Simultaneous Optimization of Deacetylation Degree and Molar Mass of Chitosan from Shrimp Waste.

Shrimp waste is a valuable source for chitin extraction and consequently for chitosan preparation. In the process of obtaining chitosan, a determining step is the chitin deacetylation. The main characteristic of chitosan is the degree of deacetylation, which must be as high as possible. The molar mass is another important parameter that defines its utilizations, and according to these, high or low molar masses are required. The present study is an attempt to optimize the deacetylation step to obtain chitosan with a high degree of deacetylation and high or low molar mass. The study was carried out based on experimental data obtained in the frame of a central composite design where three working parameters were considered: NaOH concentration, liquid:solid ratio, and process duration. The regression models defined for the degree of deacetylation (DD) and for the mean molar mass (MM) of chitosan powders were used in the formulation of optimization problems. The objectives considered were simultaneous maximum DD and maximum/minimum MM for the final chitosan samples. For these purposes, multiobjective optimization problems were formulated and solved using genetic algorithms implemented in Matlab®. The multiple optimal solutions represented by trade-offs between the two objectives are presented for each case.

Influence of continuous wave laser light at 532 nm on transmittance and on photoluminescence of DNA-CTMA-RhB solutions.

Recent results obtained in our experimental investigation on the influence of the illumination with continuous wave (c.w.) laser light at 532 nm on the transmittance at this wavelength and on the photoluminescence of the DNA-CTMA-RhB in butanol compound are reported. The temporal dependence of absorption changes induced by c. w. light at 532 nm in DNA-CTMA-RhB in butanol solution, and, for comparison, in RhB in butanol solution, is investigated experimentally and analyzed in order to assess the effect of DNA-CTMA on this light-induced process. The evolution in time of the peak's amplitude and wavelength of the photoluminescence spectra in solutions of DNA-CTMA-RhB in butanol, during their excitation with laser light at 532 nm wavelength has been also investigated and discussed.

Alternative Solid Activators from Waste Glass for One-Part Alkali-Activated Fly Ash/Red Mud Cements.

Solid activators based on waste glass for the manufacture of one-part alkali-activated fly ash/red mud materials were synthesized, characterized, and tested in this work. The synthesis was carried out via alkaline fusion with sodium hydroxide at different reaction temperatures and at different sodium hydroxide/waste glass mass ratios. The results showed that the reaction temperature decisively influences the properties of the obtained solid activators. Thus, the best results regarding the water solubility of solid activators were obtained for the synthesis temperature of 600 °C, regardless of the sodium hydroxide/waste glass mass ratio. Also, the use of these assortments of solid activators led to obtaining the best compressive strength of one-part alkali-activated fly ash/red mud materials. The best results were obtained for the solid activator synthesized at a temperature of 600 °C and a sodium hydroxide/glass waste mass ratio of two.

DNA-CTMA Matrix Influence on Rhodamine 610 Light Emission in Thin Films.

Due to the increased application of lasers in different fields (industry, medicine, etc.), there is a growing need for new laser sources with good beam quality and variable emission wavelength. At the same time, for environmental reasons, the obtaining of novel eco-friendly active optical materials, such as those based on the deoxyribonucleic acid (DNA) biopolymer, with optimal light emission properties, is of high interest. The results obtained in this study of the temporal dependence of the transmittance and of the light emission in thin films of DNA-CTMA-Rhodamine 610 (at different Rhodamine concentrations) (DNA-CTMA-Rh610), when they are illuminated with continuous wave laser light at 532 nm (frequently used in the optical pumping of dye lasers), are presented and discussed. The transmittance results obtained for thin film samples are compared to those obtained for the DNA-CTMA-Rh610 solutions in butanol, from which the films have been made, and also with those obtained for Rh610 solutions in butanol with the same concentrations. The investigation was performed in order to assess the influence of the DNA-CTMA and of the green laser light at 532 nm wavelength on relevant chromophore properties such as light transmission and fluorescence emission. The results obtained revealed that the DNA-CTMA matrix has an active influence on the Rhodamine 610 emission, in the whole range of concentrations of the investigated samples.

Optimization of Chitosan Extraction Process from Rapana venosa Egg Capsules Waste Using Experimental Design.

New green and sustainable sources were chosen to obtain chitosan, an important material, with many applications in different fields. The present study is focused on egg capsules of Rapana venosa waste as raw material for chitosan oligomers. As previous studies revealed that chitosan extraction from this material takes place with a low yield, the present research aimed to optimize this step. A 22 experimental plan, with three replicates in the center, was proposed to investigate the influence of NaOH concentration and temperature on the yield extraction. After a primary analysis of the experimental data, a favorable temperature value was selected (90 °C) at which the total dissolution of the egg capsules was obtained. Then, at this temperature, the experimental plan was extended exploring the influence of the NaOH concentration on three levels (5, 6, and 7%) and the extraction duration on two levels (60 and 85 min). Based on all experimental data, a neural model was obtained and validated. The neural model was used to maximize the yield, applying Genetic Algorithm (GA) implemented in Matlab®. The resulting optimal solution is: NaOH concentration 6.47%, temperature 90 °C, duration 120 min, with a yield value of 7.05%.

Crabs Marine Waste-A Valuable Source of Chitosan: Tuning Chitosan Properties by Chitin Extraction Optimization.

Chitin extraction from crab shells was studied experimentally and optimized aiming to obtain chitosan with predefined deacetylation degree and molecular mass. To find out the optimum operating conditions that ensure the obtaining of a chitosan with highest deacetylation degree and specific molecular mass four parameters were varied: the concentration of NaOH and the temperature for deproteinization step, respectively HCl concentration and the number of acidic treatments for the demineralization stage. The experiment was carried on following Taguchi orthogonal array L9, and the best combination of factors was found using the desirability function approach. The optimization results showed that 5% NaOH concentration and low temperatures lead to a chitosan with high deacetylation degree. High molecular mass chitosan is obtained when a single step acidic treatment is used, while a chitosan with low molar mass is obtained for multiple acid contacts and higher HCl concentration.

Micromorphological details and identification of chitinous wall structures in Rapana venosa (Gastropoda, Mollusca) egg capsules.

The present study evaluated the structural and ultrastructural characteristics of Rapana venosa egg capsules, starting from observations of their antifouling activity and mechanical resistance to water currents in mid-shore habitats. Optical microscopy, epifluorescence, and electron microscopy were used to evaluate the surface and structure of the R. venosa egg capsules. These measurements revealed an internal multilamellar structure of the capsule wall with in-plane distributions of layers with various orientations. It was found that the walls contained vacuolar structures in the median layer, which provided the particular characteristics. Mechanical, viscoelastic and swelling measurements were also carried out. This study revealed the presence and distribution of chitosan in the capsule of R. venosa. Chitosan identification in the egg capsule wall structure was carried out through SEM-EDX measurements, colorimetric assays, FT-IR spectra and physical-chemical tests. The biopolymer presence in the capsule walls may explain the properties of their surfaces as well as the mechanical resistance of the capsule and its resistance to chemical variations in the living environment.

Ciprofloxacin-Collagen-Based Materials with Potential Oral Surgical Applications.

We report in this paper the synthesis and characterization of a new collagen-based material. This material was obtained in a spongy form and was functionalized with an antibiotic, ciprofloxacin. The targeted applications of these kind of materials concern the post-operative prophylaxis. The in vitro tests (antimicrobial, cytotoxic, drug release) showed that sponges with a concentration of 0.75 g of ciprofloxacin per gram of collagen could be beneficial for the desired applications.

Oxytetracycline versus Doxycycline Collagen Sponges Designed as Potential Carrier Supports in Biomedical Applications.

Many research studies are directed toward developing safe and efficient collagen-based biomaterials as carriers for drug delivery systems. This article presents a comparative study of the properties of new collagen sponges prepared and characterized by different methods intended for biomedical applications. The structural integrity is one of the main properties for a biomaterial in order for it to be easily removed from the treated area. Thus, the effect of combining a natural polymer such as collagen with an antimicrobial drug such as oxytetracycline or doxycycline and glutaraldehyde as the chemical cross-linking agent influences the cross-linking degree of the material, which is in direct relation to its resistance to collagenase digestion, the drug kinetic release profile, and in vitro biocompatibility. The enzymatic degradation results identified oxytetracycline as the best inhibitor of collagenase when the collagen sponge was cross-linked with 0.5% glutaraldehyde. The drug release kinetics revealed an extended release of the antibiotic for oxytetracycline-loaded collagen sponges compared with doxycycline-loaded collagen sponges. Considering the behavior of differently prepared sponges, the collagen sponge with oxytetracycline and 0.5% glutaraldehyde could represent a viable polymeric support for the prevention/treatment of infections at the application site, favoring tissue regeneration.

DNA influence on norfloxacin fluorescence.

The emission properties of norfloxacin, a quinolone antibiotic, in presence of salmon sperm DNA were studied at room temperature and in conditions of acid, alkaline and neutral pH. It was found that norfloxacin molecules are inserted between the DNA base pairs, as evidenced by the emission spectra features and the significant increases in relative viscosity of DNA by the addition of norfloxacin. The fluorescence quenching process was characterized by Stern-Volmer plots which display a positive deviation from the linearity. The analysis was performed in terms of the Stern-Volmer modified equations including both dynamic and static quenching. The use of the finite sink approximation model showed that the process of quenching of the norfloxacin fluorescence with DNA was diffusion limited, irrespective to the pH of the work solution. At the same time, relying on the formation of the ground state complex model and the sphere of action static quenching model, we concluded that the quenching reaction from the norfloxacin - DNA system is due to the combined effect of both dynamic and static quenching processes.

Novel materials based on DNA-CTMA and lanthanide (Ce(3+) , Pr(3+) ).

New, deoxyribonucleic acid (DNA) based compounds, functionalized with hexadecyltrimethylammonium chloride (CTMA) and lanthanide hydroxide nanoparticles were synthesized. The spectral measurements suggest that between the DNA-CTMA complex and the lanthanide (III) ions a chemical interaction takes place. The obtained materials exhibit an improved fluorescence efficiency, showing a potential interest for application in photonics, and more particularly, in light emitting devices. © 2016 Wiley Periodicals, Inc. Biopolymers 105: 613-617, 2016.

First principle calculations of the electronic and vibrational properties of the 3-(1,1-dicyanoethenyl)-1-phenyl-4,5-dihydro-1H-pyrazole molecule.

Results of first principle quantum chemical calculations of electronic and vibrational properties of the push-pull 3-(1,1-dicyanoethenyl)-1-phenyl-4,5-dihydro-1H-pyrazole (DCNP) molecule are reported and discussed. The structure of DCNP was optimized with HF/6-311G methodology and found to be planar. On the basis of obtained geometry, infrared absorption and Raman spectra were computed within the HF/6-311++G** formalism. They allow to conclude that the changes of molecule dipole moment and variation of its polarizability appear at the same vibrational mode and affect the optical properties of the DCNP. Four different methodologies: time-dependent HF and time-dependent DFT method with B3LYP, LC-BLYP, and CAM-B3LYP potentials were used to compute the optical absorption spectra of DCNP. Influence of solvent on molecular electronic structure was studied within the C-PCM model. It predicts the DFT/B3LYP methodology as the best one to compute the NLO properties of the DCNP. The computed HOMO and LUMO orbitals show evidence that the ground state of the molecule is located at its aromatic part. The discussion of charge transfer during the excitation process for the transition S0-S1 was performed. The charge transfer parameter calculated in vacuum and in solvent gives the evidence that the solvent environment weakly enhance the molecular charge transfer. It confirms the tendency of an occurrence of the intermolecular charge transfer in DCNP which is crucial for its hyperpolarizability magnitude. It was proved that the second-order susceptibility corresponding to SHG may be calculated for host-guest polymer/DCNP composite using the simple oriented gas model and the rigorous local field approach should not necessarily be applied.

Reaching the magnetic anisotropy limit of a 3d metal atom.

Designing systems with large magnetic anisotropy is critical to realize nanoscopic magnets. Thus far, the magnetic anisotropy energy per atom in single-molecule magnets and ferromagnetic films remains typically one to two orders of magnitude below the theoretical limit imposed by the atomic spin-orbit interaction. We realized the maximum magnetic anisotropy for a 3d transition metal atom by coordinating a single Co atom to the O site of an MgO(100) surface. Scanning tunneling spectroscopy reveals a record-high zero-field splitting of 58 millielectron volts as well as slow relaxation of the Co atom's magnetization. This striking behavior originates from the dominating axial ligand field at the O adsorption site, which leads to out-of-plane uniaxial anisotropy while preserving the gas-phase orbital moment of Co, as observed with x-ray magnetic circular dichroism.

Measuring the three-dimensional structure of ultrathin insulating films at the atomic scale.

The increasing technological importance of thin insulating layers calls for a thorough understanding of their structure. Here we apply scanning probe methods to investigate the structure of ultrathin magnesium oxide (MgO) which is the insulating material of choice in spintronic applications. A combination of force and current measurements gives high spatial resolution maps of the local three-dimensional insulator structure. When force measurements are not available, a lower spatial resolution can be obtained from tunneling images at different voltages. These broadly applicable techniques reveal a previously unknown complexity in the structure of MgO on Ag(001), such as steps in the insulator-metal interface.

Green silver nanobioarchitectures with amplified antioxidant and antimicrobial properties.

Cornelian silver-based architectures were achieved from liposomes, silver nanoparticles (AgNPs) and single-walled carbon nanotubes (SWCNTs) by a "green" bottom-up strategy. Liposomes were prepared by a thin film hydration method and labelled with a natural porphyrin extracted from spinach leaves, cholorophyll a (Chla). Due to its strong visible absorption and fluorescence emission, this phytopigment was used as a spectral sensor to monitor any possible changes occurring in lipid membranes caused by the action of various agents. An aqueous extract from Cornus mas L. fruits was used for AgNP phytosynthesis. Addition of appropriate amounts of phytonanosilver particles and SWCNTs to biomimetic membranes resulted in biohybrid material with good physical stability (ZP = -34 mV) and high antioxidant activity (AA = 97.8%). Moreover, they have been shown to be a strong biocide having diameters of inhibition zones of 18.3 mm, 23.8 mm and 21.6 mm against Escherichia coli ATCC 8738, Staphylococcus aureus ATCC 25923 and Enterococcus faecalis ATCC 29212, respectively. Chla rapidly sensed the modifications that occurred in artificial lipid bilayers as a result of interactions with silver nanoparticles and carbon nanotube surfaces indicating the biohybrid formation, and these results were supported by AFM analysis. The bioconstructed hybrid material consisting of biomimetic membranes, phyto-nanosilver and SWCNTs could be applied as an antimicrobial and antioxidant coating.

Simultaneous two and three photon resonant enhancement of third-order NLO susceptibility in an azo-dye functionalized polymer film.

We report the observation of simultaneous two and three photon resonances, enhancing the third-order NLO susceptibility in a thin film of an azo-dye polymer. The possibility of 2-3 orders of magnitude increase in χ((3)) susceptibility is sustained by quantum mechanical calculations. This improves the applications of azo-polymers in all optical signal processing as well as in nonlinear optical imaging.