MMP-2-Activatable Photoacoustic Tumor Imaging Probes Based on Al- and Si-Naphthalocyanines.

Enzyme-activatable photoacoustic probes are powerful contrast agents to visualize diseases in which a specific enzyme is overexpressed. In this study, aluminum and silicon naphthalocyanines (AlNc and SiNc, respectively) conjugated with matrix metalloprotease-2 (MMP-2)-responsive PLGLAG peptide sequence and poly(ethylene glycol) (PEG) as an axial ligand were designed and synthesized. AlNc-peptide-PEG conjugates AlNc-pep-PEG formed dimeric species interacting with each other through face-to-face H-aggregation in water, while SiNc-based conjugates SiNc-pep-PEG hardly interacted with each other because of the two bulky hydrophilic axial ligands. Both conjugates formed spherical nanometer-sized self-assemblies in water, generating photoacoustic waves under near-infrared photoirradiation. The treatment of MNc-peptide-PEG conjugates (M = Al, Si) with MMP-2 smoothly induced the cleavage of the PLGLAG sequence to release the hydrophilic PEG moiety, resulting in the aggregation of MNcs. By comparing the PA signal intensity changes at 680 and 760 nm, the photoacoustic signal intensity ratios were shown to be enhanced by 3-5 times after incubation with MMP-2. We demonstrated that MNc-peptide-PEG conjugates (M = Al, Si) could work as activatable photoacoustic probes in the in vitro experiment of MMP-2-overexpressed cell line HT-1080 as well as the in vivo photoacoustic imaging of HT-1080-bearing mice.

Formulation and Characterization of Microcapsules Encapsulating PC12 Cells as a Prospective Treatment Approach for Parkinson's Disease.

Parkinson's disease (PD) is the second most common neurological disorder, associated with decreased dopamine levels in the brain. The goal of this study was to assess the potential of a regenerative medicine-based cell therapy approach to increase dopamine levels. In this study, we used rat adrenal pheochromocytoma (PC12) cells that can produce, store, and secrete dopamine. These cells were microencapsulated in the selectively permeable polymer membrane to protect them from immune responses. For fabrication of the microcapsules, we used a modified Buchi spray dryer B-190 that allows for fast manufacturing of microcapsules and is industrially scalable. Size optimization of the microcapsules was performed by systematically varying key parameters of the spraying device. The short- and long-term stabilities of the microcapsules were assessed. In the in vitro study, the cells were found viable for a period of 30 days. Selective permeability of the microcapsules was confirmed via dopamine release assay and micro BCA protein assay. We found that the microcapsules were permeable to the small molecules including dopamine and were impermeable to the large molecules like BSA. Thus, they can provide the protection to the encapsulated cells from the immune cells. Griess's assay confirmed the non-immunogenicity of the microcapsules. These results demonstrate the effective fabrication of microcapsules encapsulating cells using an industrially scalable device. The microcapsules were stable, and the cells were viable inside the microcapsules and were found to release dopamine. Thus, these microcapsules have the potential to serve as the alternative or complementary treatment approach for PD.

Binding of a Fatty Acid-Functionalized Anderson-Type Polyoxometalate to Human Serum Albumin.

The Anderson-type hexamolybdoaluminate functionalized with lauric acid (LA), (TBA)3[Al(OH)3Mo6O18{(OCH2)3CNHCOC11H23}]·9H2O (TBA-AlMo6-LA, where TBA = tetrabutylammonium), was prepared via two synthetic routes and characterized by thermogravimetric and elemental analyses, mass spectrometry, IR and 1H NMR spectroscopy, and powder and single-crystal X-ray diffraction. The interaction of TBA-AlMo6-LA with human serum albumin (HSA) was investigated via fluorescence and circular dichroism spectroscopy. The results revealed that TBA-AlMo6-LA binds strongly to HSA (63% quenching at an HSA/TBA-AlMo6-LA ratio of 1:1), exhibiting static quenching. In contrast to TBA-AlMo6-LA, the nonfunctionalized polyoxometalate, Na3(H2O)6[Al(OH)6Mo6O18]·2H2O (AlMo6), showed weak binding toward HSA (22% quenching at a HSA/AlMo6 ratio of 1:25). HSA binding was confirmed by X-ray structure analysis of the HSA-Myr-AlMo6-LA complex (Myr = myristate). These results provide a promising lead for the design of novel polyoxometalate-based hybrids that are able to exploit HSA as a delivery vehicle to improve their pharmacokinetics and bioactivity.

Oxidative Dehydrogenation of Ethanol over Vanadium- and Molybdenum-modified Mg-Al Mixed Oxide Derived from Hydrotalcite.

Hydrotalcite or Mg-Al LDHs were synthesized by co-precipitation method. The Mg-Al mixed oxide was then derived by calcination of hydrotalcite at 450°C. The metal modified catalysts (Mo/Mg-Al and V/Mg-Al) were prepared by incipient wetness impregnation method. The obtained catalysts were characterized by several useful techniques and tested the reactivity for dehydrogenation and oxidative dehydrogenation of ethanol (gas-phase) to produce acetaldehyde. The catalytic reactions were performed at temperature range from 200 to 400°C for both non-oxidative and oxidative atmospheres. The results showed that the vanadium-modified hydrotalcite (V/Mg-Al) exhibited the highest ethanol conversion (34.3%) and acetaldehyde yield (15.5%) at 400℃ in the non-oxidative atmosphere. For the oxidative dehydrogenation of ethanol, the V/Mg-Al catalyst showed the highest activity at 400°C giving the ethanol conversion and acetaldehyde yield of 73.7% and 29.5%, respectively. This result probably related to the highest base density of V/Mg-Al catalyst (6.13 µmol CO2/m2) measured by CO2-TPD. The catalytic activity of Mg-Al catalyst and metal modified catalyst slightly decreased upon time-on-stream test for 10 h on oxidative dehydrogenation of ethanol due to carbon deposition.

Local Structure Modulation Induced Highly Efficient Far-Red Luminescence of La1- xLu xAlO3:Mn4+ for Plant Cultivation.

Modulating the local environment around the emitting ions with component screening to increase the quantum yield and thermal stability is an effective and promising strategy for the design of high-performance fluorescence materials. In this work, smaller Lu3+ was introduced into the La3+ site in a Mn4+-activated LaAlO3 phosphor with the expectation of improving the luminescence properties via lattice contraction induced by cation substitution. Finally, a La1- xLu xAlO3:Mn4+ ( x = 0-0.04) perovskite phosphor with a high quantum yield of 86.0% and satisfactory thermal stability was achieved, and the emission peak at 729 nm well matches with the strongest absorption peak of the Phytochrome PFR. The favorable performances could be attributed to the suppressed cell volume and superior lattice rigidity after the substitution of Lu3+. This work not only obtains a highly efficient La1- xLu xAlO3:Mn4+ ( x = 0.02) phosphor, which holds great potential for application in plant-cultivation light-emitting diodes, but also provides an applicable strategy for further investigation of far-red-emitting phosphors.

High-capacitance Ti3C2Tx MXene obtained by etching submicron Ti3AlC2 grains grown in molten salt.

Submicron Ti3AlC2 grains are grown in molten salt. Etching the grains gives rise to small-sized Ti3C2Tx MXene particulates with capacitance more than twice that of the large ones derived from conventional high-temperature synthesis. Detailed electrochemical, structural, and spectroscopic studies demonstrate that increased capacitance predominantly originates from a decrease in the lateral size of the small Ti3C2Tx MXene particulates.

Synthesis of silver-containing calcium aluminate particles and their effects on a MTA-based endodontic sealer.

OBJECTIVE: To synthetize calcium aluminate (C3A) and silver-containing C3A particles (C3A+Ag) testing their effects on the properties of a MTA-based endodontic sealer in comparison to an epoxy resin- and a calcium silicate-based sealer. METHODS: Pure C3A and C3A+Ag particles were synthesized by a chemical method and characterized using XRD to identify crystalline phases. SEM/EDS analysis investigated morphology, particle size, and elemental composition of particles. Setting time, flow, radiopacity, water sorption and solubility of commercial and modified sealers were evaluated according to ISO 6876/2012. The pH and ions release were measured using a pHmeter and a microwave induced plasma optical emission spectrometer. The inhibition of biofilm growth was evaluated by confocal laser scanning microscopy (CLSM). Data were rank transformed and analyzed by ANOVA and Tukey test (P<0.05). RESULTS: The C3A particles showed an irregular grain agglomerated structure with voids and pores. In C3A+Ag particles, Ag modified the material morphology, confirming the deposition of Ag. The physicochemical properties of the modified MTA-based sealer were similar to the commercial material, except for the significant increase in Ca+2 release. However, there was no Ag release. Setting time, flow, radiopacity, water sorption and solubility were adequate for all materials. All the materials showed alkaline pH. Antibiofilm effect was improved in the presence of C3A particles, while the biofilm inhibition was lower in the presence of Ag. SIGNIFICANCE: The modified sealer presented improved antibiofilm properties and calcium release, without dramatic effects on the other characteristics. It is expected a positive effect in its antimicrobial behavior.

Joint L2,1 Norm and Fisher Discrimination Constrained Feature Selection for Rational Synthesis of Microporous Aluminophosphates.

Feature selection has been regarded as an effective tool to help researchers understand the generating process of data. For mining the synthesis mechanism of microporous AlPOs, this paper proposes a novel feature selection method by joint l2,1 norm and Fisher discrimination constraints (JNFDC). In order to obtain more effective feature subset, the proposed method can be achieved in two steps. The first step is to rank the features according to sparse and discriminative constraints. The second step is to establish predictive model with the ranked features, and select the most significant features in the light of the contribution of improving the predictive accuracy. To the best of our knowledge, JNFDC is the first work which employs the sparse representation theory to explore the synthesis mechanism of six kinds of pore rings. Numerical simulations demonstrate that our proposed method can select significant features affecting the specified structural property and improve the predictive accuracy. Moreover, comparison results show that JNFDC can obtain better predictive performances than some other state-of-the-art feature selection methods.

Fabrication and characterization of SrAl2O4: Eu(2+)Dy(3+)/CS-PCL electrospun nanocomposite scaffold for retinal tissue regeneration.

Millions of people around the world become blind due to losing a part of the retina cells. In tissue engineering field one way to address this issue is to develop a retina tissue by scaffolds based on structure and signals received These scaffolds can play an essential role in repair and reformation of the damaged retina tissue. Here, SrAl2O4: Eu(2+), Dy(3+) nanophosphor were prepared by sol-gel method and then coated with PEG to become biocompatible. Next 10%, 30% and 50% concentration of the coated nanophosphors were dispersed in CS-PCL copolymer and electrospuned to form SrAl2O4: Eu(2+), Dy(3+)/CS-PCL scaffolds. The aforementioned photo -luminescence-scaffolds were studied for their optical, mechanical and morphological characteristics finally the effect of these scaffolds on the mice RPCs cells' proliferation and differentiation was observed. The 30% nanophosphor dispersion scaffold while providing adequate mechanical flexibility and integrity, and exhibiting superior proliferation rates and acceptable differentiation into retinal neural cells (particularly photo receptors retinal) is suggested as a promising choice in retinal tissue repair.

One-step synthesis of honeycomb-like AlPO4-11 macrostructures based on epitaxial growth and phase transformation mechanisms.

Honeycomb-like AlPO4-11 macrostructures built of hollow tubular arrays have been directly achieved in a eutectic mixture. A time-dependent study reveals that the formation process obeys in situ epitaxial growth and phase transformation mechanisms.

A novel synthetic route for magnesium aluminate (MgAl2O4) nanoparticles using sol-gel auto combustion method and their photocatalytic properties.

In this paper a novel and inexpensive route for the preparation of spinel magnesium aluminate nanoparticles (MgAl2O4) is proposed. Magnesium aluminate photocatalyst was synthesized via sol-gel auto combustion method using oxalic acid, urea, and citric acid fuels at 350°C. Subsequently, the burnt samples were calcined at different temperatures. The pure spinel MgAl2O4 with average crystallite size 27.7, 14.6 and 15.65nm was obtained at 800°C calcinations using the aforementioned fuels, respectively. The obtained samples were characterized by powder X-ray diffraction, Fourier transform infrared, UV-Vis spectroscopy, transmission electron microscope, scanning electron microscope. The photo catalytic activity of MgAl2O4 product was studied by performing the decomposition of Reactive Red Me 4BL dye under UV illumination or sunlight irradiation. The dye considerably photocatalytically degraded by 90.0% and 95.45% under UV and sunlight irradiation, respectively, within ca. 5h with pseudo first order rate constants of 5.85×10(-3) and 8.38×10(-3)min(-1), respectively.

Nickel (II) incorporated AlPO-5 modified carbon paste electrode for determination of thioridazine in human serum.

In this approach, synthesis of nickel (II) incorporated aluminophosphate (NiAlPO-5) was performed by using hydrothermal method. The diffuse reflectance spectroscopy (DRS), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR) techniques were applied in order to characterize synthesized compounds. The NiAlPO-5 was used as a modifier in carbon paste electrode for the selective determination of thioridazine which is an antidepressant drug. This research is the first example of an aluminophosphate being employed in electroanalysis. The effective catalytic role of the modified electrode toward thioridazine oxidation can be attributed to the electrocatalytic activity of nickel (II) in the aluminaphosphate matrix. In addition, NiAlPO-5 has unique properties such as the high specific surface area which increases the electron transfer of thioridazine. The effects of varying the percentage of modifier, pH and potential sweep rate on the electrode response were investigated. Differential pulse voltammetry was used for quantitative determination as a sensitive method. A dynamic linear range was obtained in the range of 1.0×10(-7)-1.0×10(-5)mol L(-1). The determination of thioridazine in real samples such as commercial tablets and human serum was demonstrated.

Synthesis, EPR and luminescent properties of YAlO3:Fe3+ (0.1-0.9mol%) nanopowders.

A simple and inexpensive combustion method was used to prepare Fe(3+) doped YAlO3 perovskite within few minutes at low temperature (400±10°C). This might be useful in lowering the cost of the material. The final products were well characterized by various spectroscopic techniques such as PXRD, SEM, TEM, FTIR and UV-Visible. The average crystallite size was estimated from the broadening of the PXRD peaks and found to be in the range 45-90nm, the results were in good agreement with the W-H plots and TEM. The crystallites show dumbbell shape, agglomerated particles with different size. The TL glow curves of 1-5kGy γ-irradiated YAlO3:Fe(3+) (0.1mol%) nanopowder warmed at a heating rate of 3°Cs(-1) records a single glow peak at ∼260°C. The kinetic parameters namely activation energy (E), order of kinetics (b) and frequency factor (s) were determined at different gamma doses using the Chens glow peak shape method and the results were discussed in detail. The photoluminescence spectra for Fe(3+) (0.1-0.9mol%) doped YAlO3 records the lower energy band at 720nm ((4)T1 (4G)→(6)A1 (6S)) and the intermediate band located at 620nm ((4)T2 ((4)G)→(6)A1 (6S)) with the excitation of 378nm. The higher energy band located at 514nm was associated to (4)E+(4)A1 ((4)G)→(6)A1 (6S) transition. The resonance signals at g values 7.6, 4.97, 4.10, 2.94, 2.33 and 1.98 were observed in EPR spectra of Fe(3+) (0.1-0.9mol%) doped YAlO3 recorded at room temperature. The g values indicate that the iron ions were in trivalent state and distorted octahedral site symmetry was observed.

Electrolytic synthesis of aqueous aluminum nanoclusters and in situ characterization by femtosecond Raman spectroscopy and computations.

The selective synthesis and in situ characterization of aqueous Al-containing clusters is a long-standing challenge. We report a newly developed integrated platform that combines (i) a selective, atom-economical, step-economical, scalable synthesis of Al-containing nanoclusters in water via precision electrolysis with strict pH control and (ii) an improved femtosecond stimulated Raman spectroscopic method covering a broad spectral range of ca. 350-1,400 cm(-1) with high sensitivity, aided by ab initio computations, to elucidate Al aqueous cluster structures and formation mechanisms in real time. Using this platform, a unique view of flat [Al13(µ3-OH)6(µ2-OH)18(H2O)24](NO3)15 nanocluster formation is observed in water, in which three distinct reaction stages are identified. The initial stage involves the formation of an [Al7(µ3-OH)6(µ2-OH)6(H2O)12](9+) cluster core as an important intermediate toward the flat Al13 aqueous cluster.

In situ high pressure NMR study of the direct synthesis of NaAlH4.

The direct synthesis of NaAlH4 has been studied, for the first time, by in situ (27)Al and (23)Na wide-line NMR spectroscopy using high pressure NMR apparatus. Na3AlH6 formation is observed within two minutes of hydrogen addition, while NaAlH4 is detected after a total of four minutes. This indicates the formation of the hexahydride does not proceed to completion before the formation of the tetrahydride ensues.

Dinuclear aluminum complexes supported by amino- or imino-phenolate ligands: synthesis, structures, and ring-opening polymerization catalysis of rac-lactide.

Two series of ligand precursors [2-OH-3-(CH(2)NR(2))-5-MeC(6)H(2)](2)CH(2) (1: NR(2) = NMe(2); 2: NR(2) = N(CH(2))(4); 3: NR(2) = N(CH(2))(5); 4: NR(2) = N(Me)Ph) and [2-OH-3-(CH=NR)-5-MeC(6)H(2)](2)CH(2) (10: R = 2,6-Pr(2)(i)C(6)H(3); 11: R = p-MeC(6)H(4); 12: R = p-ClC(6)H(4); 13: R = p-MeOC(6)H(4); 14: R = Bu(t)) were prepared. These compounds reacted with AlMe(3) to afford corresponding dinuclear aluminum complexes [AlMe(2){2-O-3-(CH(2)NR(2))-5-MeC(6)H(2)}](2)CH(2) (6: NR(2) = NMe(2); 7: NR(2) = N(CH(2))(4); 8: NR(2) = N(CH(2))(5); 9: NR(2) = N(Me)Ph) and [AlMe(2){2-O-3-(CH=NR)-5-MeC(6)H(2)}](2)CH(2) (15: R = 2,6-Pr(2)(i)C(6)H(3); 16: R = p-MeC(6)H(4); 17: R = p-ClC(6)H(4); 18: R = p-MeOC(6)H(4); 19: R = Bu(t)). All the compounds were characterized by (1)H and (13)C NMR spectroscopy and elemental analyses. Complexes 6 and 16 were additionally characterized by single crystal X-ray diffraction techniques. Catalysis of the aluminum complexes towards the ring-opening polymerization of rac-lactide was evaluated in the presence of benzyl alcohol. All the polymerization reactions proceed in a controlled manner.

The effect of various mixing and placement techniques on the compressive strength of mineral trioxide aggregate.

INTRODUCTION: The aim of this study was to evaluate the effect of various mixing techniques including mechanical and manual mixing as well as the effect of ultrasonic agitation during placement on the compressive strength of mineral trioxide aggregate (MTA). METHODS: Tooth-colored ProRoot MTA (Dentsply Maillefer, Ballaigues, Switzerland) and white MTA Angelus (Angelus Soluções Odontologicas, Londrina, Brazil) were used. One gram of each powder was mixed with a 0.34-g aliquot of distilled water. Specimens were mixed either by mechanical mixing of capsules for 30 seconds at 4,500 rpm or by a saturation technique and the application of a condensation pressure of 3.22 MPa for 1 minute. Half of the specimens were placed in stainless steel molds and agitated using indirect ultrasonic activation. All specimens were subjected to compressive strength testing after 4 days. RESULTS: The compressive strength values of ProRoot MTA were significantly greater than those of MTA Angelus (P < .05). The highest compressive strength values were recorded from ProRoot MTA samples that were mixed mechanically and placed using ultrasonic activation (mean = 101.71 MPa), whereas the lowest values were recorded for MTA Angelus samples that were mixed manually and placed without ultrasonic activation (mean = 53.47 MPa). Ultrasonically agitated groups had higher compressive strength values (P < .001). The specimens mixed mechanically had higher compressive strength values than those mixed manually (P < .05). CONCLUSIONS: The compressive strength values of ProRoot MTA were significantly greater than those of MTA Angelus. Mechanical mixing enhanced the compressive strength of the material. Regardless of the mixing techniques applied, ultrasonic agitation improved the compressive strength of the material.

Room temperature radiolytic synthesized Cu@CuAlO(2)-Al(2)O(3) nanoparticles.

Colloidal Cu@CuAlO(2)-Al(2)O(3) bimetallic nanoparticles were prepared by a gamma irradiation method in an aqueous system in the presence of polyvinyl pyrrolidone (PVP) and isopropanol respectively as a colloidal stabilizer and scavenger of hydrogen and hydroxyl radicals. The gamma irradiation was carried out in a (60)Co gamma source chamber with different doses up to 120 kGy. The formation of Cu@CuAlO(2)-Al(2)O(3) nanoparticles was observed initially by the change in color of the colloidal samples from colorless to brown. Fourier transform infrared spectroscopy (FTIR) confirmed the presence of bonds between polymer chains and the metal surface at all radiation doses. Results of transmission electron microscopy (TEM), energy dispersive X-ray spectrometry (EDX), and X-ray diffraction (XRD) showed that Cu@CuAlO(2)-Al(2)O(3) nanoparticles are in a core-shell structure. By controlling the absorbed dose and precursor concentration, nanoclusters with different particle sizes were obtained. The average particle diameter increased with increased precursor concentration and decreased with increased dose. This is due to the competition between nucleation, growth, and aggregation processes in the formation of nanoclusters during irradiation.

Preparation and stabilization of aluminium trifluoroacetate fluoride sols for optical coatings.

For the first time, aluminium fluorides in liquid phase are available for optical applications. By modifying the conditions of the fluorolytic sol-gel synthesis of aluminium fluorides transparent sols with low viscosities were obtained. These sols consist mainly of small oligomeric or cluster units of aluminium fluoride which are not measurable by DLS, WAXS, SAXS and show unusual narrow signals in solid state NMR. Isolated particles with diameters up to five nanometers can be identified by TEM measurements and allow the use of their sols in optical and anti reflecting coatings. The sol particles were modified by trifluoroacetic acid to prevent agglomeration, and as a result, the obtained xerogels can be re-dispersed transparently in organic solvents.