Herein, we described the synthesis of a novel ion-imprinted membrane for the detection of palladium(II) prepared through the glutaraldehyde crosslinking of chitosan with a 4-[(4-Hydroxy)phenylazo]benzenesulfonic acid ligand trapped into the membrane. The imprinting technology was used to improve adsorption capacity and adsorption selectivity, and was combined with some advantages of the developed membrane, such as low cost and ease of preparation, water-friendly synthesis, and high biocompatible chitosan material. The membranes were characterized by Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), and Energy Dispersive X-ray Spectrometry (EDS). The results obtained showed a high swelling ratio with a maximum value of 16.4 (1640%) at pH 4 with a strong pH dependence. Batch rebinding experiments gave a maximum adsorption capacity of 101.6 mg of Pd(II) per gram of imprinted membrane. The Pd(II) adsorption behavior was well-described by a Langmuir model with a theoretical maximum adsorption capacity of 93.48 mg g(-1), similar to the experimental one. Finally, a selectivity study versus Ag(I), Pb(II), and Fe(III) ions demonstrated a good selectivity of chitosan-imprinted membrane towards Pd(II).

In this work, we report the synthesis of novel inorganic–organic hybrid nanomaterials (GO@Fe3O4/CuPc) and GO@Fe3O4/ZnPc) consisting of sheets of graphene oxide (GO) decorated by iron oxide nanoparticles (Fe3O4), the whole heterostructure functionalized with metallo-phthalocyanines (MPc, M:Cu or Zn). First the synthesis of nanomaterial (GO@Fe3O4) was prepared by hydrothermal self-assembly process through the mixture of graphene oxide and Fe?2/Fe?3 salt solution. The metallo-phthalocyanines anchorage on the surface of nanosystem was lately performed by facile and effective ultrasonication method. The structure, composition and morphology of nanohybrids and intermediates were investigated by Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, differential scanning calorimetry, UV–visible spectroscopy, scanning and transmission electron microscopy and impedance spectroscopy. All the results suggested that iron-based nanoparticles were successfully deposited onto graphene oxide sheet networks in the form of Fe3O4, forming nanospheres, decreasing in lattice defects of the GO sheets and dramatically increasing the dielectric properties of nanosystems. Nanomaterials presented saturation magnetization in the 52–58 emu/g and superparamagnetic behavior. It was observed that the values of dielectric constant decreased as a function of the amount of phthalocyanines in the nanomaterials. Therefore, because of their versatile magnetic and dielectric performances, the novel superparamagnetic hybrid nanomaterials, herein described, can be considered as potential for microwave devices.

Cardanol is a renewable, low cost natural material, widely available as a by-product of the cashew industry. It is a mixture of 3-n-pentadecylphenol, 3-(pentadeca-8- enyl)phenol, 3-(pentadeca-8,11-dienyl)phenol and 3-(pentadeca-8,11,14-trienyl)phenol. Olefin metathesis (OM) reaction on cardanol is an important class of reactions that allows for the synthesis of new olefins that are sometime impossible to prepare via other methods. The application of this natural and renewable material to both academic and industrial research will be discussed.

This chapter provides an overview of the progresses of research activities related with the synthesis of functional heterocyclic systems utilizing mainly cardanol—or structural analogous (i.e., anacardic acid, cardol, methylcardol) deriving from the cashew nut shell liquid—as starting material, a renewable feedstock having significant perspectives in the field of the green chemistry and design of innovative environmentally friendly chemical processes.

This manuscript describes the preparation of green nanovesicles by using cardanol as renewable starting material with embedded minor amounts of phthalazines, a class of heterocyclic bioactive compounds. The nanovesicles were prepared by stirring induced self-assembly in aqueous medium without involvement of any organic solvent. Dynamic light scattering studies and transmission electron microscopy revealed the formation of nanostructure with an average diameter in the range of 227375 nm and a well defined spherical morphology. Potential antioxidant activity of nanovesicles were evaluated for the first time by 2,20-azino-bis-(3ethylbenzothiazoline-6-sulfonic acid) (ABTS) scavenging assay and bleomycin-dependent DNA damage. Moreover, their cytotoxic effects were also investigated by 3-[4,5-dimethylthiazole-2-yl]-2,5diphenyltetrazolium bromide (MTT) assay on different tumour cell lines. Unloaded nanovesicles showed moderate antioxidant and antitumoural activity that was further enhanced particularly by embedding the 2-[4-(4-Hydrazinophthalazin-1-yl)-phenyl]-isoindole1,3-dione compound.

The global concern about the problems caused by the growing consumption of petrochemical compounds, such as global warming and the diminishing of fossil fuels reserves, has given rise to the green chemistry field—based on the design of products and processes that minimize the use and generation of hazardous substances—in both academy and industry. In face of the increasing demand for chemicals, sustainable and innovative technologies are necessary in order to overcome current difficulties and also avoid the evolution of new ones. The advent of agro-industry waste as a resource of raw materials has attracted the attention of researchers and opened a window of opportunity for the breakthrough of alternative products to the oil industry. In this sense, cashew nutshell liquid (CNSL), a by-product from cashew industrial processing and one of the richest natural sources of phenolic compounds, emerges as a promising and renewable feedstock for the development of a wide range of functional products. This chapter is focused on the discussion of the origin and chemical composition of the different types of CNSL, and also on the challenges involved in the methods of isolation and main applications of its major component, cardanol, in the context of a sustainable development.

catalysts under UV light irradiation in aqueous dispersions in the presence of H2O2. Photocatalysts with the lowest Fe content (1%) showed a considerably better behavior with respect to the unloaded TiO2 and the catalysts with higher Fe contents. Photocatalytic degradation was studied under different conditions such as amounts of 1% Fe–TiO2 catalyst, H2O2 dose and initial pH of 4-NP solution. The results indicated that about 67.53% total organic carbon of a solution containing 20mgL−1 4-NP was removed at pH 6.17 by using 4.9mMof H2O2 and 0.4 g L−1 of the catalyst in a 2-L batch photo-reactor, the complete degradation of 4-NP occurring after 60 min. It was also observed that catalytic behavior could be reproduced in consecutive experiments without a considerable decrease of the UV/Fe–TiO2/H2O2 process efficiency.

The present work made a comparative study between two purification methods, column chromatography and recrystallization, for compounds derived from cardanol, a by-product of the cashew industry (Anacardium occidentale L.). The compounds were successfully synthesized and characterized, focusing our attention to results obtained in terms of yield, purity, generation of solid waste and amount of solvent used in each purification process. For all the synthesized compounds, the amount of solvent used was greatly reduced in the recrystallization process, with purities above 80%, when compared to chromatographic column, which still demands high amounts of eluent.

Samples of manganese–zinc (MnZn) ferrites were successfully prepared by hydrothermal syntheses using different compositions of the reactive system (H2O)1-x:(EG)x (x = 0, 0.2, 0.4, 0.6, 0.8, and 1.0), where EG = ethylene glycol. The samples were fully investigated by powder X-ray diffraction, Fourier transform infrared spectroscopy for both liquid and solid specimens, Mo¨ssbauer spectroscopy, vibrating sample magnetometer, and transmission electron microscopy. All the MnZn ferrites presented spinel phase and average particle diameters between 3.1 and 12.1 nm. The increase in the x values results in a decrease in the particle sizes. The FTIR spectra performed in liquid phase showed significant interaction between EG and metallic precursors used in the synthesis. Magnetic features as for instance saturation magnetization (MS) also decreases upon increasing the x values. In addition, all synthesized samples exhibited a superparamagnetic character at room temperature. The experimental methodology presented in this work is used to obtain superparamagnetic nanoparticles with controlled size (smaller than 13 nm) and morphology.

Combined separation and purification processes are gaining considerable attention in the water engineering community as they have the potential to integrate several treatment stages in a single, space-efficient and multifunctional process able to act as a multi-barrier against a wide spectrum of recalcitrant pollutants. In this paper, the efficiency of a combined physico-chemical process, previously validated as a tertiary treatment for municipal wastewater reclamation and successfully tested at pilot scale for the removal of total phenols, chemical oxygen demand (COD) and Escherichia coli, was tested for the precipitation of low-arsenic (V) concentration (<100 μg/L) from drinking water. The combined process, consisting of simultaneously dosing, in various proportions and according to a Latin square design-of-experiment scheme, aluminum polychloride (AP), zeolite (Z), powder activated carbon (PAC) and sodium hypochlorite (SH) into dechlorinated tap water spiked with arsenic (V), was assessed at laboratory scale in order to elucidate the mechanism of arsenic (V) removal as well as to identify the optimal mixing conditions using variable-speed jar-test experiments. Results indicated that the combined process was very effective in removing low arsenic (V) concentration from drinking water in the range of 25–100 μg/L. Moreover, it was found that, among the tested variables, high-velocity gradient conditions led to an improved removal efficiency which reached 89% under optimized process conditions. Although all treating agents played a statistically significant role in terms of process performance, arsenic (V) co-precipitation by AP was found to be the dominating removal mechanism contributing up to an 85% at 1400 rpm, with Z and PAC co-operating for the remaining 5% and mostly functioning as enhancing agents for ballasted settling. Notably, the process investigated in this study was also found to be robust against variation in initial arsenic concentration, showing similar arsenic (V) removal efficiency (85.9%) when the initial arsenic (V) concentration was further reduced from 100 to 25 μg/L. In conclusion, it was demonstrated that the combined treatment process was able to efficiently and simultaneously remove not only organic micropollutants such as phenols, COD and E. coli (as demonstrated in previous studies) but also inorganic contamination by arsenic (V) from a typical drinking water matrix via co-precipitation on aluminum polychloride, a treating agent that is worldwide accessible and typically used in water treatment applications.

In this paper, a new organic–inorganic CuPp–ZnO photocatalyst was achieved by copper (II) 5- mono-[4-(2-ethyl-p-hydroxybenzoate)ethoxyl]-10,15,20-triphenylporphyrin (CuPp) impregnated onto the surface of ZnO with an effective mixing method. Then the CuPp–ZnO photocatalyst was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV–vis diffuse reflectance spectroscopy (DRS), Fourier transform infrared (FT-IR) spectroscopy and photoluminescence spectra (PL). The results revealed that CuPp successfully impregnated onto the surface of ZnO and there existed an interaction between ZnO and CuPp. The photocatalytic activities of the CuPp–ZnO photocatalyst were evaluated in the photocatalytic degradation of rhodamine B (RhB) both under UV–vis and visible light ( ≥ 420 nm) irradiation. It was found that the CuPp–ZnO photocatalyst showed much higher photodegradation efficiency than bare ZnO, which improved the separation of photogenerated electrons and holes. The active species during the photocatalytic reaction were detected by using different types of active species scavengers. Finally, the photocatalytic mechanisms both under UV–vis and visible light irradiation were proposed. In addition, the repetition test demonstrated that the CuPp–ZnO still maintained high photocatalytic activity over five recycles. Based on the present study, it could be considered as a promising photocatalyst for future applications.

Limited solar photo-activity and recovering the catalysts after photocatalysis reaction are two major drawbacks of the highly active TiO2 powder materials. In this study we propose that copper phthalocyanine (CuPc, Cu(II) tetrakis[4-(2,4-bis-(1,1-dimethylpropyl)phenoxy)]phthalocyanine), which is an metal-organic dye could be used as sensitizer of TiO2 coating to shift the absorption band toward visible light. TiO2 coating was applied inside the Pyrex glass tubes and used in the photocatalytic decomposition of ethylene gas under solar light irradiation. Two-step draining method was employed to apply the coating on the inner side of the glass tubes. At first pure TiO2 coating was prepared from a solution by dispersing the commercial P25 TiO2 powders in a TiO2 sol made by hydrolysis-condensation of titanium alkoxide. A controlled draining method was employed to coat the inner side of the glass tubes. After calcination at 500 °C, P25 powders were strongly attached on the glass surface as a thick coating. Visible light absorptive coating was prepared by applying a thin layer of CuPc that shows intense absorption in the visible wavelength region utilizing the same coating procedure. CuPc coated TiO2 film showed excellent photo-stability against solar radiation. Greater photo-oxidation rate of ethylene was achieved with the CuPcTiO2 coated glass tube compared to that without CuPc coating due to the enhanced solar light absorption.

Corrosion inhibition potentials of three phosphites namely, M(HPO3) (where M=Mn, Co and Cu), for carbon steel in saline water from oil source wells were evaluated using weight loss and electrochemical impedance spectroscopy (EIS) methods. Characterization of the surface morphology was performed by SEM/EDX investigations. The corrosion rate of carbon steel in saline water decreased with increasing M(HPO3) concentration and increased with increasing temperature. M(HPO3) inhibits the corrosion of carbon steel by an adsorption mechanism, which follows Langmuir isotherm adsorption. The order of the inhibition efficiency of inhibitors is as follows: Mn(HPO3)<Co(HPO3)<Cu(HPO3). The thermodynamic functions of dissolution and adsorption processes were calculated and discussed.

Organic coatings have been widely used to protect carbon steel pipelines from external corrosion; however, they often suffer from permeability and weak adhesion. Here we show that synthetic lanthanide bis-phthalocyanine complexes, LnPc2 (Ln ¼ lanthanide metal, Pc ¼ C32H16N8 denotes the phthalocyanine ligand) can be used to form new nanocomposite coatings to provide corrosion protection to the underlying carbon steel pipelines. Electrochemical studies (EIS and potentiodynamic polarization) showed that the incorporation of LnPc2 compound (PrPc2, SmPc2 and HoPc2) additives with alkyd coating, leads to a significant increase in the corrosion resistance of carbon steel in 0.5 M HCl solution. The alkyd@LnPc2 nanocomposite coatings absorb very low water volumes, when compared to the neat alkyd coating. LnPc2 compounds allowed enhancing the pull-off adhesion of coatings performance from 3.34 MPa to 19.94 MPa. The efficiency of alkyd@HoPc2 coating appears higher than that of alkyd@PrPc2 and alkyd@SmPc2 coatings. The protective properties of alkyd@LnPc2 coatings were confirmed by SEM, TGA, scratch hardness, impact resistance, bend test and contact angle analysis.

Cardanol is a natural and renewable organic raw material obtained as the major chemical component by vacuum distillation of cashew nut shell liquid. In this work a new sustainable procedure for producing cardanol-based micellar nanodispersions having an embedded lipophilic porphyrin itself peripherally functionalized with cardanol substituents (porphyrin-cardanol hybrid) has been described for the first time. In particular, cardanol acts as the solvent of the cardanol hybrid porphyrin and cholesterol as well as being the main component of the nanodispersions. In this way a “green” micellar nanodispersion, in which a high percentage of the micellar system is derived from renewable “functional” molecules, has been produced.

With relevance to an increasingly large set of environmentally friendly products and processes, a green nanoformulation based on renewables was proposed. Our attention was devoted to cannabidiol (CBD), a cannabis extract compound known for its intrinsically low chemical stability that limits its therapeutic potential. In this work, the environmental stability of CBD was improved, adopting a new sustainable formulation. In particular, for the first time, CBD was embedded into a vesicular nanosystem based on cardanol (CA) known for its antioxidant properties which stabilize and avoid its degradation in an aqueous environment. Chemical and physical characterization of nanovesicles was carried out by dynamic light scattering (DLS) and nuclear magnetic resonance (NMR). Exhaustive dialysis was used to purify samples, and the presence of CBD not embedded into nanodispersions was monitored by UV-vis spectrometry measurements until its disappearance. Identification and quantification of CA and CBD were performed after lysis of nanovesicles through a high-performance liquid chromatograph coupled to diode a array and mass spectrometer detectors (HPLC-DAD-MS). Furthermore, stability studies of green nanoformulations were performed at two different temperatures (20 and 4 °C) to ascertain their better preservation.

The CoFe2O4 and NiFe2O4 nanoparticles were synthesized exploiting a co-precipitation method and afterward calcinated at 400 C through two different experimental apparatus: a conventional muffle and rotatory oven. X-ray diffraction (XRD) analysis revealed that nanocrystalline ferrites grew with a face center cubic structure (fcc) and Fd3m symmetry space group. XRD, transmission electron microscopy, and magnetic measurements confirmed the compositional homogeneity and the narrow size particle distribution (6-8 nm) of the sample thermally treated in a rotary oven, in all likelihood due to the sample's constant turning movement. The size of the magnetic particles is extremely important and influences the choice of a potential technological application. For this reason, our study emerges as a new and simple innovating procedure to control the size of magnetic nanoparticles.

In this manuscript, the preparation and the comparison of the photocatalytic activity of novel TiO2@copper porphyrin composites obtained by impregnation of (5-(4-hydroxy) phenyl-10,15,20-triphenyl copper porphyrin 1a, 5-(4-ethylacetatatomethoxy) phenyl-10,15,20-triphenylcopper porphyrin 1b, and 5-(4-carboxylatomethoxy) phenyl-10,15,20-triphenyl copper porphyrin 1c respectively onto the surface of different TiO2 samples, commercial (cTiO2) and home-prepared (pTiO2), has been reported. The TiO2@copper porphyrin composites were characterized by XRD, BET, UV–vis, FT-IR and SEM-EDS techniques. For the first time, the formation of aggregated porphyrin, most likely in form of dimers 1a-1a, 1b-1b and 1c-1c, were detected on the lower and less hydroxylated surface area of cTiO2. The photocatalytic activity of the samples was evaluated on the basis of the photodegradation of 4-nitrophenol (4-NP) in aqueous solution under metal halide lamp irradiation. The highest photocatalytic efficiency in the degradation of 4-NP, observed by using the carboxylporphyrin 1c as sensitizer supported onto the surface of both pTiO2 or cTiO2, was ascribed to the optimal combination of the anchoring mode with the efficient electron injection in the conduction band that carboxylic group produced at the surface of the TiO2 samples.

The aim of this work is to investigate and characterize the photo-ignition process of dry multi-walled carbon nanotubes (MWCNTs) mixed with ferrocene (FeCp2) powder, using an LED (light-emitting diode) as the light source, a combination that has never been used, to the best of our knowledge. The ignition process was improved by adding a lipophilic porphyrin (H2Pp) in powder to the MWCNTs/FeCp2 mixtures—thus, a lower ignition threshold was obtained. The ignition tests were carried out by employing a continuous emission and a pulsed white LED in two test campaigns. In the first, two MWCNT typologies, high purity (HP) and industrial grade (IG), were used without porphyrin, obtaining, for both, similar ignition thresholds. Furthermore, comparing ignition thresholds obtained with the LED source with those previously obtained with a Xenon (Xe) lamp, a significant reduction was observed. In the second test campaign, ignition tests were carried out by means of a properly driven and controlled pulsed XHP70 LED source. The minimum ignition energy (MIE) of IG-MWCNTs/FeCp2 samples was determined by varying the duration of the light pulse. Experimental results show that ignition is obtained with a pulse duration of 110 ms and a MIE density of 266 mJ/cm2. The significant reduction of the MIE value (10–40%), observed when H2Pp in powder form was added to the MWCNTs/FeCp2 mixtures, was ascribed to the improved photoexcitation and charge transfer properties of the lipophilic porphyrin molecules.

This study reports the effect of three new titanium phosphates Li0.5M0.25Ti2(PO4)3 (where M = Mn, Co and Ni) on the protective properties of alkyd resin films applied on carbon steel substrate in 3.5% sodium chloride solution. The performance of the coatings was evaluated by electrochemical impedance spectroscopy, oxygen and water permeability and pull-off adhesion measurements. It was found that titanium phosphates improve the corrosion resistance as well as the adhesion strength of alkyd resin coatings. The incorporation of titanium phosphates into the alkyd resin coating significantly enhances the pore resistance of the alkyd resin and decreases the coating capacitance. Lower water and oxygen permeability were observed for alkyd resin containing titanium phosphates, confirming formation of a protective layer on the surface. The order of anticorrosion performance of the three coatings was as follows: Li0.5Mn0.25Ti2(PO4)3 > Li0.5Co0.25Ti2(PO4)3 > Li0.5Ni0.25Ti2(PO4)3.

Quercetin belongs to the chemical class of flavonoids and can be found in many common foods, such as apples, nuts, berries, etc. It has been demonstrated that quercetin has a wide array of biological effects that are considered beneficial to health treatment, mainly as anticancer. However, therapeutic applications of quercetin have been restricted to oral administration due to its sparing solubility in water and instability in physiological medium. A drug delivery methodology was proposed in this work to study a new quercetin release system in the form of magnetite–quercetin–copolymer (MQC). These materials were characterized through XRD, TEM, IR, and Thermal analysis. In addition, the magnetization curves and quercetin releasing experiments were performed. It was observed a nanoparticle average diameter of 11.5 and 32.5 nm at Fe3O4 and MQC, respectively. The presence of magnetic nanoparticles in this system offers the promise of targeting specific organs within the body. These results indicate the great potential for future applications of the MQC to be used as a new quercetin release system.

Magnetic nanoparticles functionalized with biomolecules have received special attention due to their various biomedical applications, such as drug delivery and magnetic hyperthermia treatment for cancer. In this study, we present the synthesis and characterization of new nanoparticles coated with anacardic acid derived from cashew nut shell liquid. The results showed that Fe3O4 nanoparticles coated with anacardic acid (AA-MAG) have superparamagnetic behavior and the magnetization is almost equal when compared with the pure Fe3O4. This coating provides stability by preventing the aggregation nanoparticles without losing its magnetization potential. The AA-MAG demonstrates excellent and fast magneto-temperature response which can be used as high-performance hyperthermia agents.

Susceptibility to interact with trifluoroacetic acid (TFA) of selected free-base porphyrins, including a novel lipophilic 3-n-pentadecyl(phenoxy)-ethoxy-phenyl-substituted porphyrin, and photostability of their diprotonated compounds was explored in benzene and N,N-dimethylformamide (DMF). Results have been discussed in terms of the commonly applied pK a -based procedure and confronted with a simple approach derived from experimentally-determined correlations reflecting the porphyrins affinity for TFA. Density functional theory (DFT) has proved the porphyrin moiety creates stable diprotonated species involving two TFA molecules, in which the fluorine atoms effectively contribute to the overall interaction of the acid with the porphyrin macrocycle. The relevance of the meso-substituent and ambient medium to the reactivity and photostability of diverse porphyrin derivatives was emphasized and referred to structural features of the investigated diprotonated porphyrins

Liposomes characterized by membranes featuring diverse fluidity (liquid-crystalline and/or gel phase), prepared from egg yolk lecithin (EYL) and dipalmitoylphosphatidylcholine (DPPC), were doped with selected metalloporphyrins and the time-related structural and dynamic changes within the lipid double layer were investigated. Porphyrin complexes of Mg(II), Mn(III), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), and the metal-free base were embedded into the particular liposome systems and tested for 350 h at 24 degrees C using the electron spin resonance (ESR) spin probe technique. 5-DOXYL, 12-DOXYL, and 16-DOXYL stearic acid methyl ester spin labels were applied to explore the interior of the lipid bilayer. Only the 16-DOXYL spin probe detected evident structural changes inside the lipid system due to porphyrin intercalation. Fluidity of the lipid system and the type of the porphyrin complex introduced significantly affected the intermolecular interactions, which in certain cases may result in self-assembly of metalloporphyrin molecules within the liposome membrane, reflected in the presence of new lines in the relevant ESR spectra. The most pronounced time-related effects were demonstrated by the EYL liposomes (liquid-crystalline phase) when doped with Mg and Co porphyrins, whereas practically no spectral changes were revealed for the metal-free base and both the Ni and Zn dopants. ESR spectra of the porphyrin-doped gel phase of DPPC liposomes did not show any extra lines; however, they indicated the formation of a more rigid lipid medium. Electronic configuration of the porphyrin's metal center appeared crucial to the degree of molecular reorganization within the phospholipid bilayer system.

Molecular Imprinting Technology (MIT) is a technique to design artificial receptors with a predetermined selectivity and specificity for a given analyte, which can be used as ideal materials in various application fields. Molecularly Imprinted Polymers (MIPs), the polymeric matrices obtained using the imprinting technology, are robust molecular recognition elements able to mimic natural recognition entities, such as antibodies and biological receptors, useful to separate and analyze complicated samples such as biological fluids and environmental samples. The scope of this review is to provide a general overview on MIPs field discussing first general aspects in MIP preparation and then dealing with various application aspects. This review aims to outline the molecularly imprinted process and present a summary of principal application fields of molecularly imprinted polymers, focusing on chemical sensing, separation science, drug delivery and catalysis. Some significant aspects about preparation and application of the molecular imprinting polymers with examples taken from the recent literature will be discussed. Theoretical and experimental parameters for MIPs design in terms of the interaction between template and polymer functionalities will be considered and synthesis methods for the improvement of MIP recognition properties will also be presented

MZnFe2O4 (M = Ni or Mn) cubic nanoparticles have been prepared by hydrothermal synthesis in mild conditions and short time without any procedure of calcinations. The structural and magnetic properties of the mixed ferrites were investigated by X-ray diffraction, Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, Mössbauer spectroscopy, vibrating sample magnetometer, and Transmission electron microscopy (TEM). X-ray analysis showed peaks characteristics of the spinel phase. The average diameter of the nanoparticles observed by TEM measurements was approximately between 4 and 10 nm. Spectroscopy study of the spinel structure was performed based on Group Theory. The predicted bands were observed in FTIR and Raman spectrum. The magnetic parameters and Mössbauer spectroscopy were measured at room temperature and superparamagnetic behavior was observed for mixed ferrites. This kind of nanoparticles can be used as precursor in drug delivery systems, magnetic hyperthermia, ferrofluids, or magnetic imaging contrast agents.

This work describes the synthesis, characterization, and photocatalytic activity of new composite nanomaterials based on ZnO nanostructures impregnated by lipophlilic porphyrins derived from cashew nut shell liquid (CNSL). The obtained nanomaterials were characterized by X-ray diffraction (XRD), UV-Vis diffuse reflectance spectroscopy (DRS), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), and steady-state photoluminescence spectra (PL). The results confirm nanostructures showing average diameter of 55 nm and an improved absorption in the visible region. Further, the FTIR analysis proved the existence of non-covalent interactions between the porphyrin molecules and ZnO. The photocatalytic activity of prepared photocatalysts was investigated by degradation of rhodamine B (RhB) in aqueous solution under visible light irradiation and natural sunlight. It was demonstrated that the photocatalytic activity increases in the presence of the porphyrins and, also, depends on the irradiation source. The development of composite photocatalysts based on porphyrins derived from CNSL provides an alternative approach to eliminate efficiently toxic wastes from water under ambient conditions.

A new class of porphyrin(Pp)/Fe co-loaded TiO2 composites opportunely prepared by impregnation of [5,10,15,20-tetra(4-tertbutylphenyl)] porphyrin (H2Pp) or Cu(II)[5,10,15,20-tetra(4-tert-butylphenyl)] porphyrin (CuPp) onto Fe-loaded TiO2 particles showed high activities by carrying out the degradation of 4-nitrophenol (4-NP) as probe reaction in aqueous suspension under heterogeneous photo-Fenton-like reactions by using UV-visible light. e combination of porphyrin-Fe-TiO2 in the presence of H2O2 showed to be more efficient than the simple bare TiO2 or Fe-TiO2.

In this study, epoxy/metal phthalocyanines nanocomposites (NiPc/Epoxy, CuPc/Epoxy, and ZnPc/Epoxy) are employed to protect carbon steel corrosion in 3.5% NaCl solution. The corrosion performances of the nanocomposites coatings were evaluated by using electrochemical impedance spectroscopy (EIS), open circuit potential (OCP) and scanning electron microscopy (SEM) measurements. The mechanical property of the coating system was investigated using nanoindentation technique. The results indicated that the incorporation of metal phthalocyanines pigments into epoxy resin coating significantly enhances the corrosion resistance as well as the hardness of epoxy coatings.Metal phthalocyanines pigments are able to cure the defect in epoxy resin and prevent the diffusion of corrosive electrolyte to carbon steel substrate. It was found that NiPc/Epoxy nanocomposite gave the best protection performance than others.

In this work, we present the synthesis and characterization of a new surfactant molecule obtained from a byproduct of the cashew nut processing (diphosphorylated cardol, DPC). It is herein used to overcoat magnetic nanoparticles showing spinel structures in order to create new ferrofluids. The nanoparticle structure and magnetic properties have been deeply investigated. DPCfunctionalized Fe3O4 and NiFe2O4 samples exhibit higher magnetic saturation than DPC–CoFe2O4. These new ferrofluids reveal appealing as possible nanoparticle stabilizing molecules, magnetic resonance imaging agents, storage systems or in any material science field that requires the employment of biocompatible magnetic stable fluids.

In this study, H2Pc/Epoxy nanocomposite coating was fabricated for anti-corrosion applications. The electrochemical, cross-cut adhesion, impact resistance, bend test, contact angle, scanning electron microscopy (SEM) and thermogravimetric analysis (TGA) analysis were employed to evaluate the performance of new nanocomposites. Corrosion monitoring was achieved in saline solution (3.0 wt.% NaCl). The improvement of the corrosion performance of the epoxy coating containing H2Pc particles by comparison with neat epoxy resin was confirmed by the high coating resistance. Degradation of H2Pc/Epoxy nanocomposite coating was observed after 14 days. It was found that H2Pc particles improved the cross-cut adhesion, impact resistance and thermal stability of epoxy resin.

Enamel resin infiltrants are biomaterials able to treat enamel caries at early stages. Nevertheless, they cannot prevent further demineralization of mineral-depleted enamel. Therefore, the aim of this work was to synthesize and incorporate specific hydroxyapatite nanoparticles (HAps) into the resin infiltrant to overcome this issue.

Novel sandwich-type phthalocyanines containing a rare earth metal core (Pr, Nd, Eu–Lu) and macrocycles peripherally substituted by pentadecylphenoxy groups were synthesized using a cardanol-based phthalonitrile precursor and the respective lanthanide acetate. Additionally, the metal free-base analog compound was studied for comparison. The purified reaction products were all found to be thick and viscous substances at room temperature, showing liquid crystalline behavior with a distinct increase in fluidity at ca. 40 °C. The complexes are readily soluble in chloroalkyl solvents and dissolve fairly well in DMF with some tendency to form aggregates. Besides they are strongly hydrophobic and reveal a peculiar affinity for lipophilic media. The compounds have been characterized by UV-Vis (absorption and emission), FTIR, MS and DSC methods. Photochemical activity in the liquid phase (dimethylformamide, dichloromethane, mineral oil) and the degree of photodegradation demonstrated under constant UV-irradiation (λ = 352 nm) have been analyzed and discussed in terms of photostability.

Dioxiranes are used as reagents in a myriad of synthetically useful oxidations performed in aqueous medium. To extend such an approach also to substrates that are highly hydrophobic, we propose here the use of microemulsions based on the surfactant hexadecyltrimethylammonium hydrogen sulphate (CTAHS) because of its high stability against peroxide species. In this paper, we examine the dioxirane (isolated or generated in situ) reactivity in different CTAHS microemulsions. Yield and selectivity of the oxidation of b-methylstyrene by dimethyldioxirane (DDO) generate ‘‘in situ’’ and of laurolactam by isolated methyl(trifluorometyl)dioxirane (TFDO) were studied. For each microemulsion, the aggregate size and the localization of the components were determined by a combination of NMR and light scattering techniques. The hydrodynamic radius of the micelles is close to the length of the surfactant and this suggests they are spherical in shape. When acetone (the precursor of DDO) is present in the formulation, it partitions itself between the aqueous bulk and the micellar palisade so that the dioxirane eventually formed is readily available to oxidize substrates secluded in the micelle. Apolar substrates, confined within the micelles, are protected from uncontrolled oxidations, leading to an astonishing high selectivity of oxidation of laurolactam to 12-nitro-lauric acid by TFDO. This opens the way to an easy procedure (performed in water under mild conditions) to synthetize x-nitroacids.

This work aims to investigate and characterize the photo-ignition phenomenon of MWCNT/ferrocene mixtures by using a continuous wave (CW) xenon (Xe) light source, in order to find the power ignition threshold by employing a different type of light source as was used in previous research (i.e., pulsed Xe lamp). The experimental photo-ignition tests were carried out by varying the weight ratio of the used mixtures, luminous power, and wavelength range of the incident Xe light by using selective optical filters. For a better explanation of the photo-induced ignition process, the absorption spectra of MWCNT/ferrocene mixtures and ferrocene only were obtained. The experimental results show that the luminous power (related to the entire spectrum of the Xe lamp) needed to trigger the ignition of MWCNT/ferrocene mixtures decreases with increasing metal nanoparticles content according to previously published results when using a different type of light source (i.e., pulsed vs CW Xe light source). Furthermore, less light power is required to trigger photo-ignition when moving towards the ultraviolet (UV) region. This is in agreement with the measured absorption spectra, which present higher absorption values in the UV–vis region for both MWCNT/ferrocene mixtures and ferrocene only diluted in toluene. Finally, a chemo-physical interpretation of the ignition phenomenon is proposed whereby ferrocene photo-excitation, due to photon absorption, produces ferrocene itself in its excited form and is thus capable of promoting electron transfer to MWCNTs. In this way, the resulting radical species, FeCp2+∙ and MWCNT−, easily react with oxygen giving rise to the ignition of MWCNT/ferrocene samples.

Hybrid photocatalysts based on TiO2-anatase matrix, representing the both micro-and nano-structures, impregnated with selected lanthanide diphthalocyanine and metalloporphyrin sensitizers, were compared to evaluate their activity and effectiveness in a water suspension catalytic system designed to degrade 4-nitrophenol (4-NP) in a UV-stimulated reaction. Either type of the anatase catalyst was proved to be effective in mineralizing of 4-NP. However, kinetic studies confirmed that the composite's efficiency basically depends on the nature of the macromolecular sensitizer and to a minor extent on the dimensions (micro/nano) of the TiO2 particles. The apparent higher activity observed for the micro-TiO2 catalysts indicates improvement of the electron transfer between the sensitizer and the micro-crystalline structure of TiO2-anatase in contrast to the nano-crystalline matrix. The mechanistic aspects of the observed catalytic performances have been discussed.

Three dichloro Sn(IV) porphyrins, trans-dichloro[5,10,15,20-tetra-[2 or 3 or 4-(3-phenoxy)-propoxy]phenyl porphyrin]tin(IV) and the corresponding dihydroxo Sn(IV) porphyrins trans-dihydroxo[5,10,15,20-tetra-[2 or 3 or 4-(3-phenoxy)-propoxy]phenyl porphyrin]tin(IV) were synthesized and characterized spectroscopically. The dihydroxo Sn(IV) porphyrin-TiO2 composites were also prepared and characterized, and an interaction between TiO2 and tin porphyrin molecules involving the axial -OH ligand with the TiO2 surface was proposed. The photocatalytic activity was investigated by testing the photodegradation of 4-nitrophenol (4-NP) in aqueous solution under both visible and UV-vis light irradiation. It was found that the distinct space tropisms of peripheral substituents in meso sites of the porphyrin ring lead to different efficiencies in photodegrading the 4-NP.

A new class of porphyrin(Pp)/Fe co-loaded TiO2 composites opportunely prepared by impregnation of [5,10,15,20-tetra(4-tert-butylphenyl)] porphyrin (H2Pp) or Cu(II)[5,10,15,20-tetra(4-tert-butylphenyl)] porphyrin (CuPp) onto Fe-loaded TiO2 particles showed high activities toward the degradation of 4-nitrophenol (4-NP) by heterogeneous photo Fenton-like processes.

Composite materials prepared by loading polycrystalline TiO2 powders with lipophilic highly branched Cu(II)- and metal-free phthalocyanines or porphyrins, which have been used in the past as photocatalysts for photodegradative processes, have been successfully tested for the efficient photoreduction of carbon dioxide in aqueous suspension affording significant amounts of formic acid. The results indicated that the presence of the sensitizers is beneficial for the photoactivity, confirming the important role of Cu(II) co-ordinated in the middle of the macrocycles. A comparison between Cu(II) phthalocyanines and Cu(II) porphyrins indicated that the Cu(II)- phthalocyanine sensitizer was more efficient in the photoreduction of CO2 to formic acid, probably due to its favorable reduction potential.

The present work is aimed to the preliminary analysis of the applicability of cardanol derivatives as renewable plasticizers for soft PVC. Two different plasticizers were studied, obtained by esterification of the cardanol hydroxyl group (cardanol acetate) and further epoxidation of the side chain double bonds (epoxidated cardanol acetate). Differential Scanning Calorimetry (DSC) was used to study the miscibility between PVC and cardanol derived plasticizers. The miscibility was correlated to the chemical structure of plasticizer by means of the Hansen solubility parameter analysis. Results obtained indicated that esterification of cardanol yields a partial miscibility with PVC, whereas esterification and subsequent epoxidation yield a complete miscibility with PVC. Therefore cardanol acetate, obtained by solvent-free esterification of cardanol, was used as a secondary plasticizer of PVC. Mechanical and rheological analysis showed that the cardanol acetate can partially replace DEHP in PVC formulation.

Magnetic Fe3O4 nanoparticles with average size approximately 11 nm were first oleic acid coated to interact with the meso-porphyrin derivative from CNSL. This procedure produced a novel superparamagnetic fluorescent nanosystem (SFN) linked by van der Waals interactions. This system was characterized by transmission electron microscope, infrared spectroscopy, thermogravimetric analysis, magnetic measurements, UV–Vis absorption, and fluorescence emission measurements. These results showed that SFN has good thermal stability, excellent magnetization, and nanosized dimensions (*13 nm). It exhibited emission peaks at 668 and 725 nm with a maximum emission at 467 nm of excitation wavelength. The type of interaction between porphyrin and magnetic nanoparticles allowed to obtain a material with interesting optical properties which might be used as an imaging agent for contrast in cells as well as heterogeneous photocatalysis.

Cardanol (CA) is a natural and renewable organic raw material obtained as the major by-product from the distillation of cashew nut shell liquid (CNSL). Thanks to its amphiphilic properties under alkaline conditions, was developed an environmental-friendly technology to produce engineered “green nanocarriers”, without use of any organic solvents, in which CA acts as the solvent as well as being the main component of the nanodispersions.

Functionalized Fe3O4 nanoparticles (NPs) have emerged as a promising contrast agent for magnetic resonance imaging (MRI). Their synthesis and functionalization methodology strongly affect their performance in vivo. The methodology most used in the literature for the synthesis of Fe3O4 NPs is thermal decomposition, which has proven to be time-consuming, expensive, and laborious, as it requires further ligand exchange strategies to transfer the as-synthesized nanoparticles from organic to aqueous solvents. This work describes a rapid and facile sonochemical methodology to synthesize and functionalize Fe3O4 NPs with excellent physicochemical properties for MRI. This sonochemistry approach was used to produce, in 12 min, Fe3O4 NPs functionalized with polysodium acrylate (PAANa), trisodium citrate (CIT), branched polyethylenimine (BPEI), and sodium oleate. X-ray diffraction and transmission electron microscopy demonstrated that the NPs were composed of a single inverse spinel phase with an average diameter of 9–11 nm and a narrow size distribution. Mössbauer spectroscopy and magnetic measurements confirmed that the obtained NPs were transitioning to the superparamagnetic regime and possessed excellent magnetization saturation values (59–77 emu/g). Fourier transform infrared spectroscopy proved that the sonochemistry approach provided conditions that induced a strong interaction between Fe3O4 and the coating agents. Furthermore, dynamic light-scattering experiments evidenced that samples coated with PAANa, CIT, and BPEI possess colloidal stability in aqueous solvents. Emphasis must be placed on PAANa-coated NPs, which also presented remarkable colloidal stability under simulated physiological conditions. Finally, the obtained NPs exhibited great potential to be applied as an MRI contrast agent. The transverse relaxivity values of the NPs synthesized in this work (277–439 mM–1 s–1) were greater than those of commercial NPs and those prepared using other methodologies. Therefore, this work represents significant progress in the preparation of Fe3O4 NPs, providing a method to prepare high-quality materials in a rapid, cost-effective, and facile manner.

The nitration reaction of 5,10,15,20-tetranaphthylporphyrin (TNP) was investigated in detail and the mono-, di-, and tri-nitro-TNPs were synthesized in high yield using 65% HNO(3). The (1)H-NMR study shows that the preferred site of nitration of the naphthyl substituted porphyrin is the carbon atom of the meso-substituents para to its bond to the porphyrin ring. The reaction leads to exquisite regioselectivity in favor of the mono, di, and tri-nitro-TNP. Quantum-chemical ab initio calculations at different levels of theory were performed in order to explain the experimentally observed reactivity.

Cashew nut shell liquid (CNSL) is a largely available by-product of the cashew agro-industry. In this paper, the main constituents (cardanol, cardol and methylcardol) obtained after separation of the CNSL mixture have been used as starting material to prepare a variety of novel mono- and bis-benzoxazines via cyclization reactions with formaldehyde and aromatic amine derivatives under mild conditions. These model reactions were successfully extended to the cardanol and cardols mixture affording the one pot synthesis monoand bis-benzoxazines.

The aim of this study was to synthesize novel cardanol-based benzoxazines, using different primary amines, and evaluate their influences on the synthesis and polymerization process. The monomers were characterized using NMR (1H and 13C), FT-IR, DSC and TGA. It was demonstrated how the amines structures influence on the stability of the oxazine ring, which relates to the onset polymerization temperature (Te). Aniline-type benzoxazines provided higher Te than aliphatic ones. Since at this elevate temperature (230-295°C) the alkyl chain of cardanol could degrade, the use of a new catalyst was also evaluated, showing the innocuous MgCl2 as an efficient alternative. The polymerization of these monomers with MgCl2 (1%) were studied using FT-IR, DSC and GPC, showing that under mild temperatures it is possible to obtain polybenzoxazines completely soluble and with high polydispersity.

Structural parameters of a range of over 100 meso-substituted zinc porphyrins were reviewed and compared to show how far the nature of the functional group may affect the interatomic distances and bond angles within the porphyrin core. It was proved that even despite evident deformations of the molecular structure, involving twisting of the porphyrin's central plane, the coupled π-bonding system remains flexible and stable. DFT calculations were applied to a number of selected porphyrins representative for the reviewed compounds to emphasize the relevance of theoretical methods in structural investigations of complex macrocyclic molecular systems. Experimental and DFT-simulated IR spectral data were reported and analyzed in context of the individual molecular features introduced by the meso substituents into the porphyrin moiety base. Raw experimental spectral data, including 1H- and 13C-NMR, UV-Vis, FTIR, XRD, and other relevant physicochemical details have been provided for a specially chosen reference zinc porphyrin functionalized by tert-butylphenyl groups.

There is a growing global interest for the development of green technologies that allow the use of products with less damage to environment, as well as for maximum and sustainable use of natural resources. The main aim of this study was to develop superparamagnetic nano-biocomposites for application as dielectric resonator antennas, from a combination of a cardanol-based thermoset plastic, chemically modified sponge gourd fibers (NaOH 10% and NaClO 1 wt%), and magnetite nanoparticles in different contents (1, 5, and 10 wt%). The magnetite particles exhibited nanometric size, high purity and crystallinity, and superparamagnetic character. All nano-biocomposites showed superparamagnetic behavior, excellent thermal stability, good biodegradation rates, and better mechanical strength for the material with magnetite 10 wt%. All dielectric resonator antennas showed satisfactory return loss and suitability for technological applications, especially for performance in broadband.

In this article, the environmentally friendly preparation of “green nanocarriers” based on the combination of natural renewable materials is described. Cardanol (CA), obtained as the major byproduct of the cashew industry, and cholesterol (CH) have been used to encapsulate chlorogenic acids (CQAs), a class of natural phenolic compounds extracted from two different rowanberries (Sorbus Americana and Vaccinium sp.). The chlorogenic acid extracts and cardanol-based vesicular nanodispersions have been characterized, respectively, by ultra-high performance liquid chromatography (UHPLC), transmission electron microscopy (TEM), and dynamic light scattering (DLS).

In the present work, blends of M-Porphyrins (Zn-Pp, Cu-Pp, and Co-Pp) with alkyd resin have been used for development of novel nanocomposite anticorrosive coatings. The nanocomposite coatings containing the synthesized M-Porphyrins were applied on carbon steel specimens, and the coated specimens were evaluated for their corrosion and mechanical properties in 0.5 M HCl solution. The performance of nanocomposite coatings was detected using potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), water permeability and pull-off adhesion measurements. Furthermore, scanning electron microscopy (SEM) analysis showed the surface characterizations of nanocomposite coatings. The coating film capacitances were monitored with the immersion time to establish water uptake of these coating films. The results showed that the incorporation of M-Porphyrins significantly improved anticorrosive performance and mechanical properties of the alkyd resin. Lower water uptake was observed for alkyd resin containing M-Porphyrins particles. The central metal atoms that were bonded to Porphyrins structure are the main reason for the difference in the protection efficiency. Best corrosion protection of the carbon steel was found for the alkyd resin with Co-Pp (98.47%).

New series of pyrido[2,3-d]pyrimidine and 1,8-naphthyridine derivatives were synthesized from 2-amino-6-(phenoxathiin-2-yl)-4-(thiophene-2-yl) nicotinonitrile as starting material, and their structures were characterized on the basis of the spectral data. Most of the synthesized compounds were evaluated for their cytotoxic activity against two cancer cell lines, namely, breast cancer Michigan Cancer Foundation-7 (MCF-7) and prostate cancer human prostatic carcinoma cell line (PC-3) using MTT assay. Some of these compounds showed potent cytotoxic effect concluded from their IC50 values.

New asymmetric cardanol-based porphyrins, free-base and coordinated with Ni, Co and Cu, were synthesized and completely characterized as A3B type. Such porphyrins were obtained aiming improved solubility in polar solvents due insertion of an -OH phenolic group. Their thermal and dielectric properties were also evaluated. Changes in the synthetic route reduced the reaction time and improved the yields of the aldehyde precursor obtainment. Electronic absorption spectra of the new porphyrins in CH2Cl2, EtOH and acetone, indicated a decrease in the ε (molar absorptivity) values with increasing solvent polarity, except for the nickel complex which, in acetone, showed a slight increase of 2% in the ε value. The dielectric measurements showed that the conductivity (σ) and the loss tangent (tan δ) increased with frequency, but the permittivity (ε′) decreased. The results showed that the coordination of the porphyrin promoted a significant change in thermal and dielectric properties, specially for to the Ni-complex compound, which presented the best dielectric properties with interesting values of permittivity and loss tangent at 100 MHz (19.46 and 0.011 a.u., respectively).

Four novel porphyrins, 5-[3-(3-phenoxy)-propoxy]phenyl porphyrin, 5,15-di-[3-(3-phenoxy)-propoxy] phenyl porphyrin, 5,10,15-tri-[3-(3-phenoxy)-propoxy]phenyl porphyrin, 5,10,15,20-tetra-[3-(3-phenoxy)- propoxy]phenyl porphyrin, and their corresponding Cu(II) porphyrins, were synthesized and characterized spectroscopically. The photodegradation of 4-nitrophenol in aq. suspension was used to determine the photocatalytic activity of polycrystalline TiO2 samples which had been impregnated with the Cu(II) porphyrins, as sensitizers. The photocatalytic activity of the composite depends mainly on the amount of sensitizer on the TiO2 surface rather than the nature of the substituted porphyrins.

Metal-free, Cu(II)- or Zn(II) tetrakis [4-(2,4-bis-(1,1-dimethylpropyl)phenoxy)]phthalocyanines loaded over TiO2 (anatase) proved to be active in the photoreduction of CO2 to formic acid (HCO2H) in water under UV–vis light. CuPc/TiO2 is catalyst of choice, allowing to reach a maximum yield of HCO2H, unequalled by any other similar catalytic systems. Because of their low environmental impact, low potential cost, and efficient power conversion, these multipurpose materials show promise in the setup of sustainable methods for CO2 valorization.

Cardanol, a well known hazardous byproduct of the cashew industry, has been used as starting material for the synthesis of useful differently substituted “cardanol-based” porphyrins and their zinc(II), copper(II), cobalt(II) and Fe(III) complexes. Novel composites prepared by impregnation of polycrystalline TiO2 powder with an opportune amount of “cardanol-based” porphyrins, which act as sensitizers for the improvement of the photo-catalytic activity of the bare TiO2, have been used in the photodegradation in water of 4-nitrophenol (4-NP), which is a toxic and bio-refractory pollutant, dangerous for ecosystems and human health.