X-Ray powder diffraction laboratory @ University of Málaga (UMA)

X-Ray Powder Diffraction (XRPD) laboratory is a facility placed at Servicios Centrales de apoyo a la Investigación (SCAI) at University of Malaga (UMA) http://www.scai.uma.es/. This facility has three XRPD diffractometers and a diffractometer to measure high-resolution thin-films. X´Pert PRO MPD from PANalytical. This is a bragg-brentano (theta/2theta) with reflection geometry diffractometer which allows to obtain high resolution XRPD data with strictly monochromatic CuKα1 radiation (λ=1.54059Å) [Ge(111) primary monochromator] and an automatic sample charger. Moreover, it has parallel monochromatic CuKα1 radiation (λ=1.54059Å) with an hybrid Ge(220) monochromator for capillary and multiproposal (bulk samples up to 1 Kg) sample holders. The HTK1200N chamber from Anton Paar allows collecting high resolution high temperature patterns. EMPYREAN from PANalytical. This diffractometer works in reflection and transmission geometries with theta/theta goniometer, using CuKα1,2 radiation (λ=1.5418Å), a focusing X-ray mirror and a ultra-fast PIXCEL 3D detector with 1D and 2D collection data modes (microstructural and preferred orientation analysis). Moreover, the TTK450N chamber allows low temperature and up to 450ºC studies. A D8 ADVANCE (BRUKER) was installed in April 2014. It is the first diffractometer in Europe equipped with a Johansson Ge(111) primary monochromator, which gives a strictly monochromatic Mo radiation (λ=0.7093 Å) [1]. It works in transmission mode (with a sample charger) with this high resolution configuration. XRPD data suitable for PDF (Pair Distribution Function) analysis can be collected with a capillary sample holder, due to the high energy and high resolution capabilities of this diffractometer. Moreover, it has a humidity chamber MHC-trans from Anton Paar working on transmission mode with MoKα1 (measurements can be collected at 5 to 95% of relative humidity (from 20 to 80 ºC) and up to 150ºC [2]). Furthermore, this diffractometer also has a reaction chamber XRK900 from Anton Paar (which uses CuKα1,2 radiation in reflection mode), which allows data collection from room temperature to 900ºC with up to 10 bar of different gases. Finally, a D8 DISVOVER A25 from BRUKER was installed on December 2014. It has a five axis Euler cradler and optics devices suitable for high resolution thin film data collection collected in in-plane and out-of-plane modes. To sum up, high-resolution thin films, microstructural, rocking-curve, Small Angle X-ray Scattering (SAXS), Grazing incident SAXS (GISAXS), Ultra Grazing incident diffraction (Ultra-GID) and microdiffraction measurements can be performed with the appropriated optics and sample holders. [1] L. León-Reina, M. García-Maté, G. Álvarez-Pinazo, I. Santacruz, O. Vallcorba, A.G. De la Torre, M.A.G. Aranda “Accuracy in Rietveld quantitative phase analysis: a comparative study of strictly monochromatic Mo and Cu radiations” J. Appl. Crystallogr. 2016, 49, 722-735. [2] J. Aríñez-Soriano, J. Albalad, C. Vila-Parrondo, J. Pérez-Carvajal, S. Rodríguez-Hermida, A. Cabeza, F. Busqué, J. Juanhuix, I. Imaz, Daniel Maspoch “Single-crystal and humidity-controlled powder diffraction study of the breathing effect in a metal-organic framework upon water adsorption/desorption” Chem. Commun., 2016, DOI: 10.1039/C6CC02908F.

In-situ Molibdenum X-ray powder diffraction study of the early hydration of cementitious systems on a humidity chamber

The durability of cement-based construction materials depends on the environmental conditions during their service life. A further factor is the microstructure of the cement bulk, established by formation of cement hydrates. The development of the phases and microstructure under given conditions is responsible of the high strength of cementitious materials. The investigation on the early hydration behavior of cements and cementing systems has been for a long time a very important area of research: understanding the chemical reactions that lead to hardening is fundamental for the prediction of performances and durability of the materials. The production of 1 ton of Ordinary Portland Cement, OPC, releases into the atmosphere ~0.97 tons of CO2. This implies that the overall CO2 emissions from the cement industry are 6% of all anthropogenic carbon dioxide. An alternative to reduce the CO2 footprint consists on the development of eco-cements composed by less calcite demanding phases, such as belite and ye'elimite. That is the case of Belite-Ye’elimite cements (BY). Since the reactivity of belite is not quick enough, these materials develop low mechanical strengths at intermediate hydration ages. A possible solution to this problem goes through the production of cements which jointly contain alite with the two previously mentioned phases, named as Belite-Alite-Ye’elimite (BAY) cements. The reaction of alite and ye'elimite with water will develop cements with high mechanical strengths at early ages, while belite will contribute to later values. The final goal is to understand the hydration mechanisms of a variety of cementing systems (OPC, BAY and pure phases) as a function of water content, superplasticizer additives and type and content of sulfate source. In order to do so, in-situ laboratory humidity chambers with Molybdenum X-ray Powder diffraction are employed. In the first 2h of hydration, reaction degree (α) of ye'elimite had been decreased for superplasticizer.

Applications of synchrotron x-ray powder diffraction in hydrated cements: high-resolution and high-pressure studies

The main aim of this study is to apply synchrotron radiation techniques for the study of hydrated cement pastes. In particular, the tetracalcium aluminoferrite phase, C4AF in cement nomenclature, is the major iron-containing phase in Ordinary Portland Cement (OPC) and in iron rich belite calcium sulfoaluminate cements. In a first study, the hydration mechanism of pure tetracalcium aluminoferrite phase with water-to-solid ratio of 1.0 has been investigated by HR-SXRPD (high resolution synchrotron X-ray powder diffraction). C4AF in the presence of water hydrates to form mainly an iron-containing hydrogarnet-type (katoite) phase, C3A0.84F0.16H6, as single crystalline phase. Its crystal structure and stoichiometry were determined by the Rietveld method and the final disagreement factors were RWP=8.1% and RF=4.8% [1]. As the iron content in the product is lower than that in C4AF, it is assumed that part of the iron also goes to an amorphous iron rich gel, like the hydrated alumina-type gel, as hydration proceeds. Further results from the high-resolution study will be discussed. In a second study, the behavior of pure and iron-containing katoites (C3AH6 and C3A0.84F0.16H6) under pressure have been analyzed by SXRPD using a diamond anvil cell (DAC) and then their bulk moduli were determined. The role of the pressure transmitting medium (PTM) has also been studied. In this case, silicone oil as well as methanol/ethanol mixtures have been used as PTM. Some “new peaks” were detected in the pattern for C3A0.84F0.16H6 as pressure increases, when using ethanol/methanol as PTM. These new peaks were still present at ambient pressure after releasing the applied pressure. They may correspond to crystalline nordstrandite or doyleite from the crystallization of amorphous aluminium hydroxide. The results from the high-pressure study will also be discussed.

Investigation of the enhanced antimicrobial activity of combination dry powder inhaler formulations of lactoferrin

The airways of most people with cystic fibrosis are colonized with biofilms of the Gram-negative, opportunistic pathogen Pseudomonas aeruginosa. Delivery of antibiotics directly to the lung in the form of dry powder aerosols offers the potential to achieve high local concentrations directly to the biofilms. Unfortunately, current aerosolised antibiotic regimes are unable to efficiently eradicate these biofilms from the airways. We investigated the ability of the innate antimicrobial, lactoferrin, to enhance the activity of two aminoglycoside antibiotics (tobramycin and gentamicin) against biofilms of P. aeruginosa strain PAO1. Biofilms were prepared in 96 well polystyrene plates. Combinations of the antibiotics and various lactoferrin preparations were spray dried. The bacterial cell viability of the various spray dried combinations was determined. Iron-free lactoferrin (apo lactoferrin) induced a 3-log reduction in the killing of planktonic cell by the aminoglycoside antibiotics (p < 0.01) and also reduced both the formation and persistence of P. aeruginosa biofilms (p < 0.01). Combinations of lactoferrin and an aminoglycoside displays potential as an effective new therapeutic strategy in the treatment of P. aeruginosa biofilms infections such as those typical of the CF lungs.

Maltodextrin-incorporated-vacuum-dried honey powder: processing and stability

Honey is rich in sugar content and dominated by fructose and glucose that make honey prone to crystallize during storage. Due to honey composition, the anhydrous glass transition temperature of honey is very low that makes honey difficult to dry alone and drying aid or filler is needed to dry honey. Maltodextrin is a common drying aid material used in drying of sugar-rich food. The present study aims to study the processing of honey powder by vacuum drying method and the impact of drying process and formulation on the stability of honey powder. To achieve the objectives, the series of experiments were done: investigating of maltodextrin DE 10 properties, studying the effect of drying temperature, total solid concentration, DE value, maltodextrin concentration and anti-caking agent on honey powder processing and stability. Maltodextrin provide stable glass compared to lower molecular weight sugars. Dynamic Dew Point Isotherm (DDI) data could be used to determine amorphous content of a system. The area under the first derivative curve from DDI curve is equal to the amount of water needed by amorphous material to crystallize. The drying temperature affected the amorphous content of vacuum-dried honey powder. The higher temperature seemed to result in honey powder with more amorphous component. The ratio of maltodextrin affected more significantly the stability of honey powder compared to the treatments of total solids concentration, DE value and drying temperature. The critical water activity of honey powder was lower than water activity of the equilibrium water content corresponding to BET monolayer water content. Addition of anti-caking agent increased stability and flow-ability of honey powder. Addition of Calcium stearate could inhibit collapse of the honey powder during storage.

Enhancement of the total phenolic compounds and antioxidant activity of aqueous Citrus limon L. pomace extracts using microwave pre-treatment on the dry powder

The effect of microwave pre-treatment on the levels of total phenolic compounds, flavonoids, proanthocyanidins and individual major compounds as well as the total antioxidant activity of the dried lemon pomace was investigated. The results showed that microwave pre-treatment significantly affected all the examined parameters. The total phenolic content, total flavonoids, proanthocyanidins, as well as the total antioxidant activity significantly increased as the microwave radiation time and power increased (e.g., 2.5 folds for phenolics, 1.4 folds for flavonoids and 5.5 folds for proanthocyanidins), however irradiation more than 480 W for 5 min resulted in the decrease of these parameters. These findings indicate that microwave irradiation time and power may enhance higher levels of the phenolic compounds as well as the antioxidant capacity of the dried lemon pomace powder. However, higher and longer irradiation may lead to a degradation of phenolic compounds and lower the antioxidant capacity of the dried lemon pomace.

Optimization of an innovative T6 heat treatment for the AlSi10Mg alloy processed by Laser-based Powder Bed Fusion: effect on microstructure, mechanical properties, and tribological behavior

Laser-based Powder Bed Fusion (L-PBF) technology is one of the most commonly used metal Additive Manufacturing (AM) techniques to produce highly customized and value-added parts. The AlSi10Mg alloy has received more attention in the L-PBF process due to its good printability, high strength/weight ratio, corrosion resistance, and relatively low cost. However, a deep understanding of the effect of heat treatments on this alloy's metastable microstructure is still required for developing tailored heat treatments for the L-PBF AlSi10Mg alloy to overcome the limits of the as-built condition. Several authors have already investigated the effects of conventional heat treatment on the microstructure and mechanical behavior of the L-PBF AlSi10Mg alloy but often overlooked the peculiarities of the starting supersatured and ultrafine microstructure induced by rapid solidification. For this reason, the effects of innovative T6 heat treatment (T6R) on the microstructure and mechanical behavior of the L-PBF AlSi10Mg alloy were assessed. The short solution soaking time (10 min) and the relatively low temperature (510 °C) reduced the typical porosity growth at high temperatures and led to a homogeneous distribution of fine globular Si particles in the Al matrix. In addition, it increased the amount of Mg and Si in the solid solution available for precipitation hardening during the aging step. The mechanical (at room temperature and 200 °C) and tribological properties of the T6R alloy were evaluated and compared with other solutions, especially with an optimized direct-aged alloy (T5 alloy). Results showed that the innovative T6R alloy exhibits the best mechanical trade-off between strength and ductility, the highest fatigue strength among the analyzed conditions, and interesting tribological behavior. Furthermore, the high-temperature mechanical performances of the heat-treated L-PBF AlSi10Mg alloy make it suitable for structural components operating in mild service conditions at 200 °C.

High-strength steels manufactured via Laser Powder Bed Fusion: effect of post-process heat treatments and surface finishing on microstructure and mechanical properties

Laser Powder Bed Fusion (LPBF) permits the manufacturing of parts with optimized geometry, enabling lightweight design of mechanical components in aerospace and automotive and the production of tools with conformal cooling channels. In order to produce parts with high strength-to-weight ratio, high-strength steels are required. To date, the most diffused high-strength steels for LPBF are hot-work tool steels, maraging and precipitation-hardening stainless steels, featuring different composition, feasibility and properties. Moreover, LPBF parts usually require a proper heat treatment and surface finishing, to develop the desired properties and reduce the high roughness resulting from LPBF. The present PhD thesis investigates the effect of different heat treatments and surface finishing on the microstructure and mechanical properties of a hot-work tool steel and a precipitation-hardening stainless steel manufactured via LPBF. The bibliographic section focuses on the main aspects of LPBF, hot-work tool steels and precipitation-hardening stainless steels. The experimental section is divided in two parts. Part A addresses the effect of different heat treatments and surface finishing on the microstructure, hardness, tensile and fatigue behaviour of a LPBF manufactured hot-work tool steel, to evaluate its feasibility for automotive and racing components. Results indicated the possibility to achieve high hardness and strength, comparable to the conventionally produced steel, but a great sensitivity of fatigue strength on defects and surface roughness resulting from LPBF. Part B investigates the effect of different heat treatments on the microstructure, hardness, tensile and notch-impact behaviour of a LPBF produced precipitation-hardening stainless steel, to assess its feasibility for tooling applications. Results indicated the possibility to achieve high hardness and strength also through a simple Direct Aging, enabling heat treatment simplification by exploiting the microstructural features resulting from LPBF.

Influenza dei difetti sul comportamento a fatica della lega AlSi10Mg prodotta con Laser Powder Bed Fusion

La tesi in oggetto ha lo scopo di valutare la fattibilità di sviluppare, sulla base di dati sperimentali, un metodo previsionale per il comportamento a fatica della lega AlSi10Mg prodotta mediante Laser Powder Bed Fusion, adattabile a componenti di dimensioni qualsiasi. La lega è stata trattata con invecchiamento diretto (T5) ottimizzato per ottenere una parziale riduzione delle tensioni residue senza comprometterne la durezza. Partendo da prove di fatica a flessione rotante condotte seguendo il metodo statistico Stair-Case per la definizione della resistenza a fatica, si vuole correlare il difetto killer, ossia quello che innesca la rottura del provino, alla caratterizzazione dei difetti condotta pre-prova con tomografia computerizzata ad alta risoluzione (µCT). Il difetto killer, osservato sulle superfici di frattura, viene analizzato in termini di dimensione, posizione e forma. Contemporaneamente è stato sviluppato un metodo per l’analisi dei difetti ottenuta con µCT tale da poter identificare quelli considerati più pericolosi, sulla base dello stato tensionale del campione, di posizione e dimensione dei difetti. Inoltre, è stata eseguita una caratterizzazione microstrutturale sulle sezioni trasversali dei campioni per valutare la quantità, dimensione e forma dei difetti e confrontarla con i dati di µCT. Per mostrare la relazione tra le dimensioni del difetto killer e la resistenza a fatica è stato adottato il diagramma di Kitagawa-Takahashi, con il modello di El Haddad. Dal confronto tra le metodologie è stata riscontrata una buona correlazione tra i difetti individuati come pericolosi dai dati di µCT e quelli che hanno effettivamente portato a rottura il campione, osservati in frattografia, supportando quindi la possibilità di sviluppare un metodo previsionale del comportamento a fatica. Quantitativamente, le dimensioni dei difetti killer sono nell’intervallo 90-130 µm e si trovano ad una distanza massima dalla superficie di non oltre 250 µm.

Aspetti microstrutturali, proprietà meccaniche e ottimizzazione del trattamento termico di un acciaio inossidabile PH processato con laser powder bed fusion

L’attività di ricerca svolta in questa tesi ha riguardato gli aspetti microstrutturali, le proprietà meccaniche e l’ottimizzazione del trattamento termico di un acciaio inossidabile indurente per precipitazione processato mediante tecnologia additiva Laser Powder Bed Fusion (L-PBF). I provini, realizzati presso il competence center Bi-REX (Bologna) e lavorati presso il laboratorio di Metallurgia del DIN, sono stati oggetto di vari trattamenti termici sperimentali in cui è stata fatta variare la temperatura e la durata di mantenimento in forno, al fine di identificare la combinazione ottimale di temperatura e tempo sia per la fase di solubilizzazione che di invecchiamento. Nello specifico, la scelta dei parametri di solubilizzazione e invecchiamento è stata fatta solo sulla base dei trend di durezza. Da queste attività sono stati scelti i parametri di trattamento che garantissero elevata durezza, prossima alla massima ottenibile, senza durate di invecchiamento eccessive. L'esito della sperimentazione ha permesso di ridurre sensibilmente temperatura e durata di solubilizzazione rispetto al trattamento benchmark senza penalizzazione della durezza risultante. Dopodiché è stata eseguita una caratterizzazione microstrutturale e meccanica dell’acciaio, in termini di durezza, trazione e resilienza, per confrontare il trattamento termico ottimizzato con la condizione As-Built (AB) e con il trattamento termico standard indicato dal produttore. L’elevata durezza misurata dopo invecchiamento si deve alla presenza di precipitati di rinforzo in grado di ostacolare il moto delle dislocazioni. Le prove meccaniche hanno confermato l’ottenimento di elevata resistenza a snervamento e a trazione, superiore al benchmark, ma di un basso allungamento a rottura e bassissima resilienza a causa di difetti quali porosità, mancate fusioni e spattering. Infine, lo studio delle superfici di frattura ha permesso di analizzare i meccanismi di rottura dei campioni di trazione e resilienza.

Ossidazione anodica al plasma della lega di alluminio A357 prodotta mediante Laser - Powder Bed Fusion: microstruttura e comportamento tribologico

In questo elaborato è stato analizzato il comportamento tribologico della lega di alluminio A357 realizzata tramite Laser Powder Bed Fusion (L-PBF). In particolare, è stato studiato l’effetto del processo di anodizzazione ECO (ElectroChemical Oxidation) su tale lega, sia allo stato as-built che dopo trattamento termico T6R, in termini di attrito e usura a temperatura ambiente (i.e. 25°C) e a 200°C. Lo studio tribologico è stato svolto mediante prove di strisciamento non lubrificato in moto reciprocante (geometria ball-on-disc contro allumina). Nella prima parte del lavoro sono state effettuate prove a temperatura ambiente, su strati ECO a rugosità variabile, con carichi applicati nell’intervallo 1-8N. Nella seconda parte l’attività sperimentale si è invece rivolta al confronto nel comportamento tribologico della lega a 25°C e 200°C, mantenendo il carico invariato pari a 1 N e analizzando la risposta in termini di attrito e usura, sia per campioni rivestiti ECO che per campioni non rivestiti. Il rivestimento anodico ha mostrato a temperatura ambiente una maggiore resistenza ad usura quando applicato su superfici pre-lucidate, nonostante un maggiore coefficiente di attrito, dando luogo a cedimento completo ad un carico di 8 N (contro i 5 N del non lucidato). Dalla seconda fase di questo studio è invece risultato come il rivestimento ECO abbia notevolmente migliorato la resistenza ad usura rispetto al materiale non rivestito, sia a 25°C che a 200°C, mantenendo invariato il coefficiente d’attrito all’aumentare della temperatura, al contrario dei campioni A357 non rivestiti, che hanno invece manifestato un aumento del coefficiente di attrito di circa il doppio. Vale inoltre la pena notare come la pre-lucidatura ed il trattamento termico dei campioni A357 ECO siano risultati superflui in termini di comportamento tribologico; i campioni a superficie rugosa hanno dato luogo addirittura a minori coefficienti di attrito sia a 25°C che a 200°C, a parità di profondità d’usura.

Studio del comportamento meccanico e tribologico della lega AlSi10Mg prodotta mediante Laser-based Powder Bed Fusion sottoposta ad un ciclo tecnologico ottimizzato

AlSi10Mg alloy is one of the most widely used alloys for producing structural components by Laser-based Powder Fusion (L-PBF) technology due to the high mechanical and technological properties. The present work aims to characterize mechanically and tribologically the L-PBF AlSi10Mg alloy subjected to both heat treatment and surface modification cycles. Specifically, the effects of three heat treatments on the tribological and mechanical properties of the alloy were analyzed: T5 (artificial aging at 160 °C for 4 h), T6 rapid solution heat treatment (solution heat treatment at 510 °C for 1h and aging at 160 °C for 6 h), and T6 benchmark (solution heat treatment at 540 °C for 1h and aging at 160 °C for 4 h), the latter used as a benchmark. The study highlighted how the better balance between strength and ductility properties induced by the introduction of heat treatments leads to lower wear resistance and not significant variations in the friction coefficient of the alloy. The tribological and mechanical behavior of the alloy coated with two different coating structures, consisting of (i) chemical Ni (Ni-P) and (ii) Ni-P + DLC, was also evaluated. The goal was the identification of a deposition cycle such as to guarantee the optimization of the mechanical and tribological behavior of the alloy. The Ni-P coating provided good wear resistance but an increase in the coefficient of friction. In contrast, using the DLC top coating resulted in excellent tribological performance in wear resistance and friction coefficient. The samples characterized by the Ni-P + DLC multilayer coating were subsequently subjected to mechanical characterization. The results obtained highlighted problems of adhesion and incipient breaking of the material due to the different mechanical behavior of the coating, considerably reducing the mechanical performance of the alloy coated with Ni-P+DLC multilayer solution compared to the specimens in the un-coated condition.

Effetto della sabbiatura sul comportamento a fatica della lega AlSi10Mg prodotta con Laser Powder Bed Fusion e trattata termicamente

La tesi in oggetto ha lo scopo di determinare l’effetto della sabbiatura sul comportamento a fatica della lega AlSi10Mg prodotta mediante Laser Powder Bed Fusion e trattata termicamente. I parametri di processo e di trattamento termico (T5 e T6) sono stati precedentemente ottimizzati. Al fine di determinare l’effetto della sabbiatura su topografia superficiale e microstruttura dei campioni, si sono condotte molteplici analisi avvalendosi di strumenti quali profilometria, microscopia ottica ed in scansione, analisi di tensioni residue con diffrazione a raggi X e prove di durezza. Attraverso prove di fatica per flessione rotante, eseguite secondo il metodo Stair-Case per la determinazione della resistenza a fatica, e successiva caratterizzazione delle superfici di frattura si vuole correlare il difetto killer, ossia quello responsabile del cedimento per fatica, alle caratteristiche morfologiche e microstrutturali. Il difetto killer viene caratterizzato in termini di dimensione e distanza dalla superficie e per mostrare la relazione fra la dimensione del difetto killer e la resistenza a fatica si adotta il diagramma di Kitagawa-Takahashi con modellazione di Murakami ed EL Haddad. Si è evidenziato che tutti i difetti killer sono riconducibili a lack-of-fusion con dimensione superiore ai 100 μm ad una profondità compresa fra i 150 e i 200 μm, indipendentemente dal trattamento termico o meccanico applicato. In termini di fatica si osserva che il trattamento T6 conferisce al materiale migliori proprietà rispetto a quello T5. Il processo di sabbiatura, confrontato con quello di lucidatura superficiale, ha portato a miglioramenti in termini di durezza e tensioni residue di compressione, ma si è rivelato quasi ininfluente sulla resistenza a fatica. Sulla base di quanto sopra, si conferma la possibilità di applicazione della sabbiatura in ambito industriale a componenti meccanici, anche in sostituzione della lucidatura, ottenendo un beneficio anche economico.

Endocytosis Of Tight Junctions Caveolin Nitrosylation Dependent Is Improved By Cocoa Via Opioid Receptor On Rpe Cells In Diabetic Conditions.

Retinal pigment epithelium cells, along with tight junction (TJ) proteins, constitute the outer blood retinal barrier (BRB). Contradictory findings suggest a role for the outer BRB in the pathogenesis of diabetic retinopathy (DR). The aim of this study was to investigate whether the mechanisms involved in these alterations are sensitive to nitrosative stress, and if cocoa or epicatechin (EC) protects from this damage under diabetic (DM) milieu conditions. Cells of a human RPE line (ARPE-19) were exposed to high-glucose (HG) conditions for 24 hours in the presence or absence of cocoa powder containing 0.5% or 60.5% polyphenol (low-polyphenol cocoa [LPC] and high-polyphenol cocoa [HPC], respectively). Exposure to HG decreased claudin-1 and occludin TJ expressions and increased extracellular matrix accumulation (ECM), whereas levels of TNF-α and inducible nitric oxide synthase (iNOS) were upregulated, accompanied by increased nitric oxide levels. This nitrosative stress resulted in S-nitrosylation of caveolin-1 (CAV-1), which in turn increased CAV-1 traffic and its interactions with claudin-1 and occludin. This cascade was inhibited by treatment with HPC or EC through δ-opioid receptor (DOR) binding and stimulation, thereby decreasing TNF-α-induced iNOS upregulation and CAV-1 endocytosis. The TJ functions were restored, leading to prevention of paracellular permeability, restoration of resistance of the ARPE-19 monolayer, and decreased ECM accumulation. The detrimental effects on TJs in ARPE-19 cells exposed to DM milieu occur through a CAV-1 S-nitrosylation-dependent endocytosis mechanism. High-polyphenol cocoa or EC exerts protective effects through DOR stimulation.