Chain length selectivity during the polycondensation of siloxane-containing esters and alcohols by immobilized Candida antarctica lipase B

We have examined the chain length selectivity for a series of acyl donors by lipase B from Candida antarctica (CalB). CalB accepted aliphatic diesters of C4, C6 and C12 chain lengths equally. The introduction of a carbon–carbon double bond into the C4 esters dramatically lowered the rate constant associated with polymerization highlighting the role of geometry in catalysis; fumarate esters were polymerized at a reduced rate compared to the succinate esters, while the maleate esters were not polymerized above 5% over the course of 24 h. A disiloxane-containing diester impeded catalysis by CalB. We examined a series of vinyl siloxane esters and alcohols, and learned that the Z arrangement around the double bond stalled esterification by CalB completely. The distance between the ester carbonyl and the dimethylsiloxy group was shown to be an important factor in mediating catalysis. The rate constants were similar when the methylene spacer was 3, 4, or 5 units in length; beyond 6 methylene units, the rate constants increased. This has been tentatively attributed to the local reduction on the steric bulk when the larger siloxane moiety lies outside of the active site of the enzyme.     

Biological silicon nanoparticles maximize the efficiency of nematicides against biotic stress induced by Meloidogyne incognita in eggplant

Nemours effective management tactics were used to reduce world crop losses caused by plant-parasitic nematodes. Nowadays the metallic nanoparticles are easily developed with desired size and shape. Nanoparticles (NPs) technology becomes a recognized need for researchers. Ecofriendly and biosafe SiNPs are developed from microorganisms. Recently, silicon nanoparticles (SiNPs) have gained novel pesticide properties against numerous agricultural pests. This study assessed the biosynthesis of SiNPs from Fusarium oxysporum SM5. The obtained SiNPs were spherical with a size of 45 nm and a negative charge of ?25.65. The nematocidal effect of SiNPs against egg hatching and second-stage juveniles (J2) of root-knot nematode (RKN) (Meloidogyne incognita) was evaluated on eggplant,Solanum melongena L. plants. In vitro, all tested SiNPs concentrations significantly (p ≤ 0.05) inhibited the percentage of egg hatching at a different time of exposure than control. Meanwhile, after 72 h, the percent mortality of J2 ranged from 87.00 % to 98.50 %, with SiNPs (100 and 200 ppm). The combination between SiNPs and the half-recommended doses (0.5 RD) of commercial nematicides namely,  fenamiphos (Femax 40 % EC)^R, nemathorin (Fosthiazate 10 % WG) ^R, and fosthiazate (krenkel 75 % EC) ^R confirmed the increase of egg hatching inhibition and J2 mortality after exposure to SiNPs (100 ppm) mixed with 0.5 RD of synthetic nematicides. The findings suggest that the combination between SiNPs, and 0.5 RD of nematicides reduced nematode reproduction, gall formation, egg masses on roots and final population of J2 in the soil. Therefore, improving the plant growth parameters by reducing the M. incognita population.     

Correction of measured Gamma-Knife output factors for angular dependence of diode detectors and PinPoint ionization chamber

Dosimetry for Gamma-Knife requires detectors with high spatial resolution and minimal angular dependence of response. Angular dependence and end effect time for p-type silicon detectors (PTW Diode P and Diode E) and PTW PinPoint ionization chamber were measured with Gamma-Knife beams. Weighted angular dependence correction factors were calculated for each detector. The Gamma-Knife output factors were corrected for angular dependence and end effect time. For Gamma-Knife beams angle range of 84°–54°. Diode P shows considerable angular dependence of 9% and 8% for the 18 mm and 14, 8, 4 mm collimator, respectively. For Diode E this dependence is about 4% for all collimators. PinPoint ionization chamber shows angular dependence of less than 3% for 18, 14 and 8 mm helmet and 10% for 4 mm collimator due to volumetric averaging effect in a small photon beam. Corrected output factors for 14 mm helmet are in very good agreement (within ±0.3%) with published data and values recommended by vendor (Elekta AB, Stockholm, Sweden). For the 8 mm collimator diodes are still in good agreement with recommended values (within ±0.6%), while PinPoint gives 3% less value. For the 4 mm helmet Diodes P and E show over-response of 2.8% and 1.8%, respectively. For PinPoint chamber output factor of 4 mm collimator is 25% lower than Elekta value which is generally not consequence of angular dependence, but of volumetric averaging effect and lack of lateral electronic equilibrium. Diodes P and E represent good choice for Gamma-Knife dosimetry.     

Functionalized silicon quantum dots tailored for targeted siRNA delivery

For RNA interference (RNAi) mediated silencing of the ABCB1 gene in Caco-2 cells biocompatible luminescent silicon quantum dots (SiQDs) were developed to serve as self-tracking transfection tool for ABCB1 siRNA. While the 2-3 nm sized SiQD core exhibits green luminescence, the QD surfaces are completely saturated with covalently linked 2-vinylpyridine that may electrostatically bind siRNA. For down-regulating P-glycoprotein (Pgp) expression of the ABCB1 gene the SiQDs were complexed with siRNA. The cellular uptake and allocation of SiQD-siRNA complexes in Caco-2 cells were monitored using confocal laser scanning microscopy and transmission electron microscopy. The release of siRNA to the cytoplasm was verified through real-time PCR quantification of the reduced ABCB1 mRNA level. Additional evidence was obtained from time-resolved in situ fluorescence spectroscopic monitoring of the Pgp efflux dynamics in transfected Caco-2 cells which yielded significantly reduced transporter efficiencies for the Pgp substrate Rhodamine 123.     

Silicon: A neglected micronutrient essential for bone health

Bone matrix is predominantly made up of collagen, and in vitro and in animal models studies have shown that silicon is linked to glycosaminoglycans and plays an important role in the formation of cross-links between collagen and proteoglycans, determining the beneficial effects on strength, composition, and mechanical properties of bone. However, there are still no precise indications regarding a possible role of silicon on bone health in humans. Given this background, the aim of this narrative review was to consider the effectiveness of silicon dietary intake and silicon dietary supplementation (alone or with other micronutrients), in order to suggest a daily dosage of Si supplementation, on bone mineral density in humans. This review included eight eligible studies: four regarding dietary intake and four considering supplementation with silicon alone or with other nutrients. Despite the number of studies considered being low, the number of subjects studied is high (10012) and the results are interesting. Although to date the available scientific evidences are not considered valid enough to allow to establish an adequate level of Silicon intake, based on extrapolations from the data obtained with studies on animal and human models, it has been suggested that an adequate intake in order to promote beneficial effects for bone could be considered to be around 25 mg silicon/day. As for silicon dietary supplements, it has been shown that the combined treatment with orthosilicic acid (6 mg), calcium, and vitamin D has a potentially beneficial effect on femoral BMD compared to only use of calcium and vitamin D.     

细胞固定化方法制备微藻光电极的研究

通过将微藻细胞固定在平面多孔碳纸上,制备微藻光电极,并在三电极体系电解液中加入电子介体进行测试,可产生与光照同步的光电流响应。考察了不同固定化方法、不同微藻及不同电子介体的光电流响应,结果表明硅溶胶-凝胶法制备的光电极光电流响应最佳,且对于亚心形四爿藻、金藻、莱茵衣藻、蛋白核小球藻、聚球藻等 5 种微藻都适用,表明该制备方法对不同微藻具有较好的通用性。电子介体的研究表明苯醌及其衍生物由于氧还电位较高,具有较好的阳极光电流响应特性,而甲基紫精氧还电位较低,具有较好的阴极光电流响应。     

Polycrystalline Silicon Thin-film Solar cells with Plasmonic-enhanced Light-trapping

One of major approaches to cheaper solar cells is reducing the amount of semiconductor material used for their fabrication and making cells thinner. To compensate for lower light absorption such physically thin devices have to incorporate light-trapping which increases their optical thickness. Light scattering by textured surfaces is a common technique but it cannot be universally applied to all solar cell technologies. Some cells, for example those made of evaporated silicon, are planar as produced and they require an alternative light-trapping means suitable for planar devices. Metal nanoparticles formed on planar silicon cell surface and capable of light scattering due to surface plasmon resonance is an effective approach.The paper presents a fabrication procedure of evaporated polycrystalline silicon solar cells with plasmonic light-trapping and demonstrates how the cell quantum efficiency improves due to presence of metal nanoparticles.To fabricate the cells a film consisting of alternative boron and phosphorous doped silicon layers is deposited on glass substrate by electron beam evaporation. An Initially amorphous film is crystallised and electronic defects are mitigated by annealing and hydrogen passivation. Metal grid contacts are applied to the layers of opposite polarity to extract electricity generated by the cell. Typically, such a ~2 μm thick cell has a short-circuit current density (Jsc) of 14-16 mA/cm², which can be increased up to 17-18 mA/cm² (~25% higher) after application of a simple diffuse back reflector made of a white paint.To implement plasmonic light-trapping a silver nanoparticle array is formed on the metallised cell silicon surface. A precursor silver film is deposited on the cell by thermal evaporation and annealed at 23°C to form silver nanoparticles. Nanoparticle size and coverage, which affect plasmonic light-scattering, can be tuned for enhanced cell performance by varying the precursor film thickness and its annealing conditions. An optimised nanoparticle array alone results in cell Jsc enhancement of about 28%, similar to the effect of the diffuse reflector. The photocurrent can be further increased by coating the nanoparticles by a low refractive index dielectric, like MgF₂, and applying the diffused reflector. The complete plasmonic cell structure comprises the polycrystalline silicon film, a silver nanoparticle array, a layer of MgF₂, and a diffuse reflector. The Jsc for such cell is 21-23 mA/cm², up to 45% higher than Jsc of the original cell without light-trapping or ~25% higher than Jsc for the cell with the diffuse reflector only.

Introduction

Light-trapping in silicon solar cells is commonly achieved via light scattering at textured interfaces. Scattered light travels through a cell at oblique angles for a longer distance and when such angles exceed the critical angle at the cell interfaces the light is permanently trapped in the cell by total internal reflection (Animation 1: Light-trapping). Although this scheme works well for most solar cells, there are developing technologies where ultra-thin Si layers are produced planar (e.g. layer-transfer technologies and epitaxial c-Si layers) ¹ and or when such layers are not compatible with textures substrates (e.g. evaporated silicon) ². For such originally planar Si layer alternative light trapping approaches, such as diffuse white paint reflector ³, silicon plasma texturing ⁴ or high refractive index nanoparticle reflector ⁵ have been suggested.Metal nanoparticles can effectively scatter incident light into a higher refractive index material, like silicon, due to the surface plasmon resonance effect ⁶. They also can be easily formed on the planar silicon cell surface thus offering a light-trapping approach alternative to texturing. For a nanoparticle located at the air-silicon interface the scattered light fraction coupled into silicon exceeds 95% and a large faction of that light is scattered at angles above critical providing nearly ideal light-trapping condition (Animation 2: Plasmons on NP). The resonance can be tuned to the wavelength region, which is most important for a particular cell material and design, by varying the nanoparticle average size, surface coverage and local dielectric environment ^6,7. Theoretical design principles of plasmonic nanoparticle solar cells have been suggested ⁸. In practice, Ag nanoparticle array is an ideal light-trapping partner for poly-Si thin-film solar cells because most of these design principle are naturally met. The simplest way of forming nanoparticles by thermal annealing of a thin precursor Ag film results in a random array with a relatively wide size and shape distribution, which is particularly suitable for light-trapping because such an array has a wide resonance peak, covering the wavelength range of 700-900 nm, important for poly-Si solar cell performance. The nanoparticle array can only be located on the rear poly-Si cell surface thus avoiding destructive interference between incident and scattered light which occurs for front-located nanoparticles ⁹. Moreover, poly-Si thin-film cells do not requires a passivating layer and the flat base-shaped nanoparticles (that naturally result from thermal annealing of a metal film) can be directly placed on silicon further increases plasmonic scattering efficiency due to surface plasmon-polariton resonance ¹⁰.The cell with the plasmonic nanoparticle array as described above can have a photocurrent about 28% higher than the original cell. However, the array still transmits a significant amount of light which escapes through the rear of the cell and does not contribute into the current. This loss can be mitigated by adding a rear reflector to allow catching transmitted light and re-directing it back to the cell. Providing sufficient distance between the reflector and the nanoparticles (a few hundred nanometers) the reflected light will then experience one more plasmonic scattering event while passing through the nanoparticle array on re-entering the cell and the reflector itself can be made diffuse - both effects further facilitating light scattering and hence light-trapping. Importantly, the Ag nanoparticles have to be encapsulated with an inert and low refractive index dielectric, like MgF₂ or SiO₂, from the rear reflector to avoid mechanical and chemical damage ⁷. Low refractive index for this cladding layer is required to maintain a high coupling fraction into silicon and larger scattering angles, which are ensured by the high optical contrast between the media on both sides of the nanoparticle, silicon and dielectric ⁶. The photocurrent of the plasmonic cell with the diffuse rear reflector can be up to 45% higher than the current of the original cell or up to 25% higher than the current of an equivalent cell with the diffuse reflector only.     

Synthesis and photophysical properties of 1,1′-binaphthol substituted phthalocyanines

We report on the synthesis, characterization and photophysical properties of a new symmetrically tetra substituted {at non-peripheral positions with tetra(1,1′-bi-binaphtoxy)} phthalocyanines containing H₂, Mg(II), Al(III)Cl, Si(IV)Cl₂ in the central cavity. The synthesized compounds were characterized by the elemental analyses, UV-Vis, FT-IR and ¹H NMR spectroscopies. The fluorescence quantum yields, triplet quantum yields and lifetimes of the newly synthesized H₂, Mg, Al, and Si phthalocyanines were explored. Triplet quantum yields ranged from 0.24 to 0.54. The triplet lifetime for the silicon phthalocyanine derivative was the highest ever reported for a phthalocyanine (∼3.5 ms).     

Silicon isotope fractionation in rice plants, an experimental study on rice growth under hydroponic conditions

Silicon (Si) isotope composition and Si distribution among different rice plant organs and different parts of rice leaf at maturity were studied, which may provide new insights into the mechanism of Si accumulation in plants and biogeochemical Si cycle. An isotope ratio mass spectrometer (IRMS) was used to examine Si isotope fractionation by rice plant grown in a hydroponic system. The observed ³⁰Si-depletion (about 0.3‰) of whole plant relative to external nutrient solutions suggested biologically mediated Si isotope fractionation occurred during uptake. However, it was not possible to judge the Si uptake mechanism with the data. For δ³⁰Si variation within plant, there was a consistent increasing trend from lower to upper tissues (stem < leaf < husk < grain; leaf sheath < leaf blade base <leaf blade middle < leaf blade top). The phenomenon, reflecting kinetic isotope effects, could be explained that isotope fractionation during Si deposition in rice plant was a Rayleigh-like behavior. The range (−2.7‰ to 2.3‰) of δ³⁰Si variation among rice plant tissues in present experiment exceeded that (−1.7‰ to 2.5‰) of phytoliths observed previously in continents, which would enhance understanding the role of phytoliths on globe Si isotope balance.