Comparison of Drying Techniques for Extraction of Bioactive Compounds from Olive-Tree Materials.

Olive tree vegetal materials are considered a powerful source for the isolation of bioactive compounds-mainly phenols and triterpenic acids. However, the high humidity content of them reduces their preservation and extractability to a liquid solvent. Accordingly, a drying step is crucial to homogenize the material and to obtain an efficient extraction. We studied the influence of the drying process on the extraction efficiency of bioactive compounds from olive vegetal material. For this purpose, we evaluated the effects of four drying processes on the solid-liquid extraction of bioactive compounds from two by-products, olive leaves and pomace, and olive fruits harvested from two cultivars, Alfafara and Koroneiki. Infrared-assisted drying (IAD) was the most suited approach to obtain extracts enriched in oleuropein from leaves (28.5 and 22.2% dry weight in Alfafara and Koroneiki, respectively). In the case of pomace, lyophilization and microwave-assisted drying led to extracts concentrated in oleacein and oleuropein aglycone, whereas IAD and oven-drying led to extracts with enhanced contents of hydroxytyrosol glucoside and hydroxytyrosol, respectively. The drying process considerably affected the chemical composition of extracts obtained from fruits. Changes in the composition of the extracts were explained essentially by the drying process conditions using auxiliary energies, temperature, and time, which promoted chemical alterations and increased the extractability of the compounds. Therefore, the drying protocol should be selected depending on the phenolic content and initial raw material.

Spatial Distribution and Antioxidant Activity of Extracts from Citrus Fruits.

Citrus fruits are recommended components of the human diet because of their enriched composition in bioactive compounds and health benefits. Among their notable components are phenols, with a special emphasis on flavonoids, limonoids, and carboxylic acids. In this research, we have carried out a spatial metabolomics analysis for the characterization of these bioactive families in three citrus fruits, namely, lemons, limes, and mandarins. Sampling was undertaken, for which the juices and three fruit tissues, namely, albedo, flavedo, and segments, were analyzed. This characterization allowed for the determination of 49 bioactive compounds in all the samples. The composition of the different extracts was correlated with the antioxidant capacity measured by the DPPH radical scavenging activity and ß-carotene bleaching assays. Flavonoids, found in the albedo and flavedo at higher concentrations, were the main components responsible for DPPH radical scavenging activity. On the other hand, the combined action of flavonoids and limonoids contributed to explaining the antioxidant activity measured by the ß-carotene bleaching assay. Generally, the antioxidant capacity of juices was lower than that estimated for extracts from citrus tissues.

Synthesis, characterisation, crystal structure and antimicrobial evaluation of novel 6-alkoxyergosta-4,6,8(14),22-tetraen-3-one derived from natural ergosta-5,7,22-trien-3ß-ol.

In this study, we report a facile transformation starting from 5α-hydroxyergosta-7,22-dien-3,6-dione (1) to afford two novel compounds: 6-methoxyergosta-4,6,8(14),22-tetraen-3-one (2) and 6-ethoxyergosta-4,6,8(14),22-tetraen-3-one (3) using alcoholic acid catalysis. Their structures were elucidated using NMR experiments, FT-IR, MS and X-ray analysis. These compounds were evaluated for antibacterial activity using the disk and broth diffusion test. In those tests, compound 3 was found to be the most significant antibacterial agent. In general, compounds 1-3 showed inhibition zone in the range of 7.00-12.3 mm for S. aureus and S. mutans, meanwhile for Gram-negative bacteria E. coli and Pseudomonas sp. was found to be in the range of 7.00-8.00 mm. For the most active, compound 3, MIC was significantly lower than that reported for ergosterol, in a value of 160 µg/mL. Overall, these compounds were more active than their natural precursor.

The luminescent Chalcones. Its potential use as a luminescent and antitumoral agents / Chalconas luminiscentes. Su uso potencial como agentes luminiscentes y antitumorales

Background: Hepatocellular carcinoma (HCC) is one of the most diagnosed cancers worldwide. Chemoprevention of HCC can be achieved using natural or synthetic compounds that reverse, suppress, detect, or prevent cancer progression. Objectives: In this study, both the antiproliferative effects and luminescent properties of 2'-hydroxychalcones were evaluated. Methods: Cell viability was evaluated using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) colorimetric assay, spectroscopy assays, and density functional theory (DFT) calculations were used to determine the luminescent properties of 2 ́-hydroxychalcones. Results: Cytotoxic effects of 2 ́-hydroxychalcones were observed over the HepG2 and EA.hy926 cells. Since the chalcone moiety could be used as a fluorescent probe, these compounds may be helpful in cancer diagnosis and tumor localization. They may enable tumor observation and regression through the fluorescence during treatment; therefore, the compounds are a potential candidate as novel anticancer agents acting on human hepatomas. Conclusions: This report describes the chalcones' use as a specific luminescent biomarker in tumor cells. We also report the cellular uptake of 2'-hydroxychalcones, their cellular distribution, and the mechanisms that may be responsible for their cytotoxic effects

ANTECEDENTES: El carcinoma hepatocelular (CHC) es uno de los cánceres más diagnosticados en todo el mundo. La quimio prevención del CHC se puede lograr utilizando compuestos naturales o sintéticos que reviertan, supriman, detecten o prevengan la progresión del cáncer. OBJETIVOS: En este estudio, se investigó tanto los efectos antiproliferativos como las propiedades luminiscentes de las 2'-hidroxicalconas. MÉTODOS: La viabilidad celular se evaluó usando el ensayo colorimétrico (MTT), los ensayos de espectroscopia y los cálculos DFT se usaron para determinar las propiedades luminiscentes de las 2 ́-hidroxichalconas. RESULTADOS: Se observaron efectos citotóxicos sobre las líneas celulares del tipo HepG2 y EA.hy926. Dado que la estructura de la 2 ́-hidroxichalcona puede ser usada como sonda fluorescente, estos compuestos pueden ser útiles en el diagnóstico del cáncer y la localización del tumor, ya que pueden permitir la observación a través de la fluorescencia y la regresión del tumor durante el tratamiento, por lo que son candidatas potenciales como nuevos agentes anticancerígenos que podrían actuar sobre hepatomas humanos. CONCLUSIONES: Este trabajo describe el uso de las 2 ́-hidroxichalconas como un biomarcador luminiscente específico para células tumorales. También informamos la captación celular de 2>-hidroxicalconas, su distribución celular y los mecanismos que pueden ser responsables de sus efectos citotóxicos

Antifungal activity screening of fractions from Annona cherimola Mill. leaf extract against Fusarium oxysporum.

The antifungal effect of ethanolic extract fractions of Annona cherimola leaves against the mycelial growth of Fusarium oxysporum was studied. The ethanolic crude extract was solvent partitioned and the ethyl acetate phase was fractionated by column or preparative thin-layer chromatography. All fractions were developed on TLC and analyzed for acetogenins (ACG) with Kedde reagent. The antifungal effect assays were carried out in vitro by the diffusion method on PDA plates. The ethanolic extract of A. cherimola leaves was highly active against F. oxysporum growth; subfractions obtained from the antifungal screening had a significant effect (p < 0.05) on the F. oxysporum growth parameters. The screening showed that as the purification steps progressed, the inhibition of mycelial growth increased. Six bioactive ACG (Annomolon-B, 34-epi annomolon B, almunequin, cherimoline 1, cherimoline 2, and isocherimoline 1) were identified by LC-QTOF-MS/MS. These findings suggested that bioactive ACG from A. cherimola leaves could be an alternative resource of a promising botanical fungicide to control plant diseases caused by F. oxysporum.

Prognosis patients with COVID-19 using deep learning.

BACKGROUND: The coronavirus (COVID-19) is a novel pandemic and recently we do not have enough knowledge about the virus behaviour and key performance indicators (KPIs) to assess the mortality risk forecast. However, using a lot of complex and expensive biomarkers could be impossible for many low budget hospitals. Timely identification of the risk of mortality of COVID-19 patients (RMCPs) is essential to improve hospitals' management systems and resource allocation standards. METHODS: For the mortality risk prediction, this research work proposes a COVID-19 mortality risk calculator based on a deep learning (DL) model and based on a dataset provided by the HM Hospitals Madrid, Spain. A pre-processing strategy for unbalanced classes and feature selection is proposed. To evaluate the proposed methods, an over-sampling Synthetic Minority TEchnique (SMOTE) and data imputation approaches are introduced which is based on the K-nearest neighbour. RESULTS: A total of 1,503 seriously ill COVID-19 patients having a median age of 70 years old are comprised in the research work, with 927 (61.7%) males and 576 (38.3%) females. A total of 48 features are considered to evaluate the proposed method, and the following results are achieved. It includes the following values i.e., area under the curve (AUC) 0.93, F2 score 0.93, recall 1.00, accuracy, 0.95, precision 0.91, specificity 0.9279 and maximum probability of correct decision (MPCD) 0.93. CONCLUSION: The results show that the proposed method is significantly best for the mortality risk prediction of patients with COVID-19 infection. The MPCD score shows that the proposed DL outperforms on every dataset when evaluating even with an over-sampling technique. The benefits of the data imputation algorithm for unavailable biomarker data are also evaluated. Based on the results, the proposed scheme could be an appropriate tool for critically ill Covid-19 patients to assess the risk of mortality and prognosis.

Process monitoring for quality - A multiple classifier system for highly unbalanced data.

In big data-based analyses, because of hyper-dimensional feature spaces, there has been no previous distinction between machine learning algorithms (MLAs). Therefore, multiple diverse algorithms should be included in the analysis to develop an adequate model for detecting/recognizing patterns exhibited by classes. If multiple classifiers are developed, the next natural step is to determine whether the prediction benchmark set by the top performer can be improved by combining them. In this context, multiple classifier systems (MCSs) are powerful solutions for difficult pattern recognition problems because they usually outperform the best individual classifier, and their diversity tends to improve resilience and robustness to high-dimensional and noisy data. To design an MCS, an appropriate fusion method is required to optimally combine the individual classifiers and determine the final decision. Process monitoring for quality is a Quality 4.0 initiative aimed at defect detection via binary classification. Because most mature organizations have merged traditional quality philosophies, their processes generate only a few defects per million of opportunities. Therefore, manufacturing data sets for binary classification of quality tends to be highly/ultra-unbalanced. Detecting these rare quality events is one of the most relevant intellectual challenges posed to the fourth industrial revolution, Industry 4.0 (I 4.0). A new MCS aimed at analyzing these data structures is presented. It is based on eight well-known MLAs, an ad hoc fitness function, and a novel meta-learning algorithm. For predicting the final quality class, this algorithm considers the prediction from a set of classifiers as input and determines which classifiers are reliable and which are not. Finally, to demonstrate the superiority of the MLAs over extensively used fusion rules, multiple publicly available data sets are analyzed.

Influence of the fatty acid profile on the volatile components of virgin olive oil subjected to thermal stress.

BACKGROUND: Virgin olive oil (VOO) is greatly appreciated for its organoleptic features, which can be ascribed mainly to the presence of very chemically diverse volatile components. It is well known that the VOO volatile fraction depends strongly on different aspects, which encompass genetic, agronomic, processing, and post-processing factors. In this research, we developed a method for the qualitative and semiquantitative determination of volatile components in VOOs subjected to thermal stress by headspace extraction online coupled to gas chromatography-mass spectrometry (HS-GC-MS). RESULTS: The method was applied to 100 extra-virgin olive oil (EVOO) samples, which led to the tentative identification of 52 volatile components, including 12 alcohols, 17 aldehydes, three ketones, one ether, two furans, two carboxylic acids, and 15 hydrocarbons. The method was used to study the cultivar effect and the main biochemical pathways involved in the synthesis of volatile compounds, with special emphasis on those formed by degradation of unsaturated fatty acids (FAs). Principal component analysis (PCA), explaining 76.7% of the total variability, showed that the volatile profile of EVOOs subjected to thermal stress allowed discriminating samples from different cultivars. CONCLUSION: Volatiles detected in EVOOs subjected to thermal stress with the highest contribution to discrimination between the selected cultivars were correlated with the concentration of the three main FAs in VOO, namely oleic, linoleic, and linolenic acids. The FA profile seems to be especially relevant to explain the concentration of certain volatile compounds with direct incidence on the organoleptic properties. © 2021 Society of Chemical Industry.

Antibacterial Effect of Luma apiculata (DC.) Burret Extracts in Clinically Important Bacteria.

Nosocomial infections caused by bacteria are one of the main public health problems. Moreover, the resistance to antibiotics by these bacteria makes it necessary to find new treatments to fight them. Objective. To evaluate the antibacterial activity of Luma apiculata (DC.) Burret extracts on bacteria of clinical importance. Materials and Methods. In this study, extracts were obtained at room temperature by successive extraction of L. apiculata leaves, flowers, and branches and treated separately with solvents of ascending polarity (i.e., hexane, methylene dichloride, ethyl acetate, ethanol, methanol, and water) to extract the compounds depending on their polarity. Then, the extract's antibacterial activity was tested against Staphylococcus aureus, Staphylococcus epidermidis, Staphylococcus saprophyticus, Enterococcus sp, Acinetobacter baumanii, Pseudomonas aeruginosa, and Escherichia coli. Results. The hexane extract of L. apiculata leaves resulted to be active against all bacteria tested. Among them, S. aureus showed to be the more susceptible, showing a minimum inhibitory concentration (MIC) of 120 µg/ml. In addition, a growth curve was performed, and colonies were counted. A decrease in bacterial growth was observed when the hexane extract of L. apiculata leaves was added. Besides, the hexane extracts of L. apiculata flowers resulted to be active against all Gram-positive tested bacteria. However, at higher concentrations, this extract resulted inactive for the Gram-negative bacteria tested. The hexane extract of L. apiculata branches resulted to be inactive in all cases. The extracts obtained treating separately leaves, flowers, or branches with solvents of major polarity than the hexane in a successive extraction of ascending polarity methodology resulted also to be inactive as an antimicrobial against all bacteria tested. Discussion/Conclusion. The hexane extract of L. apiculata leaves showed the lower MIC against S. aureus when compared with extracts obtained from other parts of the plant. The growth curve and the colonies count suggest a bacteriostatic activity of the L. apiculata leaves extract against Staphylococcus aureus.

GC-MS study of changes in polar/mid-polar and volatile compounds in Persian lime (Citrus latifolia) during fruit growth.

BACKGROUND: Citrus fruits possess a high content of bioactive compounds whose changes during fruit maturation have not been studied in depth. Fruits were sampled from week 1, after fruit onset (7 days after flowering), to week 14. Volatile compounds isolated by headspace-solid-phase microextraction and polar extracts from all samples were analyzed by gas chromatography-mass spectrometry. RESULTS: The relative abundance of 107 identified metabolites allowed differences among samples at different stages of fruit growth to be established. Principal component analysis showed a clear discrimination among samples, and analysis of variance revealed significant differences in 94 out of the 107 metabolites. Among total volatiles, monoterpenes increased their relative abundance from 86% to 94% during fruit growth, d-limonene, γ-terpinene and ß-pinene being the most abundant; conversely, sesquiterpenes decreased from 11.5% to 2.8%, ß-bisabolene and α-bergamotene being the most concentrated. Sugars, in general, exhibited a gradual increase in abundance, reaching a maximum between weeks 9 and 12. Citric and malic acids, representing approximately 90% of the total identified carboxylic acids, reached a maximum concentration at commercial maturity (week 14). CONCLUSION: Of the 107 tentatively identified metabolites during Persian lime growth, sugars, carboxylic acids, and volatiles were those that experienced more significant changes and more clearly created differences among fruit growth stages. © 2018 Society of Chemical Industry.

Tunable Polarity Carbon Fibers, a Holistic Approach to Environmental Protection.

The pollution of environmental resources is an issue of social concern worldwide. Chemistry is essential for the design of decontamination strategies and analytical approaches to detect and monitor the contamination. Sorptive materials are usually required in both approaches and green synthesis should be used to minimize their own environmental impact. Carbon fibers (CFs) obtained by the pyrolysis of natural cellulose-rich materials fulfill these requirements. In this article, thirty CFs obtained under different conditions are chemically characterized and their sorption ability towards selected pollutants, covering a wide range of polarity, is evaluated. This study provides more profound knowledge related to the polarity of these materials, their interactions with chemical substances and allows the prediction of more appropriate materials (pyrolysis temperature and time) in order to remove the given pollutant. Furthermore, the use of CFs as sorptive materials for the extraction of contaminants from water samples to assist with their instrumental detection is outlined. In this sense, the use of CFs and gas chromatography with mass spectrometric detection allows the detection of selected pollutants in the low ng/mL range. Thus, this article provides an integrated approach to the potential of CFs for environmental protection.

Targeted Analysis of the Concentration Changes of Phenolic Compounds in Persian Lime (Citrus latifolia) during Fruit Growth.

Citrus fruits possess a high content of phenolic compounds; however, few studies have focused on the changes occurring during fruit growth. In this study, the changes in the concentration of 20 flavonoids, 4 phenolic acids, and their biosynthetic precursors phenylalanine and tyrosine have been evaluated during fruit maturation (14 weeks). Extracts from all samples, obtained by ultrasound assistance, were analyzed by liquid chromatography coupled to tandem mass spectrometry with a triple quad system (LC-QqQ MS/MS). In general, the concentration of flavanones, which represented over 70% of the studied phenols, and flavones increased during fruit growth, reaching their maximum concentration around week 12. In general, flavanols and phenolic acids exhibited their maximum concentration at week 5 and then decreasing significantly during the rest of maturation. Phenylalanine and tyrosine showed a sinuous behavior during fruit growth. Partial least-squares showed a clear differentiation among fruits belonging to different maturation stages, coumaric acid derivatives being the most influential variables on the projection.

Effect of sample pretreatment on the extraction of lemon (Citrus limon) components.

A study on the key role of lemon sample pretreatment on the analytical results is here presented. The objective of the study was to analyze the differences between extracts obtained from lyophilized and air-dried samples-the most common sample pretreatment in citrus studies-in comparison to extracts from fresh samples. All the extracts were obtained with ultrasound assistance and analyzed by LC-QTOF MS/MS. The dataset, constituted by 74 tentative identified metabolites, was first evaluated by ANOVA, which showed significant differences in the concentration of 44 out of 74 metabolites (p≤0.01). Also, the pairwise mean comparison (Tukey HSD; p≤0.01) revealed that the concentration of metabolites in the extracts from fresh and air-dried samples was quite similar and differed from that in lyophilized samples. On the other hand, application of principal component analysis (PCA) showed a clear discrimination between pretreatments, explaining 86.20% of the total variability. The results of this study suggest that the main differences between extracts could be attributed to the effect of freezing or heating on metabolic pathways, and not only to thermolability of the compounds.

Chalcone-Induced Apoptosis through Caspase-Dependent Intrinsic Pathways in Human Hepatocellular Carcinoma Cells.

Hepatocellular carcinoma (HCC) is one of the most commonly diagnosed cancers worldwide. Chemoprevention of HCC can be achieved through the use of natural or synthetic compounds that reverse, suppress or prevent the development of cancer progression. In this study, we investigated the antiproliferative effects and the mechanism of action of two compounds, 2,3,4'-trimethoxy-2'-hydroxy-chalcone (CH1) and 3'-bromo-3,4-dimethoxy-chalcone (CH2), over human hepatoma cells (HepG2 and Huh-7) and cultured mouse hepatocytes (HepM). Cytotoxic effects were observed over the HepG2 and Huh-7, and no effects were observed over the HepM. For HepG2 cells, treated separately with each chalcone, typical apoptotic laddering and nuclear condensation were observed. Additionally, the caspases and Bcl-2 family proteins activation by using Western blotting and immunocytochemistry were studied. Caspase-8 was not activated, but caspase-3 and -9 were both activated by chalcones in HepG2 cells. Chalcones also induced reactive oxygen species (ROS) accumulation after 4, 8 and 24 h of treatment in HepG2 cells. These results suggest that apoptosis in HepG2 was induced through: (i) a caspase-dependent intrinsic pathway; and (ii) by alterations in the cellular levels of Bcl-2 family proteins, and also, that the chalcone moiety could be a potent candidate as novel anticancer agents acting on human hepatomas.

Comparative Study of the Effect of Sample Pretreatment and Extraction on the Determination of Flavonoids from Lemon (Citrus limon).

BACKGROUND: Flavonoids have shown to exert multiple beneficial effects on human health, being also appreciated by both food and pharmaceutical industries. Citrus fruits are a key source of flavonoids, thus promoting studies to obtain them. Characteristics of these studies are the discrepancies among sample pretreatments and among extraction methods, and also the scant number of comparative studies developed so far. OBJECTIVE: Evaluate the effect of both the sample pretreatment and the extraction method on the profile of flavonoids isolated from lemon. RESULTS: Extracts from fresh, lyophilized and air-dried samples obtained by shaking extraction (SE), ultrasound-assisted extraction (USAE), microwave-assisted extraction (MAE) and superheated liquid extraction (SHLE) were analyzed by LC-QTOF MS/MS, and 32 flavonoids were tentatively identified using MS/MS information. ANOVA applied to the data from fresh and dehydrated samples and from extraction by the different methods revealed that 26 and 32 flavonoids, respectively, were significant (p≤0.01). The pairwise comparison (Tukey HSD; p≤0.01) showed that lyophilized samples are more different from fresh samples than from air-dried samples; also, principal component analysis (PCA) showed a clear discrimination among sample pretreatment strategies and suggested that such differences are mainly created by the abundance of major flavonoids. On the other hand, pairwise comparison of extraction methods revealed that USAE and MAE provided quite similar extracts, being SHLE extracts different from the other two. In this case, PCA showed a clear discrimination among extraction methods, and their position in the scores plot suggests a lower abundance of flavonoids in the extracts from SHLE. In the two PCA the loadings plots revealed a trend to forming groups according to flavonoid aglycones. CONCLUSIONS: The present study shows clear discrimination caused by both sample pretreatments and extraction methods. Under the studied conditions, liophilization provides extracts with higher amounts of flavonoids, and USAE is the best method for isolation of these compounds, followed by MAE and SE. On the contrary, the SHLE method was the less favorable to extract flavonoids from citrus owing to degradation.

Comparative study of the effect of auxiliary energies on the extraction of Citrus fruit components.

A comparative study of methods for ultrasound-assisted extraction (USAE), microwave-assisted extraction (MAE) and superheated liquid extraction (SHLE) of compounds from citrus has been performed. The suited conditions for each method were evaluated to maximize the concentration of 10 representative compounds (sugars, carboxylic acids, phenolic acids and flavonoids) by a desirability function approach based on the chromatographic peaks obtained by LC-DAD. Extracts obtained under the suited conditions were analyzed by LC-QTOF MS/MS. The ANOVA on the molecular entities showed 232 significant entities (p<0.01), and pairwise comparison revealed that USAE and MAE methods are the most similar (50 different entities), and USAE and SHLE the most dissimilar (224 different entities). A discrimination test by PCA showed a clear discrimination among the extraction methods, explaining 78.51% of the total variability. Similarities in the abundance of the monitored compounds was tested by ANOVA showing that the extraction of carboxylic acids (malic and citric acids) was equal by all methods; while for each of the other eight compounds, at least one extraction method is different from the others. Under the evaluated conditions the SHLE method is the less favorable to extract metabolites from citrus, being the best the USAE method.

Electrical Control of near-Field Energy Transfer between Quantum Dots and Two-Dimensional Semiconductors.

We investigate near-field energy transfer between chemically synthesized quantum dots (QDs) and two-dimensional semiconductors. We fabricate devices in which electrostatically gated semiconducting monolayer molybdenum disulfide (MoS2) is placed atop a homogeneous self-assembled layer of core-shell CdSSe QDs. We demonstrate efficient nonradiative Förster resonant energy transfer (FRET) from QDs into MoS2 and prove that modest gate-induced variation in the excitonic absorption of MoS2 leads to large (∼500%) changes in the FRET rate. This in turn allows for up to ∼75% electrical modulation of QD photoluminescence intensity. The hybrid QD/MoS2 devices operate within a small voltage range, allow for continuous modification of the QD photoluminescence intensity, and can be used for selective tuning of QDs emitting in the visible-IR range.

Gold nanoparticles for photothermally controlled drug release.

In this article, we describe how nanoparticles work in photothermally triggered drug delivery, starting with a description of the plasmon resonance and the photothermal effect, and how this is used to release a drug. Then, we describe the four major functionalization strategies and each of their different applications. Finally, we discuss the biodistribution and toxicity of these systems and the necessary requirements for the use of gold nanoparticles for spatially and temporally controlling drug release through the photothermal effect.

Reproducing superhydrophobic leaves as coatings by micromolding surface-initiated polymerization.

Micromolding surface-initiated polymerization enables the fabrication of polymer coatings that reproduce the microscale surface topography of superhydrophobic leaves onto solid supports. Here, the surfaces of superhydrophobic leaves from Trifolium repens and Aristolochia esperanzae are molded and reproduced as the topography of a partially fluorinated polymer coating through the surface-initiated ring-opening metathesis polymerization of 5-(perfluorooctyl)norbornene (NBF8). The polymer coatings have thicknesses exceeding 100 µm, which can be tailored by the amount of monomer added to the mold. These coatings are robustly bound to the substrate, contain compositions not found in nature, and achieve superhydrophobicity that is comparable to the actual leaf.

Amplification of surface-initiated ring-opening metathesis polymerization of 5-(perfluoro-n-alkyl)norbornenes by macroinitiation.

This article reports the enhanced rate of the surface-initiated polymerization (SIP) of 5-(perfluoro-n-alkyl)norbornenes (NBFn) by combining two SIP techniques, namely surface-initiated atom-transfer polymerization (SI-ATRP) to grow a macroinitiator and surface-initiated ring-opening metathesis polymerization (SI-ROMP) to produce the final coating. This polymerization approach promotes the rapid growth of dense partially fluorinated coatings that are highly hydrophobic and oleophobic and yield thicknesses from 4-12 µm. Specifically, the growth rate and the limiting thickness of pNBFn with different side chain lengths (n = 4, 6, 8, and 10) at various monomer concentrations and temperatures are evaluated through two approaches: growing the polymer from an initiator-terminated monolayer (control) or from a modified poly(2-hydroxyethyl methacrylate) (PHEMA) macroinitiator. X-ray photoelectron spectroscopy (XPS) analysis shows that 38% of the hydroxyl termini in the macroinitiator react with a norbornenyl diacid chloride (NBDAC) molecule, and 7% of such anchored norbornenyl groups react with a catalyst molecule. The kinetic data have been modeled to determine the propagation velocity and the termination rate constant. The PHEMA macroinitiator provides thicker films and faster growth as compared to the monolayer, achieving a 12 µm thick coating of pNBF8 in 15 min. Increasing the monomer side chain length, n, from 4 to 10 improves the growth rate and the limiting polymer thickness. Performing the polymerization process at higher temperature increases the growth rate and the limiting thickness as evidenced by an increase in the film growth rate constant. Arrhenius plots show that the reactions involved in the macroinitiation process exhibit lower activation energies than those formed from a monolayer. Electrochemical impedance spectroscopy reveals that the films exhibit resistance against ion transport in excess of 1 × 10(10) Ω·cm(2).