Tailored doxycycline delivery from MCM-41-type silica carriers

Doxycycline, an antibiotic from the tetracycline class with a broad spectrum of activity, was used to prepare drug delivery systems based on pristine and functionalized mesostructured silica supports. MCM-41-type materials with different textural, structural, and surface properties were used to assess their influence on the drug release kinetics. Small- and wide-angle XRD, FTIR spectroscopy and N₂ adsorption/desorption isotherms were used to characterize the carriers before and after doxycycline loading. The drug release experiments were performed in vitro in 0.2 M phosphate buffer solution at 37 °C, and the slowest drug release kinetics was obtained for magnesium-modified MCM-41 carrier. All drug-loaded materials exhibited good antibacterial activity against Klebsiella pneumoniae ATCC 10031 strain, similar to the drug alone.     

On the concept of code-isomorphy

LetF be a finite set of cardinality ¦F¦ =q 2,n 1 an integer and :F ⁿ×Fⁿ₀ theHamming metric. Acode isomorphism C D between two block codesC,D Fⁿ is defined as an isometry which can be extended to an isometry of the whole space Fⁿ. Any permutation S _n of the positions canonically induces a so-calledequivalence map Aut Fⁿ; any system (₁,₂,...,_n) ofn permutations of the character setF induces a so-calledconfiguration Aat Fⁿ. The group Aut Fⁿ of all isometries of Fⁿ turns out to be semidirect product of the configuration group with the symmetric group of degreen. The codeword estimating failure probability of a maximum likelihood codeword estimator for aq-nary symmetric channel does not depend on the transmitted codeword, if the automorphism group of the code acts transitively on the set of codewords. When using a systematic (n, k)-encoder, the symbol decoding failure probability does not depend on the transmitted symbol or on the time of transmission if the configuration group and the automorphism group act transitively on the set of codewords resp. on the set of thek information positions.In memoriam Giuseppe Tallini     

High-resolution MALDI imaging mass spectrometry allows localization of peptide distributions at cellular length scales in pituitary tissue sections

Matrix assisted laser desorption/ionization (MALDI) imaging mass spectrometry (IMS) has been used to determine peptide distributions directly from rat, mouse and human pituitary tissue sections. Since these organs are small (10²–10³ μm) the spatial resolution of IMS is a key issue in molecular imaging of pituitary tissue sections. Here we show that high-resolution IMS allows localization of neuropeptide distributions within different cell clusters of a single organ of a pituitary tissue section. The sample preparation protocol does not result in analyte redistribution and is therefore applicable to IMS experiments at cellular length scales. The stigmatic imaging mass spectrometer used in this study produces selected-ion-count images with pixel sizes of 500 nm and a resolving power of 4 μm, yielding superior spatial detail compared to images obtained in microprobe imaging experiments. Furthermore, we show that with imaging mass spectrometry a distinction can be made between different mammalian tissue sections based on differences in the amino acid sequence of neuropeptides with the same function. This example demonstrates the power of IMS for label-free molecular imaging at relevant biological length scales.     

Carotenoid Recovery from Tomato Processing By-Products through Green Chemistry

The recovery of bioactive compounds from agro-industry-derived by-products sustains circular economy principles by encouraging maximized recycling and minimized waste. Tomato processing by-products are abundant in carotenoids, which have several health-promoting properties, and their reintegration into functional food products represents a major interest for scientists and manufacturers. In the present study, carotenoids were recovered from tomato processing by-products based on the principles of green chemistry by using generally recognized as safe (GRAS) solvents, freeze-drying as pretreatment, and ultrasound in the recovery procedure. Spectrophotometric measurements and HPLC were used to identify and quantify total and individual carotenoids from the extracts. The highest values for lycopene (1324.89 µg/g dw) were obtained when ethyl lactate was applied as a solvent, followed by ethyl acetate with slightly smaller differences (1313.54 µg/g dw). The extracts obtained from freeze-dried samples presented significantly lower amounts of lycopene, indicating that carotenoids are highly susceptible to degradation during lyophilization. Flaxseed, grape seed, and hempseed oils were enriched with carotenoids and their rheological measurements showed favorable viscoelastic properties, especially hempseed and flaxseed oil, with viscosity under 50 mPa·s. Considering the results and the economic perspective of carotenoid recovery from tomato processing by-products, ethyl acetate is suitable, sustainable, and environmentally friendly for carotenoid extraction.     

Source motion detection, estimation, and compensation for underwater acoustics inversion by wideband ambiguity lag-Doppler filtering

Acoustic channel properties in a shallow water environment with moving source and receiver are difficult to investigate. In fact, when the source-receiver relative position changes, the underwater environment causes multipath and Doppler scale changes on the transmitted signal over low-to-medium frequencies (300 Hz-20 kHz). This is the result of a combination of multiple paths propagation, source and receiver motions, as well as sea surface motion or water column fast changes. This paper investigates underwater acoustic channel properties in a shallow water (up to 150 m depth) and moving source-receiver conditions using extracted time-scale features of the propagation channel model for low-to-medium frequencies. An average impulse response of one transmission is estimated using the physical characteristics of propagation and the wideband ambiguity plane. Since a different Doppler scale should be considered for each propagating signal, a time-warping filtering method is proposed to estimate the channel time delay and Doppler scale attributes for each propagating path. The proposed method enables the estimation of motion-compensated impulse responses, where different Doppler scaling factors are considered for the different time delays. It was validated for channel profiles using real data from the BASE'07 experiment conducted by the North Atlantic Treaty Organization Undersea Research Center in the shallow water environment of the Malta Plateau, South Sicily. This paper provides a contribution to many field applications including passive ocean tomography with unknown natural sources position and movement. Another example is active ocean tomography where sources motion enables to rapidly cover one operational area for rapid environmental assessment and hydrophones may be drifting in order to avoid additional flow noise.     

Simultaneous Determination of Some Analgesic Drugs Using Mixed Mode Stationary Phase

A new HPLC method based on a mixed mode stationary phase Hypersil Duet C18/SAX was developed and applied for the simultaneous determination of acetaminophen, acetylsalicylic acid and codeine. Parameters, such as the composition of the mobile phase, the nature of the organic modifier, the buffer type and the flow rate were investigated to optimize the separation. The results obtained show that the new HPLC method is rapid, highly efficient and selective. The studied compounds are separated in 10 min, by means of a mobile phase containing phosphate buffer (pH 7.50) and methanol (65:35 v v⁻¹). The retention mechanisms of each analyte were investigated using both the linear solvent strength theory and stoichiometric displacement model. The method was fully validated and showed good linearity for each compound for a concentration ranging between 2.0 and 40 μg mL⁻¹. The limits of detection and quantification were determined and they are lower than 0.1 μg mL⁻¹. The precision (RSD) of the method does not exceed 2 % for all studied compounds. The method was successfully applied for the assay of acetaminophen, acetylsalicylic acid and codeine in pharmaceutical formulations.

     

An electronic signature of hydrolysation in the X-ray absorption spectrum of aqueous formaldehyde

Formaldehyde in aqueous solution is hydrolysed and forms methanediol. Using X-ray absorption spectroscopy we show that the hydrolysation product can be identified by a distinct electronic signature in the spectra. This is manifested by the disappearance of the oxygen 1s → π* absorption line. The X-ray absorption spectrum of aqueous formaldehyde is compared with those of the structurally similar formamide and urea, which are in contrast not hydrolysed in aqueous solution. We thereby demonstrate the exceptional sensitivity and simplicity of the technique to monitor this fundamental process in the aqueous phase.     

Novel fluorescence nanostructured materials obtained by entrapment of an ornamental bush extract in hybrid silica glass

Synthesis of some novel fluorescence nanomaterials loaded with photoactive polyphenols originated from plants with a high spectrum of biological activity, by replacing synthetic chemicals, may open new opportunities for optical and bio-medical applications. This paper presents the synthesis, characterization and fluorescence properties of a new class of materials based on host hybrid matrices obtained through templated sol–gel route, by hydrolysis and co-condensation of tetraorthoethylsilicate with octaisobutyltetracyclo [7.3.3.1^5,11] octasiloxane-endo-3,7-diol. The aim of paper is focused on the evaluation of the behavior of the fluorescence properties of ornamental bush extract at immobilization in a templated silica matrix and in a silica-silsesquioxane network, using as templates a neutral, non-toxic and biodegradable surfactant from poly(ethyleneglycol) class and a high biocompatible non-surfactant from glucidic class. The proofs of ornamental bush extract entrapment by physical interactions in silica based networks were provided by FT-IR and UV–VIS spectroscopy. The changes of polymer network due to the hydrogen bond interactions between residual Si–OH groups and functional groups of organic molecules from extract were evidenced by shifts of specific vibrations. In UV–VIS-NIR domain, the chromophore groups from ornamental bush extract were also evidenced by similar small shifts. As a result of ornamental bush extract entrapment, in all the immobilized samples the fluorescence intensity was more than 10 times amplified in samples templated with poly(ethylenglycol) surfactant) and of about 5 times in samples with glucidic template due to the physical adsorption of polyphenolic molecules from extract, excellent synergistic optical properties of SiO₂ and silsesquioxane compound and also due to a favorable conformational arrangement. The size of synthesized polymeric materials, estimated by dynamic light scattering technique showed main diameters less then 1.4 μm, namely 1,060 and 211 nm—for samples with d-glucose template and 1,330 and 531 nm—for samples with poly(ethyleneglycol) template, respectively, with a narrow size distribution and a polidispersity varying between 0.022 and 0.426. These results are in good accordance with TEM images that evidenced the presence of some polymeric aggregates which contain the vegetal extract immobilized inside hybrid SiO₂-Sq polymeric network of about hundred nanometers size. This study bring new contributions to the development of the sol–gel procedure by entrapment of a complex vegetable mixture in polymeric matrices as integral component of silica and hybrid silica-silsesquioxane networks which leads to a significant enhancement of the functional properties of the final material, thus diversifying the potential applications of organic doped sol–gel glasses.     

Syntheses and structure-activity relationships of novel 3′-difluoromethyl and 3′-trifluoromethyl-taxoids

A series of novel 3′-difluoromethyl-taxoids and 3′-trifluoromethyl-taxoids with modifications at the C2 and C10 positions were synthesized and evaluated for their in vitro cytotoxicities against human breast carcinoma (MCF7-S, MCF7-R, LCC6-WT, LCC6-MDR), non-small cell lung carcinoma (H460) and colon adenocarcinoma (HT-29) cell lines. These second-generation fluoro-taxoids exhibited several times to more than 20 times better potency than paclitaxel against drug-sensitive cancer cell lines, MCF7-S, LCC6-WT, H460, and HT-29. These fluoro-taxoids also possess two orders of magnitude higher potency than paclitaxel against drug-resistant cancer cell lines, MCF7-R and LCC6-MDR. Structure-activity relationship study shows the importance of the C10 modification for increasing the activity against multidrug-resistant cancer cell lines. Effects of the C2-benzoate modifications on the potency in the 3′-difluoromethyl-taxoid series are very clear (i.e., F < MeO < Cl < N₃), while those in the 3′-trifluoromethyl-taxoid series are less obvious. Also, different trends in the sensitivity to the C2-substitution are observed between drug-sensitive cell lines and drug-resistant cancer cell lines that overexpress efflux pumps.