Solid-state NMR study of bioactive binary borosilicate glasses

A series of binary borosilicate glasses prepared by the sol-gel method are shown to be bioactive. Tetraethyl orthosilicate (TEOS) and trimethylborate (TMB) in acidic medium are used to prepare xB(2)O(3)center dot(1-x)SiO2 glass systems for x = 0.045-0.167. The formation of a layer of apatite-like mineral on the glass surface becomes apparent after soaking in simulated body fluid for 48 h. We have measured the B-11-B-11 homonuclear second moments of the borosilicate glasses and inferred that no macroscopic phase separation occurred in our glasses. The B-11 chemical shift data also show that the formation of clustered boroxol rings is negligible in our glass system. Although the bioactivity of our borosilicate glasses is less than that of CaO-SiO2 sol-gel glasses, these simple binary systems could be taken as reference glass systems for the search of new bioactive borosilicate glasses. (C) 2008 Elsevier Ltd. All rights reserved.

碱金属和碱土金属氟化物对掺Er^3＋氟磷酸盐玻璃光谱性质的影响

研究了碱金属和碱土金属离子修饰的掺Er^3＋氟磷酸盐玻璃的光谱性质，讨论了碱金属和碱土金属对铒氟磷玻璃的吸收和发射截面、荧光半高宽，Judd-Ofelt强度参数和上转换发光强度等光谱性质的影响，并与一些传统氧化物玻璃系统进行了比较．研究表明碱金属K^＋和碱土金属Sr^2＋掺杂高的玻璃更适宜用作光放大器基质．含12mol％K^＋的氟磷玻璃展现出7．83×10^-21cm^2的高发射截面和最小的荧光上转换强度；含23mol％Sr^2＋的氟磷玻璃则有7．58×10^-21cm^2的高发射截面、65nm的荧光半高

Oceanic migration rates of Upper Chesapeake Bay striped bass (Morone saxatilis), determined by otolith microchemical analysis*

Oceanic incidence and spawning frequency of Chesapeake Bay striped bass (Morone saxatilis) were estimated by using microchemical analysis of strontium in otoliths. Otoliths from 40 males and 82 females sampled from Maryland’s portion of the Chesapeake Bay were analyzed for seasonal and age-specific patterns in strontium and calcium levels. The proportion of oceanic females increased from 50% to 75% between ages seven to 13; the proportion of oceanic males increased from 20% to ~50% between ages four to 13. Contrary to an earliermodel of Chesapeake Bay striped bass migration, results indicated that a substantial number of males undertook oceanic migrations. Further, we observed no mass emigration of females from three to four years of age from the Chesapeake Bay. Seasonal patterns of estuarine habitat use were consistent with annual spawning runs by striped bass of mature age classes, but with noteworthy exceptions for newly mature females. Evidence of an early oceanic presence indicated that Chesapeake Bay yearlings move into coastal regions—a pattern observed also for Hudson River striped bass. Otolith microchemical analyses revealed two types of behaviors (estuarine and oceanic) that confirm migratory behaviors recently determined for other populations of striped bass and diadromous species (e.g., American eels [Anguilla rostrata] American shad [Alosa sapidissima] and white perch [Morone Americana]).

Propriedades fotoluminescentes e higroscopia do composto SrAl2O4 dopado com íons de Ni2+

Amostras foram preparadas pelo método de difusão a partir dos reagentes químicos SrCO3, Al2O3 e NiO em proporções estequiométricas. Medidas por difração de raios X mostraram que as amostras possuem uma única fase: SrAl2O4. Neste trabalho apresentamos imagens de microscopia eletrônica de varredura das amostras SrAl2O4 dopadas com 0,1%, 0,5%, 1,0%, 2,0%, 5,0% e 10,0% de íons de Ni2+, medidas de fotoluminescência, excitação da fotoluminescência da amostra SrAl2O4 dopada com 1,0% de íons de Ni2+, medidas de absorção fotoacústica das amostras SrAl2O4 dopadas com 1,0%, 2,0%, 5,0% e 10,0% de íons de Ni2+. Estas medidas foram realizadas a temperatura ambiente para investigar as transições eletrônicas dos íons divalente de níquel que entraram substitucionalmente nos sítios de Sr2+ da rede do SrAl2O4. Os resultados ópticos mostram a existência de três centros emissores de Ni2+. De acordo com a literatura, a estrutura do SrAl2O4 é composta de dois sítios octaédrico distintos de íons de Sr2+, o Sr12+ e o Sr22+, cujas distâncias médias Sr1 O e Sr2 O são, respectivamente, 2,800 Ǻ e 2,744 Ǻ. Visto que os íons de Ni2+ tendem a substituir os íons de Sr2+, devido ao fato de possuírem a mesma valência, é necessário considerar que uma parte dos íons de Ni2+ ocuparam os sítios dos íons de Al3+ na rede do SrAl2O4 para justificar a existência de um terceiro centro emissor de Ni2+ nesse composto. Uma novo sítio octaédrico para os íons de Ni2+ foi estimado a partir do valor da aresta do sítio tetraédrico ocupado pelos íons de Al3+ na rede do SrAl2O4 (considerando o raio iônico do Ni2+ como aproximadamente 40% maior do que o raio iônico do Al3+). As transições eletrônicas presentes nos espectros de excitação e absorção fotoacústica permitiram determinar os parâmetros de campo cristalino (Dq) e Racah (B e C) para os três sítios diferentes ocupados pelos íons de Ni2+ no SrAl2O4. Neste caso, os resultados mostraram que o sítio II dos íons de Ni2+ é associado à posição do Sr1 e possuem um parâmetro Dq menor e que o parâmetro Dq associado aos íons de Ni2+ que substituíram os íons de Sr no sitio I, o qual, por sua vez é associado à posição do Sr2. E, por fim, o sítio III que possui o menor parâmetro de campo cristalino Dq, portanto a maior distância íon ligante, é identificado como aquele relacionado ao rearranjo octaédrico local das antigas posições de Al3+. O caráter higroscópico do SrAl2O4:Ni2+ é observado a partir dos espectros de absorção fotoacústica e os modos de vibração de estiramento das ligações Ni OH e O H são identificadas nos espectros.

Physical properties of a hybrid and a nanohybrid dental light-cured resin composite.

This work was aimed at the study of some physical properties of two current light-cured dental resin composites, Rok (hybrid) and Ice (nanohydrid). As filler they both contain strontium aluminosilicate particles, however, with different size distribution, 40 nm-2.5 mum for Rok and 10 nm-1 mum for Ice. The resin matrix of Rok consists of UDMA, that of Ice of UDMA, Bis-EMA and TEGDMA. Degree of conversion was determined by FT-IR analysis. The flexural strength and modulus were measured using a three-point bending set-up according to the ISO-4049 specification. Sorption, solubility and volumetric change were measured after storage of composites in water or ethanol/water (75 vol%) for 1 day, 7 or 30 days. Thermogravimetric analysis was performed in air and nitrogen atmosphere from 30 to 700 degrees C. Surface roughness and morphology of the composites was studied by atomic force microscopy (AFM). The degree of conversion was found to be 56.9% for Rok and 61.0% for Ice. The flexural strength of Rok does not significantly differ from that of Ice, while the flexural modulus of Rok is higher than that of Ice. The flexural strengths of Rok and Ice did not show any significant change after immersion in water or ethanol solution for 30 days. The flexural modulus of Rok and Ice did not show any significant change either after immersion in water for 30 days, while it decreased significantly, even after 1 day immersion, in ethanol solution. Ice sorbed a higher amount of water and ethanol solution than Rok and showed a higher volume increase. Thermogravimetric analysis showed that Rok contains about 80 wt% inorganic filler and Ice about 75 wt%.

Development of functionalized terbium fluorescent nanoparticles for antibody labeling and time-resolved fluoroimmunoassay application

Silica-based functionalized terbium fluorescent nanoparticles were prepared, characterized and developed as a fluorescence probe for antibody labeling and time-resolved fluoroimmunoassay. The nanoparticles were prepared in a water-in-oil (W/O) microemulsion containing a strongly fluorescent Tb3+ chelate. N,N.N-1,N-1-12,6-bis(3'-aminomethyl-1'-pyrazolyl)phenylpyridine] tetrakis(acetate)-Tb3+ (BPTA-Tb3+), Triton X-100, octanol, and cyclohexane by controlling copolymerization of tetraethyl orthosilicate (TEOS) and 3-[2-(2- aminoethylamino)-ethylamino]propyl-trimethoxysilane (AEPS) with ammonia water. The characterizations by transmission electron microscopy and fluorometric quantum methods show that the nanoparticles are spherical and uniform in size, 45 +/- 3 nm in diameter, strongly fluorescent with fluorescence yield of 10% and a long fluorescence lifetime of 2.0 ms. The amino groups directly introduced to the nanoparticle's surface by using AEPS in the preparation made the surface modification and bioconjugation of the nanoparticles easier. The nanoparticle-labeled anti-human alpha-fetoprotein antibody was prepared and used for time-resolved fluoroimmunoassay of (x-fetoprotein (AFP) in human serum samples. The assay response is linear from 0.10 ng ml(-1) to about 100 ng ml(-1) with the detection limit of 0.10 ng ml(-1). The coefficient variations (CVs) of the method are less than 9.0%. and the recoveries are in the range of 84-98% for human serum sample measurements. (C) 2004 Elsevier B.V. All rights reserved.

Direct synthesis of Al-SBA-15 mesoporous materials via hydrolysis-controlled approach

Aluminum-substituted mesoporous SBA-15 (Al-SBA-15) materials were directly synthesized by a hydrolysis-controlled approach in which the hydrolysis of the silicon precursor (tetraethyl orthosilicate, TEOS) is accelerated by fluoride or by using tetramethyl orthosilicate (TMOS) as silicon precursor rather than TEOS. These materials were characterized by powder X-ray diffraction (XRD), N-2 sorption isotherms, TEM, Al-27 MAS NMR, IR spectra of pyridine adsorption, and NH3-TPD. It is found that the matched hydrolysis and condensation rates of silicon and aluminum precursors are important factors to achieve highly ordered mesoporous materials. Al-27 MAS NMR spectra of Al-SBA-15 show that all aluminum species were incorporated into the silica framework for the samples prepared with the addition of fluoride. A two-step approach (sol-gel reaction at low pH followed by crystallization at high pH) was also employed for the synthesis of Al-SBA-15. Studies show that the two-step approach could efficiently avoid the leaching of aluminum from the framework of the material. The calcined Al-SBA-15 materials show highly ordered hexagonal mesostructure and have both Bronsted and Lewis acid sites with medium acidity.

Surface-modified Nafion membranes with mesoporous SiO2 layers via a facile dip-coating approach for direct methanol fuel cells

In this study. Nafion (R) 117 membrane is surface-modified with mesoporous silica layers through in situ surfactant-templated sol-gel reaction. The reaction makes use of tetraethyl orthosilicate (TEOS) under acidic condition via dip-coating technique on both sides. Scanning electron microscopy (SEM), Fourier transformation infrared (FTIR), and thermogravimetric analysis (TGA) are employed to characterize the resultant membranes. Proton conductivity and methanol permeability of the membranes are also studied.

SrF2 hierarchical flowerlike structures: Solvothermal synthesis, formation mechanism, and optical properties

We present a solvothermal route to the synthesis of SrF2 hierarchical flowerlike structures based on thermal decomposition of single source precursor (SSP) of strontium trifluoroacetate in benzylamine solvent. These flowerlike superstructures are actually composed of numerous aggregated nanoplates, and the growth process involves the initial formation of spherical nanoparticles and subsequent transformation into nanoplates. which aggregated together to form microdisks and finally flowerlike superstructures. The results demonstrate the important role of benzylamine in the formation of well-defined SrF2 superstructures, not only providing size and shape control to form nanoplates but also contributing to the self-assembly behavior of nanoplates to build into flower-like superstructures. Additionally, the photoluminescence properties of the obtained SrF2 superstructures are studied.

Electrospinning Synthesis and Luminescence Properties of One-Dimensional Zn2SiO4:Mn2+ Microtibers and Microbelts

One-dimensional Mn2+-doped Zn2SiO4 rnicrobelts and microfibers were prepared by a simple and cost-effective electrospinning process. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric and differential thermal analysis (TG-DTA), scanning electron microscopy (SEM), energy-dispersive X-ray spectrum (EDS), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), photoluminescence (PL), and cathodoluminescence (CL) spectra as well as kinetic decays were used to characterize the samples. The XRD and DTA results show that the Zn2SiO4 phase begins to crystallize at 800 degrees C and crystallizes completely around 1000 degrees C. SEM results indicate that the as-prepared microbelts/fibers are smooth, whose diameters decrease with increasing the annealing temperature. The average diameter of the Zn2SiO4:Mn2+ microfibers annealed at 1000 degrees C is 0.32 mu m, and their lengths reach up to several millimeters. The average width and thickness of the Zn2SiO4:Mn2+ microbelts fired at 1000 degrees C are around 0.48 and 0.24 mu m, respectively.

Hydrothermal synthesis of SrCO3 : Eu3+/Tb3+ microneedles and their luminescence properties

SrCO3:Eu3+ /Tb3+ microneedles that grow along the a-axis were successfully prepared through a large-scale and facile hydrothermal method without any template and further annealing treatment. X-ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence (PL) spectra as well kinetic decays, were used to characterize the samples. The preferential growth along a-axis for SrCO3:Eu3+/Tb3+ microneedles has been proposed through analysis of the XRD patterns of samples obtained at different hydrothermal treatment time. Under ultraviolet excitation, the SrCO3:Eu3+ and SrCO3:Tb3+ microncedle samples show a strong red and green emission corresponding to the D-5(0)-F-7(j) (J = 1, 2, 3, 4) transitions of Eu3+ and the D-5(4)-(7) F-j (J = 6, 5, 4, 3) transitions of Tb3+, respectively, which have potential applications in lighting fields.

Thermoluminescence studies of LiBa2B5O10 : RE3+ (RE = Dy, Tb and Tm)

LiBa2B5O10:RE3+ (RE = Dy, Tb and Tm) was synthesized by the method of high-temperature solid-state reaction and the thermoluminescence (TL) properties of the samples under the irradiation of the gamma-ray were studied. The result showed that Dy3+ ion was the most efficient activator. When the concentration of Dy3+ was 2 mol%, LiBa2B5O10:Dy3+ exhibited a maximum TL output. The kinetic parameter of LiBa2B5O10:0.02Dy was estimated by the peak shape method, for which the average activation energy was 0.757 eV and the frequency factor was 1.50 x 10(7) s(-1). By the three-dimensional (3D) TL spectrum, the TL of the sample was contributed to the characteristic f-f transition of DY3+. The dose-response of LiBa2B5O10:0.02Dy to gamma-ray was linear in the range from 1 to 1000 mGy. In addition, the decay of the TL intensity of LiBa2B5O10:0.02Dy was also investigated.

In situ synthesis of silica gel nanowire/Na+-montmorillonite nanocomposites by the sol-gel route

Silica-gel nanowire/Na+-montmorillonite (Na+-MMT) nanocomposites were prepared by the in situ sol-gel process of tetraethyl orthosilicate (TEOS) in the presence of Na+-MMT and ammonia as catalyst. Microstructure characterization of the nanocomposites was done by SEM, , EDX, XRD and FTIR. It was found that a lot of silica-gel nanowires grew along the edges of Na+-MMT. The combination between the nanowires and Na+-MMT was accomplished via polycondensation of the hydrolyzed TEOS and the edge-OH groups of Na+-MMT.

DNA network structures on various solid substrates investigated by atomic force microscopy

We have fabricated DNA network structures on glass and sapphire substrates. As a comparison, we also formed the network structure on mica substrate. For titanate strontium substrate, however, DNA network can not be obtained even if it is wet-treated by Na2HPO4 solution to make it hydrophilic. We also discuss the factors that affect the DNA networks formed on various substrates.