Spectrometry/methods , Mytilus/metabolism , Animals , Marine Toxins/analysis , Marine Toxins/chemistry
13.
Ann Thorac Surg ; 114(3): 800-808, 2022 09.
Article in English | MEDLINE | ID: mdl-34237293

ABSTRACT

BACKGROUND: Aortic root translocation (Nikaidoh), Rastelli, and réparation à l'etage ventriculaire (REV) are repair options for transposition of the great arteries (TGA) with ventricular septal defects and left ventricular outflow tract obstruction (VSD-LVOTO) or double outlet right ventricle TGA type (DORV-TGA). METHODS: This retrospective study using The Society of Thoracic Surgeons Congenital Heart Surgery Database evaluates surgical procedure utilization and outcomes of patients undergoing repair of TGA-VSD-LVOTO and DORV-TGA with a Nikaidoh, Rastelli, or REV procedure. RESULTS: A total of 293 patients underwent repair at 82 centers (January 2010 to June 2019). Most patients underwent a Rastelli (n = 165, 56.3%) or a Nikaidoh (n = 119, 40.6%) operation; only 3.1% (n = 9) underwent a REV. High-volume centers performed the majority of the repairs. Fewer Nikaidoh than Rastelli patients had prior cardiac operations (n = 57 [48.7%] vs n = 102 [63.0%]; P = .004). Nikaidohs had longer median cardiopulmonary bypass time (227 [interquartile range (IQR), 167-299] minutes vs 175 [IQR, 133-225] minutes; P < .001) and median aortic cross-clamp times (131 [IQR, 91-175] minutes vs 105 [IQR, 82-141] minutes; P = .0015). Operative mortality was 3.1% (95% confidence interval [CI], 1.0%-7.0%; n = 5) for Rastelli, 4.4% (95% CI, 1.4%-9.9%; n = 5) for Nikaidoh, and 11.1% (95% CI, 0.3%-48.3%, n = 1) for REV. The rates of cardiac arrest, unplanned reoperation, mechanical circulatory support, prolonged ventilation, and permanent pacemaker placement were higher in the Nikaidoh population but with 95% CIs overlapping those of the other procedures. CONCLUSIONS: Rastelli and Nikaidoh procedures are the prevalent repair strategies for patients with DORV-TGA and TGA-VSD-LVOTO. Most are performed at high-volume institutions, and early outcomes are similar.


Subject(s)
Double Outlet Right Ventricle , Heart Defects, Congenital , Heart Septal Defects, Ventricular , Surgeons , Transposition of Great Vessels , Ventricular Outflow Obstruction , Heart Defects, Congenital/surgery , Heart Septal Defects, Ventricular/surgery , Humans , Infant , Retrospective Studies , Transposition of Great Vessels/surgery , Treatment Outcome , Ventricular Outflow Obstruction/surgery
14.
Int J Cardiol ; 339: 36-42, 2021 09 15.
Article in English | MEDLINE | ID: mdl-34265312

ABSTRACT

BACKGROUND: Patients with Tetralogy of Fallot with pulmonary stenosis (ToF/PS), the most common form of cyanotic congenital heart disease (CHD), develop adverse right ventricular (RV) remodeling, leading to late heart failure and arrhythmia. We recently demonstrated that overactive ß-adrenergic receptor signaling inhibits cardiomyocyte division in ToF/PS infants, providing a conceptual basis for the hypothesis that treatment with the ß-adrenergic receptor blocker, propranolol, early in life would increase cardiomyocyte division. No data are available in ToF/PS infants on the efficacy of propranolol as a possible novel therapeutic option to increase cardiomyocyte division and potentially reduce adverse RV remodeling. METHODS: Using a randomized, double-blind, placebo-controlled trial, we will evaluate the effect of propranolol administration on reactivating cardiomyocyte proliferation to prevent adverse RV remodeling in 40 infants with ToF/PS. Propranolol administration (1 mg/kg po QID) will begin at 1 month of age and last until surgical repair. The primary endpoint is cardiomyocyte division, quantified after 15N-thymidine administration with Multi-isotope Imaging Mass Spectrometry (MIMS) analysis of resected myocardial specimens. The secondary endpoints are changes in RV myocardial and cardiomyocyte hypertrophy. CONCLUSION: This trial will be the first study in humans to assess whether cardiomyocyte proliferation can be pharmacologically increased. If successful, the results could introduce a paradigm shift in the management of patients with ToF/PS from a purely surgical approach, to synergistic medical and surgical management. It will provide the basis for future multi-center randomized controlled trials of propranolol administration in infants with ToF/PS and other types of CHD with RV hypertension. CLINICAL TRIAL REGISTRATION: The trial protocol was registered at clinicaltrials.gov (NCT04713657).


Subject(s)
Pulmonary Valve Stenosis , Tetralogy of Fallot , Humans , Infant , Myocytes, Cardiac , Randomized Controlled Trials as Topic , Receptors, Adrenergic, beta-2 , Tetralogy of Fallot/diagnostic imaging , Tetralogy of Fallot/surgery , Ventricular Remodeling
15.
Ann Thorac Surg ; 111(6): e455-e458, 2021 06.
Article in English | MEDLINE | ID: mdl-33631155

ABSTRACT

The ideal conduit for reconstruction of the right ventricular outflow tract in pediatric patients remains a topic of discussion. We present a technique for construction of a handmade tricuspid valved polytetrafluoroethylene conduit for use in patients of all ages requiring right ventricular outflow tract reconstruction at the time of congenital cardiac surgery. This conduit provides an economically advantageous and readily available option globally when compared with homograft, without sacrificing surgical results.


Subject(s)
Heart Valve Prosthesis , Polytetrafluoroethylene , Prosthesis Design , Tricuspid Valve/surgery , Ventricular Outflow Obstruction/surgery , Cardiac Surgical Procedures/methods , Humans
16.
Photochem Photobiol Sci ; 19(10): 1364-1372, 2020 Oct 14.
Article in English | MEDLINE | ID: mdl-32844861

ABSTRACT

Extending the applications of Photoremovable Protecting Groups (PPGs) to "cage" phenols has generally met with unusually complex PPG byproducts. In this study, we demonstrate that the p-hydroxyphenacyl (pHP) cage for both simple and complex phenolics, including tyrosine, dispenses free phenols. With the simpler unsubstituted phenols, the reaction is governed by their Brønsted Leaving Group ability. On the other hand, the byproducts of the cage vary with these phenols. For the more acidic phenols the cage byproduct follows the Favorskii rearrangement to form p-hydroxyphenylacetic acid whereas for the weaker phenols other reactions such as reduction and hydrolysis begin to emerge. When the photolysis is conducted in octa acid (OA) containers, non-Favorskii, unrearranged fragments of the cage and other byproducts arise.

17.
Photochem Photobiol Sci ; 18(10): 2411-2420, 2019 Oct 09.
Article in English | MEDLINE | ID: mdl-31347647

ABSTRACT

ortho-Nitrobenzyl (oNB) triggers have been extensively used to release various molecules of interest. However, the toxicity and reactivity of the spent chromophore, o-nitrosobenzaldehyde, remains an unaddressed difficulty. In this study we have applied the well-established supramolecular photochemical concepts to retain the spent trigger o-nitrosobenzaldehyde within the organic capsule after release of water-soluble acids and alcohols. The sequestering power of organic capsules for spent chromophores during photorelease from ortho-nitrobenzyl esters, ethers and alcohols is demonstrated with several examples.

18.
Chemistry ; 25(14): 3477-3482, 2019 Mar 07.
Article in English | MEDLINE | ID: mdl-30632649

ABSTRACT

The discovery of stimuli-responsive high affinity host-guest pairs with potential applications under biologically relevant conditions is a challenging goal. This work reports a high-affinity 1:1 complex formed between cucurbit[8]uril and a water-soluble photochromic diarylethene derivative. It was found that, by confining the open isomer within the cavity of the receptor, a redshift in the absorption spectrum and an enhancement of the photocyclization quantum yield from Φ=0.04 to Φ=0.32 were induced. This improvement in the photochemical performance enables quantitative photocyclization with visible light that, together with the near-infrared light-induced ring-opening reaction and the 100-fold selectivity for the closed isomer, confirms this as an outstanding light-responsive affinity pair.

19.
Clin Exp Rheumatol ; 37(4): 641-648, 2019.
Article in English | MEDLINE | ID: mdl-30418126

ABSTRACT

OBJECTIVES: Depressive symptoms are common among patients with rheumatoid arthritis (RA). This study was aimed at developing a multifactorial explanatory model that evaluated the influence of personality traits, disease activity, perceived disease impact, and comorbidities. METHODS: This cross-sectional study used structural equation modelling estimation to analyse the associations between these dimensions, pursuing three hypotheses. Depressive symptoms were assessed using the Hospital Anxiety and Depression Scale, disease impact by the Rheumatoid Arthritis Impact of Disease score, personality by the Ten Item Personality Inventory and the disease activity through the Disease Activity Score 28 joints. The influence of comorbidities was investigated by multigroup analysis. RESULTS: The final model derived from data of 254 patients presented a good fit. Disease activity had an indirect relation with depressive symptoms mediated by disease impact (ß=0.17, p<0.001), but the direct relationship between disease activity and depressive symptoms was not significant (ß=0.09; p=0.07). "Positive" personality had a strong negative direct relation with depressive symptoms as well as an indirect relationship mediated by disease impact (total effect ß=-0.61, p<0.001). The final proposed model explained 58% of the variance of depressive symptoms. Multigroup analysis showed an invariant model when comparing patients with and without comorbidities (dχ2=9.03; df=12; p=0.70). CONCLUSIONS: Personality characteristics seem to have a major influence upon the impact of disease and the patient's adjustment to RA, including the vulnerability or resilience to depression. Individual personality traits deserve attention in tailored assessment and treatment of patients with RA, in order to optimise outcomes.


Subject(s)
Arthritis, Rheumatoid , Cost of Illness , Depressive Disorder , Arthritis, Rheumatoid/epidemiology , Arthritis, Rheumatoid/psychology , Cross-Sectional Studies , Depression , Depressive Disorder/epidemiology , Humans , Personality , Personality Inventory
20.
Sci Rep ; 8(1): 239, 2018 01 10.
Article in English | MEDLINE | ID: mdl-29321586

ABSTRACT

The importance of chemical communication in reproduction has been demonstrated in many marine broadcast spawners. However, little is known about the use of chemical communication by echinoderms, the nature of the compounds involved and their mechanism(s) of action. Here, the hypothesis that the sea cucumber Holothuria arguinensis uses chemical communication for aggregation and spawning was tested. Water conditioned by males, but not females, attracted both males and females; gonad homogenates and coelomic fluid had no effect on attraction. Male spawning water, but not female spawning water, stimulated males and females to release their gametes; the spermatozoa alone did not induce spawning. H. arguinensis male spawning water also induced spawning in the phylogenetically related H. mammata. This indicates that males release pheromones together with their gametes that induce spawning in conspecifics and possibly sympatric species. Finally, the male pheromone seems to be a mixture with at least one labile compound (biological activity is lost after four hours at ambient temperature) possibly including phosphatidylcholines. The identification of pheromones in sea cucumbers offers a new ecological perspective and may have practical applications for their aquaculture.


Subject(s)
Behavior, Animal , Biomarkers , Sea Cucumbers/physiology , Animals , Chromatography, Liquid , Female , Gonads/metabolism , Male , Mass Spectrometry , Maze Learning
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