Search

Biosolids are considered a potentially major input of microplastics (MPs) to agricultural soils. Our study aims to identify the polymeric origin of MPs extracted from biosolid samples by comparing their Attenuated Total Reflection (ATR) - Fourier-transform infrared (FTIR) spectra with the corresponding near-infrared (NIR) spectra. The reflectance spectra were preprocessed by Savitzky-Golay (SG), first derivative (FD) and compared with analogous spectra acquired on a set of fifty-two selected commercial plastic (SCP) materials collected from readily available products. According to the results portrayed in radar chart and built from both ATR-FTIR and NIR spectral datasets, the MPs showed high correlations with polymers such as polyethylene (LDPE, HDPE), polyethylene terephthalate (PET), polystyrene (PS), polypropylene (PP) and polyamide (PA), determined in SCP samples. Each unknown MP sample had on average three or more links to several types of SCP, according to the correlation coefficients for each polymer ranging from 0.7 up to 1. The comparison analysis classified the majority of MPs as composed mainly by LDPE/HDPE, according to the top correlation coefficients (r > 0.90). PP and PET were better identified with NIR than ATR-FTIR. In contrast to ATR-FTIR analysis, NIR was unable to identify PS. Based on these results, the primary sources of MPs in the biosolids could be identified as discarded consumer packaging (containers, bags, bottles) and fibers from laundry, disposable glove, and cleaning cloth. SYNOPSIS: Microplastics (MPs) are considered contaminants of emerging concern. This study compares two simple and fast spectroscopy techniques to identify microplastics in the biosolid matrix., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Polymeric micelles (PMs) are promising platforms for enhanced tissue targeting of entrapped therapeutic agents. Strategies to circumvent premature release of entrapped drugs include cross-linking of the micellar core as well as covalent attachment of the drug cargo. The chemistry employed to obtain cross-linked micelles needs to be mild to also allow entrapment of fragile molecules, such as certain peptides, proteins, oligonucleotides, and fluorescent dyes. Native chemical ligation (NCL) is a mild bio-orthogonal reaction between a N- terminal cysteine residue and a thioester that proceeds under physiological conditions. Here, we designed a trifunctional cross-linker containing two cysteine residues for the micelle core-cross-linking reaction and an azide residue for ring-strained alkyne conjugation of fluorescent dyes. We applied this approach to thermosensitive methoxypolyethylene glycol- b - N -(2-hydroxypropyl)methacrylamide-lactate (mPEG- b -HPMAmLac n ) based block copolymers of a core-cross-linked polymeric micelle (CCPM) system by attaching thioester residues (using ethyl thioglycolate-succinic anhydride, ETSA) for NCL cross-linking with the trifunctional cross-linker under physiological conditions. By use of mild copper-free click chemistry, we coupled fluorescent dyes, Sulfo.Cy5 and BODIPY, to the core via the azide residue present on the cross-linker by triazole ring formation. In addition, we employed a recently developed cycloheptyne strain promoted click reagent (TMTHSI, CliCr) in comparison to the frequently employed cyclooctyne derivative (DBCO), both achieving successful dye entrapment. The size of the resulting CCPMs could be tuned between 50 and 100 nm by varying the molecular weight of the thermosensitive block and ETSA content. In vitro cell experiments showed successful internalization of the dye entrapped CCPMs, which did not affect cell viability up to a polymer concentration of 2 mg/mL in PC3 cells. These fluorescent dye entrapped CCPMs can be applied in diagnostic imaging and the chemistry developed in this study serves as a steppingstone toward covalently entrapped fragile drug compounds with tunable release in CCPMs.

The aim of this research was to highlight the impact of urbanization and agriculture on soil quality, mainly by focusing on heavy metal accumulation (Cd, Cu, Fe, Mn, Ni, Pb and Zn) in the fragile riparian ecosystems of the Medjerda river (Souk-Ahras, Algeria). This study was performed in three cultivated soils (0-10, 10-20, 20-60 cm depth) along an increasing gradient of anthropogenic pressure in non-urban (NU), peri-urban (PU) and urban areas (U). Geo-accumulation index (Igeo), Enrichment factor (EF), Pollution load index (PLI) and Potential ecological risk index (RI) were calculated, as well as the potential non-carcinogenic risk for humans (HI). Additionally, to corroborate the role of Bufo spinosus D. as biosentinel, a skin biopsy was performed to quantify the concentration of heavy metals in both terrestrial and aquatic ecosystems. The results showed that when compared to NU, U and PU areas were richer in heavy metals. In particular, Igeo-Cd displayed strongly contaminated soil in U (>3), EF showed high enrichment of heavy metals (>2) for all the soils except for Ni, PLI presented no contamination for all (<1) while RI was significantly higher in U (>300), denoting a strong impact of heavy metals on soil quality. However, HI was below 1 for all the studied areas, although the highest values were related to U and PU. The skin biopsy showed the highest values for Cu, Fe and Pb in PU (0.328, 0.713 and 0.524 mg kg -1 , respectively) similarly to trends observed in the soil of that area. This study shed light on the rising pollution of heavy metals due to urbanization and agricultural input in these fragile ecosystems where Bufo spinosus D. plays the role of potential bio-indicator for environmental pollution., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Goethite, hematite, ferrihydrite, and other iron oxides bind through various sorption reactions with humic substances (HS) in soils creating nano-, micro-, and macro-aggregates with a specific nature and stability. Long residence times of soil organic matter (SOM) have been attributed to iron-humic substance (Fe-HS) complexes due to physical protection and chemical stabilization at the organic-mineral interface. Humic acids (HA) and fulvic acids (FA) contain many acidic functional groups that interact with Fe oxides through different mechanisms. Due to the numerous interactions between mineral Fe and natural SOM, much research has led into a better identification and definition of HS. In this review, we first focus on the surface colloidal properties of Fe oxides and their reactivity toward HS. These minerals can be efficiently identified by usual techniques, such as XRD, FTIR spectroscopy, XAS, Mössbauer, diffuse reflectance spectroscopies (DRS), HRTEM, ATM, NanoSIMS. Second, we present the recent state of art regarding the adsorption/precipitation of HS onto iron mineral surfaces and their effects on binding metalloid and trace elements. Finally, we consider future research directions based on recent scientific literature, with particular focus on the ability of Fe nano-particles to increase Fe bioavailability, improve carbon sequestration, reduce greenhouse gas emissions, and decrease the impact of persistent organic and inorganic pollutants. The methodology in this field has rapidly developed over the last decade. However, new procedures to estimate the nature of Fe-HA bonds will be important contributions in clarifying the role of natural iron oxides in soil for carbon stabilization., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

The successful use of visible and near-infrared (Vis-NIR) reflectance spectroscopy analysis requires selecting an optimal procedure of data acquisition and an accurate modeling approach. In this study, Vis-NIR with 350-2500 nm wavelengths were applied to detect different forms of lead (Pb) through the spectrally active soil constituents combining principal component regression (PCR) and Partial least-square regression (PLSR) for the Vis-NIR model calibration. Three clouds with different soil spectral properties were divided by the Linear discriminant analysis (LDA) in categories of Pb contamination risks: "low," "health," "ecological," ranging from 200 to 750 mg kg -1 . Farm soils were used for calibration (n = 26), and more polluted garden soils (n = 36) from New York City were used for validation. Total and bioaccessible Pb concentrations were examined with PLSR models and compared with Support Vector Machine (SVM) Regression and Boosting Regression Tree (BRT) models. Performances of all models' predictions were qualitatively evaluated by the Root Mean Square Error (RMSE), Residual Prediction Deviation (RPD), and coefficient of determination (R 2 ). For total Pb, the best predictive models were obtained with BRT (R 2  = 0.82 and RMSE 341.80 mg kg -1 ) followed by SVM (validation, R 2  = 0.77 and RMSE 337.96 mg kg -1 ), and lastly by PLSR (validation, R 2  = 0.74 and RMSE 499.04 mg kg -1 ). The PLSR technique is the most accurate calibration model for bioaccessible Pb with an R 2 value of 0.91 and RMSE of 68.27 mg kg -1 . The regression analysis indicated that bioaccessible Pb is strongly influenced by organic content, and to a lesser extent, by Fe concentrations. Although PLSR obtained lower accuracy, the model selected many characteristic bands and, thus, provided accurate approach for Pb pollution monitoring., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Background: CriPec technology enables the generation of drug-entrapped biodegradable core-crosslinked polymeric micelles (CCPM) with high drug loading capacity, tailorable size, and drug release kinetics. Docetaxel (DTX)-entrapped CCPM, also referred to as CPC634, have demonstrated favorable pharmacokinetics, tolerability, and enhanced tumor uptake in patients. Clinical efficacy evaluation is ongoing. CPC634 is currently stored (shelf life > 5 years) and shipped as a frozen aqueous dispersion at temperatures below -60°C, in order to prevent premature release of DTX and hydrolysis of the core-crosslinks. Consequently, like other aqueous nanomedicine formulations, CPC634 relies on cold chain supply, which is unfavorable for commercialization. Lyophilization can help to bypass this issue., Methods and Results: Freeze-drying methodology for CCPM was developed by employing CPC634 as a model formulation, and sucrose and trehalose as cryoprotectants. We studied the residual moisture content and reconstitution behavior of the CPC634 freeze-dried cake, as well as the size, polydispersity index, morphology, drug retention, and release kinetics of reconstituted CPC634. Subsequently, the freeze-drying methodology was validated in an industrial setting, yielding a CPC634 freeze-dried cake with a moisture content of less than 0.1 wt%. It was found that trehalose-cryoprotected CPC634 could be rapidly reconstituted in less than 5 min at room temperature. Critical quality attributes such as size, morphology, drug retention, and release kinetics of trehalose-cryoprotected freeze-dried CPC634 upon reconstitution were identical to those of non-freeze-dried CPC634., Conclusion: Our findings provide proof-of-concept for the lyophilization of drug-containing CCPM and our methodology is readily translatable to large-scale manufacturing for future commercialization., (© 2021 The Authors. Biotechnology Journal published by Wiley-VCH GmbH.)

Aim: We aimed to investigate the effectiveness of traction therapy in reducing pain by performing a systematic review with meta-analysis. We also explore the best modality for administering traction to patients with cervical radicular syndrome (CRS)., Methods: We searched the Medline, Physiotherapy Evidence Database (PEDro), Cochrane Central Register of Controlled Trials, and Cumulative Index to Nursing and Allied Health Literature (CINAHL) electronic databases. Two reviewers independently selected randomized controlled trials (RCTs) that compared traction in addition to other treatments versus the effectiveness of other treatments alone for pain outcome. We calculated the mean differences (MDs) and 95% confidence intervals (CIs). We used Cochrane's tool to assess risk of bias and the Grading of Recommendations Assessment, Development and Evaluation (GRADE) system to evaluate the quality of evidence and summarize the study conclusions., Results: A total of seven studies (589 patients), one with low risk of bias, were evaluated. An overall estimate of treatment modalities showed low evidence that adding traction to other treatments is statistically significant (MD -5.93 [95% CI, -11.81 to -0.04] P = 0.05 and I 2 = 57%) compared to other treatments alone. The subgroup analyses were still statistically significant only for mechanical and continuous modalities., Conclusions: Overall analysis showed that, compared to controls, reduction in pain intensity after traction therapy was achieved in patients with cervical radiculopathy. However, the quality of evidence was generally low and none of these effects were clinically meaningful.

To remove the mineral oil impregnating the insulating paper present in old, disconnected, underground electrical cables, which represents a threat to the environment, two approaches are investigated at laboratory (1 m) and pilot (10 m) scales. The first one involves in situ polymerization to clog the inner channel of the cables and to enable the washing of the outer paper region impregnated by the oil by axial flow of a displacing fluid (water). The second approach leaves the inner channel open and employs repeated cycles of pressurization and rest to displace the oil contained in the paper by radially pushing the water from the inner channel into the outer layers. The pressurization and rest times were optimized to obtain the highest oil extraction rate. While the first approach showed limitations in terms of required pressures and operating time, which increase with the length of the cables, the second one was effective at removing 97% of the oil impregnating the paper layers within 25 cycles. Even more relevant, this second solution, in contrast to the first one, can be easily scaled up as it does not depend on the length of the cable, and was successfully tested on a 10 m cable, showing 98% oil recovery.

Cadmium (Cd), one of the most toxic contaminants in groundwater, can cause a severe threat to human health and ecological systems. In this study, alumina nanoparticles were synthesized and tested for high-efficiency Cd removal from simulated groundwater. Furthermore, the synthesized alumina nanoparticles were successfully modified using negatively charged glycerol, to alleviate the challenge of its low mobility in groundwater for the Cd removal. The maximum removal efficiency of both synthesized and glycerol-modified alumina nanoparticles were more than 99%. The sorption isotherm and kinetic data of both synthesized and glycerol-modified alumina nanoparticles were best fitted to the Freundlich model and the pseudo-second-order model, respectively, indicating that the sorption of Cd ions occurs on heterogeneous surfaces of both alumina nanoparticles via the chemisorption mechanism. X-ray photoelectron spectroscopy and energy dispersive X-ray analysis revealed the presence of Cd peak in both sorbents after contact with Cd. In addition, the FTIR analyses demonstrated that hydroxyl group participated in the sorption of Cd on both synthesized and glycerol-modified alumina nanoparticles, while other glycerol associated groups contributed to the removal of Cd ions by the glycerol-modified alumina nanoparticles. It was concluded that Cd removal by synthesized and glycerol-modified alumina nanoparticles were mainly due to ion exchange and electrostatic attraction, respectively. Desorption experiment suggested that both alumina nanoparticles are effective and practically significant sorbents to remediate Cd from contaminated groundwater. However, the stronger bond between Cd and glycerol-modified alumina, plus its potential of higher mobility due to the negative charge on the surface, warrant glycerol-modified alumina nanoparticles a better performance in remediating Cd contaminated groundwater than that of the synthesized alumina nanoparticles., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

An optimal drug delivery system should be characterized by biocompatibility, biodegradability, high drug loading and favorable drug release profile. To achieve this goal a hydrazone linked doxorubicin-poly(lactic acid) prodrug (PLA-DOX) was synthesized by the functionalization of a short polymer chain produced by ring opening polymerization. The hydrophobic prodrug generated in this way was nanoprecipitated using a block copolymer to form polymeric nanoparticles (NPs) with a quantitative loading efficiency and a high and tunable drug loading. The effects of the concentration of the PLA-DOX prodrug and surfactant were studied by dynamic light scattering showing a range of NP size between 50 and 90 nm and monodispersed size distributions with polydispersity indexes lower then 0.27 up to a maximum DOX concentration of 27% w/w. The release profile of DOX from these NPs, tested at different pH conditions, showed a higher release rate in acidic conditions, consistent with the nature of the hydrazone bond which was used to conjugate the drug to the polymer. In vitro cytotoxicity studies performed on BV2 microglia-like cell line highlighted a specific cytotoxic effect of these NPs suggesting the maintenance of the drug efficacy and a modified release profile upon encapsulation of DOX in the NPs.

Olive mill wastewaters (OMW) contain significant levels of phenolic compounds with antimicrobial/phytotoxic activity and high amounts of undecomposed organic matter that may exert negative effects on soil biology. Among OMW detoxification techniques, those focusing on oxidative degradation of phenolic compounds are relevant. The composting (bio-oxidation) process in particular, exploits exothermic oxidation reactions by microorganisms to transform the organic matrix of OMW into an amendment biologically stable and feasible to use in agriculture. This process consists of an active phase during which organic compounds are rapidly decomposed, and a curing phase characterized by a slow breakdown of the remaining materials with the formation of humic substances (HS) as by-products. In this study, bio-oxidation of OMW was performed using a pre-treated organic material derived from municipal solid waste (MSW). The obtained amendment (OMWF) was stable and in accordance with the legislative parameters of mixed organic amendments. HS were then extracted from OMWF and MSW (control amendment, Amd-C), and differences in structural properties of their humic acid (HA) fraction were highlighted via spectroscopy (Fourier Transform Infrared) and Dynamic Light Scattering. To assay a potential use of HA as biostimulants for crops, 12-day old Zea Mays L. plants were supplied with HA at 0.5 mg and 1 mg C L -1 for 2 days. HA from both amendments increased plant growth, but HA from OMWF was more effective at both dosages (plus 35-37%). Also, HA from OMWF enhanced both nitrogen assimilation and glycolysis by increasing the activity of nitrate reductase (∼1.8-1.9 fold), phosphoglucose isomerase (PGI) (∼1.8-2 fold) and pyruvate kinase (PK) (∼1.5-1.8 fold), while HA from Amd-C targeted glycolysis preferentially. HA from OMWF, however, significantly stimulated plant nutrition only at lower dosage, perhaps because certain undetermined compounds from detoxified OMW and incorporated in HA altered the root membrane permeability, thus preventing the increase of nutrient uptake. Conversely, HA from Amd-C increased nutrient accumulation in maize at both dosages. In conclusion, our results indicate that the amendment obtained via OMW composting using MSW had a reduced pollution load in terms of phenolic compounds, and HA extracted from OMWF could be used as valuable biostimulants during maize cultivation.

Interactions between proteins and surfaces in combination with hydrodynamic flow and mechanical agitation can often trigger the conversion of soluble peptides and proteins into aggregates, including amyloid fibrils. Despite the extensive literature on the empirical effects of surfaces and mechanical forces on the formation of amyloids, the molecular details of the mechanisms underlying this behavior are still elusive. This limitation is, in part, due to the complex reaction network underlying the formation of amyloids, where several microscopic reactions of nucleation and growth can occur both at the interfaces and in bulk. In this work, we design a high-throughput assay based on nanoparticles and we apply a chemical kinetic platform to analyze the mechanisms underlying the effect of surfaces and mechanical forces on the formation of amyloid fibrils from human insulin under physiological conditions. By considering a variety of polymeric nanoparticles with different surface properties we explore a broad range of repulsive and attractive interactions between insulin and surfaces. Our analysis shows that hydrophobic interfaces induce the formation of amyloid fibrils by specifically promoting the primary heterogeneous nucleation rate. In contrast, mechanical forces accelerate the formation of amyloid fibrils by favoring mass transport and further amplify the number of fibrils by promoting fragmentation events. Thus, surfaces and agitation have a combined effect on the kinetics of protein aggregation observed at the macroscopic level but, individually, they each affect distinct microscopic reaction steps: the presence of interfaces generates primary nucleation events of fibril formation, which is then amplified by mechanical forces. These results suggest that the inhibition of surface-induced heterogeneous nucleation should be considered a primary target to suppress aggregation and explain why in many systems the simultaneous presence of surfaces and hydrodynamic flow enhances protein aggregation.

Specific therapeutic targeting of kidney podocytes, the highly differentiated ramified glomerular cells involved in the onset and/or progression of proteinuric diseases, could become the optimal strategy for preventing chronic kidney disease. With this aim, we developed a library of engineered polymeric nanoparticles (NPs) of tuneable size and surface properties and evaluated their interaction with podocytes. NP cytotoxicity, uptake, and cytoskeletal effects on podocytes were first assessed. On the basis of these data, nanodelivery of dexamethasone loaded into selected biocompatible NPs was successful in repairing damaged podocytes. Finally, a three-dimensional in vitro system of co-culture of endothelial cells and podocytes was exploited as a new tool for mimicking the mechanisms of NP interaction with glomerular cells and the repair of the kidney filtration barrier., Competing Interests: The authors declare no competing financial interest.

Objectives: To analyze the effects of kinesio taping (KT) -applied with three different strains that induced or not the formation of skin creases (called convolutions)- on color intensity of post-surgical superficial hematomas., Design: Single-blind paired study., Setting: Rehabilitation clinic., Participants: A convenience sample of 13 inpatients with post-surgical superficial hematomas., Interventions: The tape was applied for 24 consecutive hours. Three tails of KT were randomly applied with different degrees of strain: none (SN); light (SL); and full longitudinal stretch (SF). We expected to obtain correct formation of convolutions with SL, some convolutions with SN, and no convolutions with SF., Main Outcome Measures: The change in color intensity of hematomas, measured by means of polar coordinates CIE L*a*b* using a validated and standardized digital images system., Results: Applying KT to hematomas did not significantly change the color intensity in the central area under the tape (p > 0.05). There was a significant treatment effect (p < 0.05) under the edges of the tape, independently of the formation of convolutions (p > 0.05)., Conclusions: The changes observed along the edges of the tape could be related to the formation of a pressure gradient between the KT and the adjacent area, but were not dependent on the formation of skin convolutions., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

An integrated platform to assess the interaction between nanocarriers and biological matrices has been developed by our group using poly methyl-methacrylate nanoparticles. In this study, we exploited this platform to evaluate the behavior of two biodegradable formulations, poly-ε-caprolactone (PCL3) and poly lactic-acid (PLA8), respectively, in cellular and animal models of triple-negative breast cancer (TNBC). Both NPs shared the main physicochemical parameters (size, shape, ζ-potential) and exclusively differentiated on the material on which they are composed. Our results showed that (1) PLA8 NPs, systemically injected in mice, underwent rapid degradation without penetration into tumors; (2) PLA8 NPs were not internalized in the human TNBC cell line (MDA-MB-231); (3) PCL3 NPs had a longer bioavailability, reached the tumor parenchyma, and efficiently penetrated in MDA-MB-231 cells. Our data highlight the relevance of the material selection to both improve bioavailability and target tropism, and make PCL3 NPs an interesting tool for the development of nanodrugs against TNBC.

Polymer nanoparticles (NPs) represent a promising way to deliver poorly water-soluble anticancer drugs without the use of unwanted excipients, whose presence can be the cause of severe side effects. In this work, a Cremophor-free formulation for paclitaxel (PTX) has been developed by employing PEGylated polymer nanoparticles (NPs) as drug delivery carriers based on modified poly(ε-caprolactone) macromonomers and synthesized through free radical emulsion polymerization. Paclitaxel was loaded in the NPs in a postsynthesis process which allowed to obtain a drug concentration suitable for in vivo use. In vivo experiments on drug biodistribution and therapeutic efficacy show comparable behavior between the NPs and the Cremophor formulation, also showing good tolerability of the new formulation proposed.

Many efforts have been performed in order to understand the role of recruited macrophages in the progression of spinal cord injury (SCI). Different studies revealed a pleiotropic effect played by these cells associated to distinct phenotypes (M1 and M2), showing a predictable spatial and temporal distribution in the injured site after SCI. Differently, the role of activated microglia in injury progression has been poorly investigated, mainly because of the challenges to target and selectively modulate them in situ. A delivery nanovector tool (poly-ε-caprolactone-based nanoparticles) able to selectively treat/target microglia has been developed and used here to clarify the temporal and spatial involvement of the pro-inflammatory response associated to microglial cells in SCI. We show that a treatment with nanoparticles loaded with minocycline, the latter a well-known anti-inflammatory drug, when administered acutely in a SCI mouse model is able to efficiently modulate the resident microglial cells reducing the pro-inflammatory response, maintaining a pro-regenerative milieu and ameliorating the behavioral outcome up to 63 days post injury. Furthermore, by using this selective delivery tool we demonstrate a mechanistic link between early microglia activation and M1 macrophages recruitment to the injured site via CCL2 chemokine, revealing a detrimental contribution of pro-inflammatory macrophages to injury progression after SCI., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Atomic force microscopy in contact (AFM-C) mode was used to investigate the molecular dynamics of leonardite humic acid (HA) aggregate formed at different pH values. HA nanoparticles dispersed at pH values ranging from 2 to 12 were observed on a mica surface under dry conditions. The most clearly resolved and well-resulted AFM images of single particle were obtained at pH 5, where HA appeared as supramolecular particles with a conic shape and a hole in the centre. Those observations suggested that HA formed under these conditions exhibited a pseudo-amphiphilic nature, with secluded hydrophobic domains and polar subunits in direct contact with hydrophilic mica surface. Based on molecular simulation methods, a lignin-carbohydrate complex (LCC) model was proposed to explain the HA ring-like morphology. The LCC model optimized the parameters of β-O-4 linkages between 14 units of 1-4 phenyl propanoid, and resulted in an optimized structure comprising 45-50 linear helical molecules looped spirally around a central cavity. Those results added new insights on the adsorption mechanism of HA on polar surfaces as a function of pH, which was relevant from the point of view of natural aggregation in soil environment., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

In this work a large number of polymer nanoparticles (NPs) with different features have been synthesized through emulsion polymerization-based methods. Poly(methyl methacrylate) (PMMA), poly-ɛ-caprolactone (PCL), and poly(lactic acid) (PLA) based NPs with different size, hydrophobicity, surface charge, PEGylation degree, type of emulsifier and ζ potential have been produced and characterized. All the different NPs have been adopted for cellular uptake studies, leading to a precise quantification of the number of internalized NPs into a selected tumor cell line. The experiments summarize, emphasize and improve the comprehension of the influence of NPs features on the uptake efficiency. In detail, a linear relationship between uptake and both size and NP concentration independently upon other NP characteristics was found. Moreover, it was confirmed that cells are able to internalize and retain for a long time preferentially positively charged NPs. Finally, by coupling results of uptake studies with cell viability measurements, an easy and fast check to control the effectiveness of a selected polymer as drug carrier has been proposed. In particular, we observed that biodegradable PLA-based NPs with high molecular weight, non-PEGylated and positively charged PCL NPs are the better choice to maximize the uptake and minimize side effect against cells., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Humic acids (HA) have a colloidal character whose size and negative charge are strictly dependent on surface functional groups. They are able to complex large amount of poorly ordered iron (hydr)oxides in soil as a function of pH and other environmental conditions. Accordingly, with the present study we intend to assess the colloidal properties of Fe(II) coprecipitated with humic acids (HA) and their effect on Fe hydroxide crystallinity under abiotic oxidation and order of addition of both Fe(II) and HA. TEM, XRD and DRS experiments showed that Fe-HA consisted of Ferrihydrite with important structural variations. DLS data of Fe-HA at acidic pH showed a bimodal size distribution, while at very low pH a slow aggregation process was observed. Electrophoretic zeta-potential measurements revealed a negative surface charge for Fe-HA macromolecules, providing a strong electrostatic barrier against aggregation. Under alkaline conditions HA chains swelled, which resulted in an enhanced stabilization of the colloid particles. The increasing of zeta potential and size of the Fe-HA macromolecules, reflects a linear dependence of both with pH. The increase in the size and negative charge of the Fe-HA precipitate seems to be more affected by the ionization of the phenolic acid groups, than by the carboxylic acid groups. The main cause of negative charge generation of Fe/HA is due to increased dissociation of phenolic groups in more expanded structure. The increased net negative surface potential induced by coprecipitation with Ferrihydrite and the correspondent changes in configuration of the HA could trigger the inter-particle aggregation with the formation of new negative surface. The Fe-HA coprecipitation can reduce electrosteric repulsive forces, which in turn may inhibit the aggregation process at different pH. Therefore, coprecipitation of Ferrihydrite would be expected to play an important role in the carbon stabilization and persistence not only in organic soils, but also in waters containing dissolved organic matter., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

The possibility to control the fate of the cells responsible for secondary mechanisms following spinal cord injury (SCI) is one of the most relevant challenges to reduce the post traumatic degeneration of the spinal cord. In particular, microglia/macrophages associated inflammation appears to be a self-propelling mechanism which leads to progressive neurodegeneration and development of persisting pain state. In this study we analyzed the interactions between poly(methyl methacrylate) nanoparticles (PMMA-NPs) and microglia/macrophages in vitro and in vivo, characterizing the features that influence their internalization and ability to deliver drugs. The uptake mechanisms of PMMA-NPs were in-depth investigated, together with their possible toxic effects on microglia/macrophages. In addition, the possibility to deliver a mimetic drug within microglia/macrophages was characterized in vitro and in vivo. Drug-loaded polymeric NPs resulted to be a promising tool for the selective administration of pharmacological compounds in activated microglia/macrophages and thus potentially able to counteract relevant secondary inflammatory events in SCI., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Much evidence shows that acute and chronic inflammation in spinal cord injury (SCI), characterized by immune cell infiltration and release of inflammatory mediators, is implicated in development of the secondary injury phase that occurs after spinal cord trauma and in the worsening of damage. Activation of microglia/macrophages and the associated inflammatory response appears to be a self-propelling mechanism that leads to progressive neurodegeneration and development of persisting pain state. Recent advances in polymer science have provided a huge amount of innovations leading to increased interest for polymeric nanoparticles (NPs) as drug delivery tools to treat SCI. In this study, we tested and evaluated in vitro and in vivo a new drug delivery nanocarrier: minocycline loaded in NPs composed by a polymer based on poly-ε-caprolactone and polyethylene glycol. These NPs are able to selectively target and modulate, specifically, the activated proinflammatory microglia/macrophages in subacute progression of the secondary injury in SCI mouse model. After minocycline-NPs treatment, we demonstrate a reduced activation and proliferation of microglia/macrophages around the lesion site and a reduction of cells with round shape phagocytic-like phenotype in favor of a more arborized resting-like phenotype with low CD68 staining. Treatment here proposed limits, up to 15 days tested, the proinflammatory stimulus associated with microglia/macrophage activation. This was demonstrated by reduced expression of proinflammatory cytokine IL-6 and persistent reduced expression of CD68 in traumatized site. The nanocarrier drug delivery tool developed here shows potential advantages over the conventionally administered anti-inflammatory therapy, maximizing therapeutic efficiency and reducing side effects.

A delivery system based on polymer nanoparticles (NPs) is developed and tested in relevant biological conditions for breast cancer treatment. ɛ-Caprolactone (CL) and polyethylene glycol (PEG) copolymers have been used for the one pot synthesis of surfactant free PEGylated NPs which are monodispersed, stable in physiological conditions and have size in the range 90-250 nm. The degradation behavior of these NPs has been investigated in cell medium and a relation between degradation time and molecular weight of the starting CL-based material has been established. This allows producing NPs with controlled degradation kinetics. Finally, selected NPs have been tested in 4T1 breast cancer cells to check their toxicity and to investigate the uptake process, in order to validate their use as targeted vectors for breast cancer treatment., (Copyright © 2013 Elsevier B.V. All rights reserved.)

The aim of this work was to investigate the surface structure of aqueous hematite dispersions characterized by a large variability of morphology and particle size combining structural investigations obtained from Atomic Force Microscopy (AFM) and Transmission Electron Microscopy (TEM) techniques with in vitro particle size distributions and zeta potential measurements from Dynamic Light Scattering (DLS) technique, and we achieved a self-consistent and detailed characterization of hematite particles whose sizes and morphologies could be correlated to the synthesis conditions (type of added anion, Al substitution and pH). Surface AFM characterization provided an accurate analysis of particle microstructure and also indicated that the growth of microcrystals followed different surface roughness. DLS, AFM, and TEM techniques furnished complementary information on the average particle dimensions, whose variation could be attributed to the morphological difference of hematites, ranging from platy to regular or irregular hexagonal or ellipsoidal shape. Finally, a correlation between the average particle dimensions and the measured zeta potential was also been found in aqueous dilute suspensions characterized by neither pH nor-ionic-strength-control, for which a drop of zeta potential from positive to negative values was detected for hematite particle dimensions larger than a threshold size of ~150 nm., (Copyright © 2012 Elsevier Inc. All rights reserved.)

In vivo studies of LDL oxidation following consumption of natural phenolic compounds have yielded mixed results. It is reported that the amphiphilic hydroxytyrosol, after addition to human plasma, does not accumulate in LDL but protects plasma lipids, which are extracted together with hydroxytyrosol, from chemically-induced oxidation. Thus, a novel methodology was proposed, which does not rely on LDL separation and subsequent oxidation but is based on the oxidation of total lipids - simultaneously extracted from plasma with antioxidants - to evaluate the effects of micronutrients that do not partition into LDL, after in vivo supplementation., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Background & Aims: The biological role of fatty acids (FA) in the perinatal period is under active investigation. We here describe the application of a simplified microanalytical procedure to compare the FA profile of maternal, umbilical cord and infant whole blood, inclusive of all circulating lipid fractions and cells., Methods: The FA composition has been analyzed with a micromethod in 16 triplets, including maternal blood, cord blood at delivery and infant blood at day 4, respectively., Results: As expected, the FA composition of blood samples withdrawn from the umbilical cord is more similar to the FA composition of blood from 4-day old infants than the FA pattern of maternal blood at delivery. Nevertheless, infant blood FA profile differed from cord for lower long-chain polyunsaturated FA and higher monounsaturated FA., Conclusions: Our explorative data using whole blood microanalysis confirm the progressive increase of long-chain polyunsaturated FA levels from the mothers towards cord and then infant blood., (Copyright © 2011 Elsevier Ltd and European Society for Clinical Nutrition and Metabolism. All rights reserved.)

Objectives: To assess fatty acid (FA) profiles in whole blood of 90 cystic fibrosis patients (CF) and 30 control subjects (C) and to correlate FA changes to the severity of respiratory disease., Methods: Whole blood FA were assessed by GC with a micromethod-based analysis., Results: Saturated and monounsaturated FA are higher, whereas polyunsaturated FA are lower in CF versus C with reduction of total n-6 FA, 22:5n-3 and 22:6n-3 (DHA). The product of linoleic acid (LA) x DHA, proposed as a marker for the disease, is 30% lower in CF than in C. Correlations with the severity of the respiratory disease are present for different FA and for the LA x DHA product. There is a reduction of Delta5 desaturase activity in CF, greater in severe disease, suggesting a basic metabolic alteration., Conclusions: The micromethod-based analysis of blood FA facilitates the assessment of the FA status while confirming alterations of FA profiles already reported in specific blood compartments of CF.

The aim of this study was to compare blood fatty acid profiles of two population groups: Italian and Tibetan, differing with regard to ethnic, life style and environmental aspects. Additionally the collection of two staple foods provided the opportunity to analyze typical Tibetan dishes. A new, simple, rapid, and substantially non invasive method for fatty acid (FA) analysis of blood lipids was applied to healthy Italian (n=14) and Tibetan (n=13) subjects. Blood drops obtained from the ear lobe of Tibetans or the fingertip of Italians were adsorbed by a special strip of paper and processed for fatty acid analysis. The fatty acid profiles of the two groups are different, and environmental factors, such as dietary fats and altitudes of Milan, Italy (a low altitude site), and Lhasa, Tibet (a high altitude site) appear to contribute to these differences. More specifically, in Ti-betans higher levels of monounsaturated fatty acids, including the 22 and 24 carbon molecules, were found. This appears to be derived mainly from locally consumed fats (mustard seed oil), and are associated with lower levels of total polyunsaturated fatty acids and higher levels of selected omega 3 fatty acids, when compared to the Italians. These relatively higher levels of monounsaturated fatty acids may also indicate means of adaptation to local prooxidant conditions. The observed differences in blood fatty acid profiles in Tibetans vs. Italians appear to result both from dietary factors and adaptation to local environmental conditions such as the high altitude of the Tibetan location.

Background and Aims: Ingestion of alpha linolenic acid (ALA), with the richest source among dry fruits such as walnuts, is associated with cardiovascular prevention. The aim of this study was to selectively evaluate the effects of moderate walnut consumption on the levels of ALA and its metabolic derivatives in human blood., Methods and Results: After a 2-week run-in period, 10 volunteers consumed 4 walnuts per day (in addition to their habitual diet) for 3 weeks. Fatty acid profiles, with special attention to levels of ALA and long chain polyunsaturated fatty acids (LC-PUFA), were assessed in blood drops collected from fingertips. The data indicate that the administration of a few walnuts a day for 3 weeks significantly increases blood levels, not only of ALA (from 0.23+/-0.07 SD to 0.47+/-0.13 SD), but also of its longer chain derivative eicosapentaenoic acids (EPA) (from 0.23+/-0.37 to 0.82+/-0.41) with levels remaining elevated over basal values after washout., Conclusion: The findings of this pilot study indicate that plant ALA in appropriate food items favourably affects the n-3 LC-PUFA status.

Background: Infants in developing countries require early dietary interventions to prevent nutritional deficiencies, above all protein, energy, iron and zinc. To what extent these interventions may affect the fatty acid (FA) status is still unknown., Objectives: To examine and compare the effects of 2 micronutrient "sprinkles" supplementations (iron 12.5 mg + folic acid 150 microg, iron/folate and iron 12.5 mg + folic acid 150 microg + zinc 5 mg + vitamins A, C and D3, mineral/micronutrient [MMN]) versus placebo on the FA status of Cambodian infants., Methods: A total of 204 infants age 6 mo and living in Kompong Chhnang Province, Cambodia, were randomly assigned to receive daily supplementation of MMN (n = 68) and iron/folate (n = 68) or placebo (n = 68) for a 12-mo period in powder form as sprinkles. At the end of the intervention period, FAs in the range of 16 to 24 C were determined in blood drops absorbed on a strip collected from 182 subjects, and values among the 3 intervention subgroups and those of 21 Italian 18-mo-old, normal-growing infants as the reference group were compared., Results: At the end of the supplementation trial, higher levels of the 2 essential FAs (EFAs) (linoleic acid, 18:2n-6, and alpha-linolenic acid, 18:3n-3) were found in the MMN group. No differences occurred for the major longer chain derivatives of both EFAs arachidonic acid (20:4n-6) and docosahexaenoic acid (22:6n-3). In MMN supplemented Cambodians, blood levels of linoleic acid approached those of Italian infants, and in addition their alpha-linolenic acid levels were improved. Cambodian infants, mostly still breast-fed through the second year of life, showed significantly higher levels of long-chain derivatives of both the n-6 and the n-3 series compared with Italians., Conclusions: Supplementation with iron, folic acid, zinc and vitamins was associated with an increase of linoleic acid and alpha-linolenic acid levels in Cambodian infants versus placebo, without significant changes in the concentrations of their longer chain derivatives, resulting in a FA status closer to Italian counterparts for the essential polyunsaturated FA levels. The iron/folate-treated infants showed no differences compared with the other 2 groups. Studies are needed to differentiate the potential effects of the supplemented micronutrients on the FA status.

In newborn infants, progressive decrease in anthropometric values and impairment of the docosahexaenoic acid (DHA) status was associated with maternal smoking during pregnancy, with a parallel increase of the metabolic precursor of DHA, alpha-linolenic acid. Maternal smoking may impair DHA synthesis which may contribute to reduced fetal growth.

The activity of a range of enzymes related to the cycling of the main biologically important nutrients C, N, P and S was investigated in cultivated and non-cultivated soils from various parts of Europe. Two agricultural sites from North Italy under continuous corn (Zea mays L.) with and without organic fertilization were compared. Two other agricultural sites from South Italy under hazel (Corylus avellana L.) never flooded or repeatedly flooded over by uncontrolled urban and industrial wastes were investigated. The non-cultivated soils were from Middle and South Europe with different pollution history such as no-pollution and pollution with organic contaminants, which is phenanthrene and other polycyclic aromatic hydrocarbons (PAHs). Agricultural soils showed significant differences in some of physical-chemical properties (i.e. organic C, total and labile phosphate contents, available Ca and Mg) between the two sites studied. Enzyme activities of hazel sites periodically flooded by wastes were mainly higher than in the hazel sites never flooded. Sites under many years of continuous corn showed dehydrogenase, invertase, arylsulphatase and beta-glucosidase activities generally lower than the soils under hazel either flooded or not by wastes. As compared to agricultural soils, non-cultivated soils heavily or moderately polluted by organic contaminants displayed much lower values or complete absence of enzymatic activities. Dissimilar, contradictory correlations between soil enzyme activities and the majority of soil properties were observed separately in the two groups of soils. When the whole set of enzyme activities and soil properties were considered, all significant correlations found separately for the groups of soils were lost. The overall results seem to confirm that no direct cause-effect relationships can be derived between the changes of a soil in response to a given factor and both the variations of the activity and the behaviour of the enzymes in soil.

Maternal smoking during pregnancy has been associated with a reduced content of n-3 long-chain PUFA (LC-PUFA) in breast milk, thereby reducing the intake of key nutrients by the infants. We postulated that the mammary gland is affected by maternal smoking in the process of n-3 LC-PUFA secretion into milk. This prompted us to investigate the effects of cigarette smoke on the synthesis of n-3 LC-PUFA in vitro by using a line of healthy epithelial cells from the human mammary gland, MCF-10A. Cells were exposed to cigarette smoke under controlled conditions by adding to the medium aliquots of horse serum containing smoke components, as analyzed by GC-MS. The major findings concern the inhibition of both the conversion of the precursor 14C-ALA (alpha-linolenic acid) to n-3 LC-PUFA and of the A5 desaturation step (assessed by HPLC analysis with radiodetection of n-3 FAME) following exposure to minimal doses of smoke-enriched serum, and the dose-dependent relationship of these effects. The data indicate that exposure to cigarette smoke negatively affects the synthesis of n-3 LC-PUFA from the precursor in mammary gland cells.

Several studies have shown that the fatty acid composition of circulating lipids reflects dietary fat intake, in turn being related to health status. The fatty acid composition of plasma lipids is therefore an important parameter in studies on dietary interventions. The aim of our study was to develop a rapid and inexpensive method for the analysis of circulating fatty acids applicable to large population groups. Drops of blood collected from fingertips have been directly subjected to transmethylation for gas chromatography analysis. This new method, validated for reproducibility, has been compared with the conventional method, based on withdrawal of blood from the antecubital vein followed by lipid extraction, and identical data have been obtained with the two techniques. Observed and predicted differences between blood and plasma fatty acids are related to the contribution of circulating cell membranes in blood. Finally the application of the methods to samples from 100 healthy subjects and the assessed correlation between dietary habits and blood fatty acid profiles demonstrate the validity of the new method and its applicability to nutritional and epidemiological studies.