Green Synthesis of Advanced Carbon Materials Used as Precursors for Adsorbents Applied in Wastewater Treatment.

Huge amounts of vegetable waste, mainly resulting from the food industry, need large areas for storage, as they could cause hazardous environmental impact, leading to soil and water pollution or to CO2 emissions during accidental incineration. This work was aimed at recycling certain lignocellulosic waste (walnut shells, kernels of peach, apricot, and olive) to design advanced carbon material precursors (ACMP) to be used for obtaining nano-powders with high applicative potential in pollution abatement. Both waste and ACMP were characterized using proximate and elemental analysis, and by optical microscopy. Complex characterization of raw materials by FTIR, TGA-DTG, and SEM analysis were carried out. The ACMP were synthetized at 600-700 °C by innovative microwave heating technology which offers the advantages of lower energy consumption using 3.3 kW equipment at laboratory level. The ACMP ash < 3% and increased carbon content of 87% enabled the development of an extended pore network depending on degassing conditions during heating. TEM analysis revealed a well-developed porous structure of the synthesized ACMP carbonaceous materials. Due to the presence of oxygen functional groups, ACMPs exhibit adsorption properties highlighted by an iodine index of max. 500 mg/g and surface area BET of 300 m2/g, which make them attractive for removal of environmental pollutants such as dyes having molecule sizes below 2 nm and ions with pore dimensions below 1 nm, widely used industrially and found in underground waters (NO3-) or waste waters (SO42-).

Collagen-Based Hydrogels Composites from Hide Waste to Produce Smart Fertilizers.

The study aims at reusing and recycling the protein hide waste from the leather industry in ecological conditions by elaborating an innovative procedure in order to obtain a collagen matrix functionalized with nitrogen, phosphorus, and potassium (NPK) nutrients to be used for preparing smart fertilizers. This is an interdisciplinary approach, as it starts from hide waste raw material as a critical industrial waste, which is then subjected to several technological steps by selection of optimal processing parameters, followed by product fabrication at the laboratory, and next scales to the industrial pilot plant to obtain novel agro-hydrogels. In this context, the technology scheme for collagen hydrolysate with encapsulated nutrients was proposed and the process parameters were optimized by functionalization of agro-hydrogels with various natural and synthetic polymers, such as polyacrylamide, poly(sodium 4-styrenesulfonate-co-glycidyl methacrylate) copolymer, starch or dolomite. Based on the laboratory experiments, a pilot plant was constructed and tested. Taking as reference the collagen hydrolysate with encapsulated nutrients, the new fertilizers were adequately characterized by chemical analysis, determination of biodegradability and the degree of release of oxidable compounds in water. Based on the biodegradation mechanism and kinetic analysis of oxidable compounds release, adequate arguments are evidenced to demonstrate that these fertilizers can be applied for amendment of poor agricultural soils.

Modification of Collagen Derivatives with Water-Soluble Polymers for the Development of Cross-Linked Hydrogels for Controlled Release.

Novel cross-linked hydrogels were synthesized as potential materials for the development of smart biofertilizers. For this purpose, hydrogels were prepared using collagen hydrolysate recovered from tannery waste. The water-soluble polymer poly(sodium 4-styrenesulfonate-co-glycidyl methacrylate) (P(SSNa-co-GMAx)) was among others used for the cross-linking reaction that combined hydrophilic nature with epoxide groups. The synthetic procedure was thoroughly investigated in order to ensure high percentage of epoxide groups in combination with water-soluble behavior. The copolymer did not show cytotoxicity against normal lung, skin fibroblasts, or nasal polyps fibroblasts. Through the present work, we also present the ability to control the properties of cross-linked hydrogels by altering copolymer's composition and cross-linking parameters (curing temperature and time). Hydrogels were then studied in terms of water-uptake capacity for a period up to six days. The techniques Proton Nuclear Magnetic Resonance (1H NMR), Thermogravimetric Analysis (TGA), Size Exclusion Chromatography (SEC), and Attenuated Total Reflection Fourier Transform Infrared Spectroscopy (ATR-FTIR) were applied for the characterization of the synthesized copolymers and the cross-linked hydrogels. Three samples of biofertilizers based on collagen hydrolysate functionalized with P(SSNa-co-GMAx) and starch and having nutrients encapsulated (N, P, K) were prepared and characterized by physical-chemical analysis and Energy Dispersive X-ray analysis-Scanning Electron Microscope (EDAX-SEM) in terms of microstructure. Preliminary tests for application as fertilizers were performed including the release degree of oxidable organic compounds.

New Approach to Prepare Willow Bark Extract-Lipid Based Nanosystems with Enhanced Antioxidant Activity.

In this study the conventional oils used for lipid nanocarriers (NLCs) synthesis were replaced by high concentration of fish oils (e.g., fish oil concentrated in omega-3 fatty acids, fish oil enriched in omega-3 and omega-6 fatty acids and salmon oil), in order to produce appropriate lipid based nanosystems able to entrap willow bark extract (WBE). Formulation factors such as the nature of the fish oil, glycerol content and WBE loading were evaluated to produce optimum lipid based nanosystems with suitable physical stability and enhanced antioxidant activity. The synthesized WBE-NLC showed spherical and homogeneous particles and average diameters in the range of 200-250 nm, as determined by TEM measurements. The electrokinetic potentials were negative for all free- and WBE-loaded NLCs, with values between -29.1 ÷ - 35.8 mV, which reveal an excellent physical stability. By scanning calorimetry measurements it has been shown that the lipid crystallization and melting behavior of NLCs before and after loading with WBE were no significantly influenced by the type of fish oil used and only in a few NLCs formulations an obvious perturbation of lipid network have been detected. The chemiluminescence technique has been used to assess the effect of fish oil type on the in vitro antioxidant activity of WBE-NLCs. Ability of WBE entrapped within NLCs to scavange the free radicals was greater than for native WBE and fish oils. The difference between the antioxidant activity of WBE-NLC (98%) and those of pure WBE (AA% = 77.2) and fish oil (AA% = 83.7), may be explained by the occurrence of a synergistic effect between the components of lipid nanocarriers.

Integrative approach in prevention and therapy of basal cellular carcinoma by association of three actives loaded into lipid nanocarriers.

Basal cell carcinoma (BCC) is one of the commonest malignancies occurred on sun-exposed skin, mainly by UV-B radiation, of lighter-skinned individuals. The aim of the present study was to develop advanced drug delivery formulations used in BCC therapy that overcomes chemotherapy-induced side-effects of skin photosensitivity by an integrative approach of nanoencapsulation in conjunction with combination therapy that uses chemotherapeutic, chemoprotective and sunscreen agents. The combination of anticancer drug together with sunscreen agent is very useful in therapy, especially for individuals who are more exposed to the sun without using a sunscreen. Nanostructured lipid carriers (NLCs) employed as drug delivery systems were co-loaded with 5-fluorouracil (5-FU), a hydrophilic chemotherapeutic drug, and ethylhexyl salicylate (EHS), a lipophilic UV-B sunscreen agent. The NLCs were developed using bioactive squalene (50.8% w/w) from amaranth seed oil as chemoprotective agent. By varying the concentrations of 5-FU and EHS, the co-loaded NLCs presented particle sizes of about 100nm, acceptable physical stability with values smaller than -25mV and appropriate entrapment efficiency that reaches values over 65% for both types of drugs. The UV-B blocking ability of EHS loaded into NLCs were influenced by the concentration of 5-FU. The amaranth oil offered a capacity of 70% in scavenging the free radicals. In vitro drug release showed that NLCs presented sustained release of 5-FU that followed the Fick's law of diffusion.

Rice bran and raspberry seed oil-based nanocarriers with self-antioxidative properties as safe photoprotective formulations.

The aim of this research was to develop advanced lipid nanocarriers based on renewable vegetable resources (rice bran oil and raspberry seed oil) that possess self-antioxidative properties, having advantages in terms of minimal side effects and exhibiting the ability to simultaneously co-encapsulate and co-release two active compounds. The focus has been oriented towards developing safe cosmetic formulations with broad-spectrum photoprotection based on these new lipid nanocarriers that contain large amounts of vegetable oils and low concentrations of synthetic UVA and UVB filters (butyl-methoxydibenzoylmethane - BMDBM and octocrylene - OCT). The lipid nanocarriers have a spherical shape and show good physical stability, with a zeta potential in the range of -25.5 to -32.4 mV. Both vegetable oils play a key role in the preparation of efficient nanocarriers, leading to a less ordered arrangement of the lipid core that offers many spaces for the entrapment of large amounts of BMDBM (79%) and OCT (90%), as wells as improved antioxidant activity and UV absorption properties, particularly for the lipid nanocarriers prepared from rice bran oil. By formulating the lipid nanocarriers into creams containing only 3.5% of the UV filters and 10.5% of the vegetable oils, the resulting sunscreens exhibited improved photoprotection, reflecting up to 91% and 93% of UVA and UVB rays, respectively. A new direction of research achieved by this study is the multiple release strategy of both UV filters from the same lipid nanocarrier. After 24 hours, a slow release of BMDBM (less than 4%) and OCT (17.5%) was obtained through a Fick diffusion process. This study demonstrates a significant advance in the areas of both nanotechnology and cosmetics, developing safer cosmetic formulations that possess broad antioxidant, photoprotective and co-release effectiveness due to the existence of a high content of nanostructured vegetable oils combined with a low amount of synthetic UV filters in the same carrier system.

Coencapsulation of butyl-methoxydibenzoylmethane and octocrylene into lipid nanocarriers: UV performance, photostability and in vitro release.

The coencapsulation of two UV filters, butyl-methoxydibenzoylmethane (BMDBM) and octocrylene (OCT), into lipid nanocarriers was explored to develop stable cosmetic formulations with broad-spectrum photoprotection and slow release properties. Different types of nanocarriers in various concentrations of the two UV filters were tested to find the combination with the best absorption and release properties. Solid lipid nanoparticles (SLNs) and nanostructured lipid carriers (NLCs) have been the two types of lipid nanocarriers used. The NLCs were based on either medium chain triglycerides (MCT) or squalene (Sq). The following physicochemical properties of the nanocarriers have been evaluated: particle size, morphology, zeta potential (ZP), entrapment efficiency, loading capacity, and thermal behavior. The nanocarriers have been formulated into creams containing low amounts of UV filters (2.5% BMDBM and 1% OCT). The best photoprotection results were obtained with the cream based on NLCs prepared with MCT, having a sun protection factor (SPF) of 17.2 and an erythemal UVA protection factor (EUVA-PF) of 50.8. The photostability of the encapsulated BMDBM filter was confirmed by subjecting the nanocarriers-based creams to in vitro irradiation. The prolonged UV-protection efficacy was coupled with a slow in vitro release of the synthetic UV filters, which followed the Higuchi release model.

The encapsulation effect of UV molecular absorbers into biocompatible lipid nanoparticles.

The efficiency of a cosmetic product depends not only on the active ingredients, but also on the carrier system devoted to improve its bioavailability. This article aims to encapsulate two couples of UV molecular absorbers, with a blocking action on both UV-A and UV-B domains, into efficient lipid nanoparticles. The effect of encapsulation on the specific properties such as sun protection factor and photostability behaviour has been demonstrated. The lipid nanoparticles with size range 30-350 nm and a polydispersity index between 0.217 and 0.244 are obtained using a modified high shear homogenisation method. The nanoparticles had spherical shapes with a single crystallisation form of lipid matrices characteristic for the least ordered crystal structure (α-form). The in vitro determination of photoprotection has led to high SPF ratings, with values of about 20, which assure a good photoprotection and filtering about 95% of UV radiation. The photoprotection effect after irradiation stage was observed to be increased more than twice compared to initial samples as a result of isomerisation phenomena. All the results have shown that good photoprotection effect and improved photostability could be obtained using such sunscreen couples, thus demonstrating that UV absorbers-solid lipid nanoparticles are promising carriers for cosmetic formulations.

Pharmaceuticals and cosmeceuticals based on soft nanotechnology techniques with antioxidative, immunostimulative and other therapeutic activities.

A number of 46 out of a total of more than 200 recent patents in soft nanotechnology referring to applications of nanoemulsions for pharmaceutical and cosmetical formulations has been selected and reviewed. As key factors to maximize the efficiency of bioactive principles embedded within colloidal drug delivery systems are the nature and ratio of hydrophilic/lipophilic components, of surfactants/cosurfactants as emulsifiers, their mutual solubility and biocompatibility, the size and polydispersity of nanoparticles. The antioxidant and immunostimulative actions are discussed in relation to the specific therapeutic effects of galenical compositions used for preventing and/or treating various diseases.

The antioxidative activity of riboflavin in the presence of antipyrin. Spectroscopic studies.

The effect of Antipyrin upon the antioxidant activity of the riboflavin has been evidenced using chemiluminescent system luminol-hydrogen peroxide, in Tris-HCl buffer, pH 8.5. It was found that riboflavin antioxidant activity depends on the reaction time and the Antipyrin concentration. Using ESR spectroscopy the hydroxyl radical generation, in the mentioned chemiluminescent system, was evidenced. The interaction between reactants was also investigated by UV-VIS and fluorescence spectroscopy. The effect of Antipyrin concentration upon the riboflavin fluorescence has also been investigated. The fluorescence quenching by Antipyrin is not significant and subsequently the riboflavin fluorescence quenching doesn't indicate an electron transfer process through diffusion-controlled mechanism. The results are discussed with relevance to the redox processes of riboflavin.

Effects of prooxidants on human serum exposed to 50 Hz magnetic fields.

The purpose of this article is to evaluate magnetic field effects (50 Hz, different magnetic intensities) on the chemiluminescence intensity of human serum. We find that 1 and 2 h of exposure increased the chemiluminescence emission. The addition to the serum of prooxidants FeCl(2) and H(2)O(2) in different concentrations increased the chemiluminescence intensity even more.

Decrease of luminol chemiluminescence upon exposure of human blood serum to 50 Hz electric fields.

The chemiluminescence of luminol, after 1 and 2h in vitro exposure of human serum to 50 Hz electric fields of different intensities, decreases as compared to the controls. This indicates a field-induced decrease in the concentration of the free radicals. The report is limited to the key kinetic and field data, inviting independent kinetic analysis of the data in terms of reaction moments or reaction susceptibilities for the various normal modes indicated by the data.