Injection Of Precursor Research Articles

Retinol metabolism in the mollusk Osilinus lineatus indicates an ancient origin for retinyl ester storage capacity.

Although retinoids have been reported to be present and active in vertebrates and invertebrates, the presence of mechanisms for retinoid storage in the form of retinyl esters, a key feature to maintain whole-organism retinoid homeostasis, have been considered to date a vertebrate innovation. Here we demonstrate for the first time the presence of retinol and retinyl esters in an invertebrate lophotrochozoan species, the gastropod mollusk Osilinus lineatus. Furthermore, through a pharmacological approach consisting of intramuscular injections of different retinoid precursors, we also demonstrate that the retinol esterification pathway is active in vivo in this species. Interestingly, retinol and retinyl esters were only detected in males, suggesting a gender-specific role for these compounds in the testis. Females, although lacking detectable levels of retinol or retinyl esters, also have the biochemical capacity to esterify retinol, but at a lower rate than males. The occurrence of retinyl ester storage capacity, together with the presence in males and females of active retinoids, i.e., retinoic acid isomers, indicates that O. lineatus has a well developed retinoid system. Hence, the present data strongly suggest that the capacity to maintain retinoid homeostasis has arisen earlier in Bilateria evolution than previously thought.

AQUEOUS SYNTHESIS OF HIGH QUANTUM YIELD AND MONODISPERSED THIOL-CAPPED CdxZn1-xTe QUANTUM DOTS BASED ON ELECTROCHEMICAL METHOD

A facile green approach has been developed to control the growth regime in the aqueous synthesis of CdxZn1-xTe semiconductor quantum dots (QDs) based on the electrochemistry method. The Low growth temperature and slow injection of Te precursor are used to prolong the diffusion controlled stage and thus suppress Ostwald ripening during the nanocrystal growth. The experimental results showed that a low concentration of Te precursor will definitely influence the growth procedure. The UV–visible absorption spectra, as well as transmission electron microscopy (TEM) shows the QDs a good monodispersity at any interval of the reaction procedure. The high-resolution transmission electron microscopy (HRTEM) images and powder X-ray diffraction (XRD) pattern suggested that the as-prepared QDs have high crystallinity and cubic structure. The size and composition-dependent fluorescent emission wavelength of the resultant CdxZn1-xTe alloyed QDs can be tuned from 460 to 610 nm, and their photoluminescent quantum yield can reach up to 70%. Especially in the wavelength range of 510–578 nm, the overall PL QYs of the as-prepared CdxZn1-xTe QDs were above 50%. The current work suggests that electrochemical method is an attractive approach to the synthesis of high-quality II-VI ternary alloyed semiconductor QDs at large-scale with a prominent cost advantage.

Bimetallic Nanoparticles: Kinetic Control Matters

Morphologies à la carte: a kinetic control strategy has been utilized to fabricate bimetallic nanoparticles. Using cubic Pd nanocrystals as seeds and a syringe pump that enables precise control over precursor injection rate, it is possible to synthesize Pd-Ag bimetallic nanoparticles with tailored shapes and tunable localized surface plasmon resonances.

Sidewall GaAs tunnel junctions fabricated using molecular layer epitaxy

In this article we review the fundamental properties and applications of sidewall GaAs tunnel junctions. Heavily impurity-doped GaAs epitaxial layers were prepared using molecular layer epitaxy (MLE), in which intermittent injections of precursors in ultrahigh vacuum were applied, and sidewall tunnel junctions were fabricated using a combination of device mesa wet etching of the GaAs MLE layer and low-temperature area-selective regrowth. The fabricated tunnel junctions on the GaAs sidewall with normal mesa orientation showed a record peak current density of 35 000 A cm-2. They can potentially be used as terahertz devices such as a tunnel injection transit time effect diode or an ideal static induction transistor.

Unique Challenges Accompany Thick-Shell CdSe/nCdS (n > 10) Nanocrystal Synthesis

Thick-shell CdSe/nCdS (n ≥ 10) nanocrystals were recently reported that show remarkably suppressed fluorescence intermittency or “blinking” at the single-particle level as well as slow rates of Auger decay. Unfortunately, whereas CdSe/nCdS nanocrystal synthesis is well-developed up to n ≤ 6 CdS monolayers (MLs), reproducible syntheses for n ≥ 10 MLs are less understood. Known procedures sometimes result in homogeneous CdS nucleation instead of heterogeneous, epitaxial CdS nucleation on CdSe, leading to broad and multimodal particle size distributions. Critically, obtained core/shell sizes are often below those desired. This article describes synthetic conditions specific to thick-shell growth (n ≥ 10 and n ≥ 20 MLs) on both small (sub2 nm) and large (>4.5 nm) CdSe cores. We find added secondary amine and low concentration of CdSe cores and molecular precursors give desired core/shell sizes. Amine-induced, partial etching of CdSe cores results in apparent shell-thicknesses slightly beyond those desired, especially for very-thick shells (n ≥ 20 MLs). Thermal ripening and fast precursor injection lead to undesired homogeneous CdS nucleation and incomplete shell growth. Core/shells derived from small CdSe (1.9 nm) have longer PL lifetimes and more pronounced blinking at single-particle level compared with those derived from large CdSe (4.7 nm). We expect our new synthetic approach will lead to a larger throughput of these materials, increasing their availability for fundamental studies and applications.

Seeded growth induced amorphous to crystalline transformation of niobium oxide nanostructures

A novel high-temperature synthesis of niobium oxide nanostructures has been developed through an amorphous intermediate that crystallizes into anisotropic crystalline structures through a complex mechanism of nucleation-dissolution-selective growth induced by seeded growth. The amorphous materials formed by the thermolysis of niobium oleate transformed into crystalline platelets, wires or bundled wires after the injection of additional niobium oleate at different temperatures. The temperature of the solution during injection of the additional precursor determined the morphology of the formed crystalline structure. The time- and temperature-dependent evolution of the niobium oxide nanostructures demonstrates that amorphous materials progressively turned to crystalline materials. We tuned the size of wires and platelets by the consecutive injection of the precursor solution into the reaction mixture under isothermal conditions. With the sequential injection of the precursor solution, we demonstrate that the anisotropic growth of individual nanowires occurs exclusively along the ends, without the formation of any new nuclei. A mechanism for the transformation of well-defined platelets from wires has been proposed and is due to the exclusive loss of mass at the ends of the wires while growth of the platelets initially occurs along the (001) direction which is then replaced by the (110) face.

Negative thermal diffusivity enhancement in semiconductor nanofluids

Colloidal suspensions of semiconductor InP@ZnS nanoparticles were prepared using single-step procedure without precursor injection. Thermal properties of toluene containing InP@ZnS semiconductor with different sizes (3.1, 4.2, and 4.6 nm) were measured by mode mismatched dualbeam thermal lens technique. This was done in order to measure the effect of the presence of semiconductor nanoparticles and size on the nanofluids thermal diffusivity. The characteristic time constant of the transient thermal lens was estimated by fitting the experimental data to the theoretical expression for transient thermal lens. The thermal diffusivity of the nanofluids (toluene, containing InP@ZnS semiconductor nanoparticles) it seems to be strongly dependent on the presence of semiconductor nanoparticles and particles size. For the case of nanofluids consisting of InP@ZnS nanoparticles dispersed in toluene, it was observed a decrease in the thermal diffusivity. Such behavior differs from other nanofluids, in the sense that they had shown positive thermal diffusivity enhancement. The minimum diffusivity was achieved for the nanoparticles with lowest size. Plausible explanation for such nanofluids low thermal diffusivity with semiconductor nanoparticles is given. UV-Vis spectroscopy, TEM and high-resolution electron microscopy (HRTEM), and energy dispersive spectroscopy (EDS) techniques were used to characterize the InP@ZnS nanoparticles.

The life and death of carbon nanotubes

We investigate the growth of aligned arrays of carbon nanotubes by the pyrolysis of ferrocene and toluene. These arrays are typically grown with ferrocene being introduced throughout the reaction. This continuous injection of a catalyst precursor is unusual when compared with other substrate bound carbon nanotube production routes. We have studied the activity and lifetime of the catalyst by switching from the ferrocene–toluene catalyst precursor solution to a pure toluene feedstock during growth which was monitored in situ using a laser micrometre. The catalysts' activity after the cessation of ferrocene injection was found to depend on both the concentration of the ferrocene in the initial feedstock and the time over which it was injected. The mode of growth of the array and the causes of carbon nanotube growth termination are elucidated from the data obtained.

Strategies for photoluminescence enhancement of AgInS2 quantum dots and their application as bioimaging probes

We report the effect of the initial Ag : In stoichiometry, capping ligand concentration, and reaction temperature on the optical properties (such as photoluminescence [PL] quantum yield, PL full width at half-maximum, and wavelength of maximum PL emission) of AgInS2 quantum dots (QDs). The fabricated QDs exhibit excellent optical characteristics, including PL quantum yields of up to 22% and the appearance of an excitonic absorption peak. This is the first reported observation of such a well-defined exciton absorption feature in AgInS2 QDs. Its appearance could indicate a relatively narrow size distribution or minimization of nonradiative recombination at the surface sites of the QDs. Moreover, we report one-pot two-step synthesis of highly luminescent AgInS2–ZnS QDs by injection of ZnS precursors directly into the same reactor with existing AgInS2 cores without any purification. In addition, to demonstrate their potential biomedical application, the AgInS2–ZnS QDs were coated with poly(maleic anhydride-alt-1-octadecene) and further conjugated with folic acid for human liver carcinoma (HepG2) tumor cell labeling. The folate-receptor-mediated cellular uptake of the folic-acid-conjugated AgInS2–ZnS QDs was confirmed by confocal imaging characterization. Additionally, the small dimensions and high solubility of the folic-acid-conjugated AgInS2–ZnS QDs were also exploited in prefixed-cell staining; the QDs entered the complex cellular matrix and stained both the nucleoli and cytoplasm of HepG2 cells.

InP nanowires from surfactant-free thermolysis of single molecule precursors

Indium phosphide nanofibres were grown from a single-molecule precursor, [(PhCH(2))(2)InP(SiMe(3))(2)](2), using hot injection techniques by a solution-liquid-solid (SLS) process, under "surfactant-free" conditions and without the use of protic additives. The fibres are 85-95 nm in diameter and grow from In metal droplets of 100 nm diameter. The length of the nanofibres is a function of the precursor injection temperature (rather than the growth temperature) and can be varied from 6000 nm at 210 °C to 1000 nm at 310 °C. The indium metal tip can be readily removed under mild, non-etching conditions by treatment with thiophenol-P(SiMe(3))(3) mixtures.

Asymmetric quantum dot growth via temperature cycling

The morphology of semiconductive quantum dots (qdots) and quantum rods (qrods) has been shown to be tailored by choice of ligand, size, and crystal structure. In this paper, we show that temperature cycling during nucleation and growth can also tailor morphology. By quenching nucleation and growth after precursor injection, followed by slow temperature ramping, we are able to first synthesis CdSe qdots with teardrop morphology and Wurtzite crystallinity. Using these teardrops as core seeds, CdS shells can be epitaxially deposited also using temperature cycling to fabricate CdSe/CdS core/shell structures with novel asymmetric head–tail morphology. These qdots and qrods were characterized for optical absorption, photoluminescent emission, morphology, and crystal structure.

Emerging roles for gasotransmitters

Emerging roles for gasotransmitters

Quasi-solid-state dye-sensitized solar cells assembled by in-situ chemical cross-linking at ambient temperature

Cross-linked gel polymer electrolytes containing aluminum oxide nanoparticles are successfully prepared using in-situ chemical cross-linking at room temperature after injection of the gel precursor into a dye-sensitized solar cell (DSSC). This makes it possible to directly solidify the electrolyte in the cell without leakage of solvent and to maintain close interfacial contact with the porous TiO 2 electrode. The quasi-solid-state DSSC assembled with gel polymer electrolyte containing 20 wt.% Al 2O 3 particles yields an overall conversion efficiency of 5.25% under AM 1.5 illumination at 100 mW cm − 2 .

A Facile “Dispersion–Decomposition” Route to Metal Sulfide Nanocrystals

In this paper, we demonstrate a simple and general "dispersion-decomposition" approach to the synthesis of metal sulfide nanocrystals with the assistance of alkylthiol. This is a direct heating process without precursor injection. By using inorganic metal salts and alkylthiol as the raw materials, high-quality Ag(2)S, Cu(2)S, PbS, Ni(3)S(4), CdS, and ZnS nanocrystals were successfully synthesized. The mechanism study shows that the reaction undergoes two steps. A key intermediate compound, metal thiolate, is generated first. It melts and disperses into the solvent at a relatively low temperature, and then it decomposes into metal sulfide as a single precursor upon heating. This method avoids using toxic phosphine agent and injection during the reaction process. The size and shape of the nanocrystal can be also controlled by the concentration of the reactant and ligands. Furthermore, the optical properties and assembly of the nanocrystals have also been studied. This report provides a facile, direct-heating "dispersion-decomposition" approach to synthesize metal sulfides nanocrystals that has potential for future large-scale synthesis.

Shape-Controlled Colloidal Synthesis of Rock-Salt Lead Selenide Nanocrystals

Developing simple synthetic methods to control the size and morphology of nanocrystals is an active area of research as these parameters control the material's electronic and optical properties. For a semiconductor with a symmetrical crystal structure such as lead selenide, anisotropic colloidal growth has been previously accomplished via the use of templates, seeds, or by block assembly of smaller, symmetrical subunits. Here, we present a simple method to create monodisperse lead selenide nanorods and multipods at low temperatures. The size distribution and the observed morphologies are consistent with a continuous, anisotropic growth of material. The syntheses of these anisotropic shapes are due to the nature of the nuclei that form upon injection of precursors into partially oxidized alkene solvents that may contain lactone and carbonate-functional derivatives.

The effects of the perinatal treatment with 5-hydroxytryptophan or tranylcypromine on the peripheral and central serotonin homeostasis in adult rats

Serotonin (5HT) is a biologically active amine present in mammals in the brain and the peripheral tissues. Autism is a neurodevelopmental disorder in which 5HT homeostasis is disturbed both centrally and peripherally, but the relationship between the 5HT disturbances in the two compartments is not understood. In an attempt to explore the relationship between the disturbed peripheral 5HT homeostasis and central 5HT functioning, we exposed the developing rat brain to increased 5HT concentrations, by treatment of rats with subcutaneous injections of the immediate 5HT precursor 5-hydroxy-l-tryptophan (5HTP, 25mg/kg), or the non-selective MAO inhibitor tranylcypromine (TCP, 2mg/kg), during the period of the most intensive development of 5HT neurons – from gestational day 13 to post-natal day 21. The effects of the mentioned treatments on peripheral and central 5HT levels were then studied in adult rats. Platelet and plasma 5HT concentrations (measured by ELISA), as well as cortical and midbrain 5HT, tryptophan and 5-hydroxyindoleacetic acid levels (measured by HPLC) were determined in twelve 5HTP treated and eight TCP treated rats, and compared with the values measured in 10 control, saline treated rats. Treatment with 5HTP significantly raised peripheral but not central 5HT concentrations. At adult age, peripheral 5HT homeostasis was re-established, while modest decrease in 5HT concentration was observed in frontal cortex, presumably due to hyperserotonemia-induced loss of 5HT terminals during brain development. Treatment with TCP induced significant 5HT elevations in both compartments. At adult age, permanent changes in 5HT homeostasis were observed, both peripherally (as hyperserotonemia) and centrally (as altered 5HT metabolism with decreased 5HT concentrations). Further studies are planned in order to explore the nature of the different disturbances of 5HT homeostasis induced by the two compounds, and their results are expected to shed some light on the role of hyperserotonemia in autism.

The omega-3 fatty acid-derived neuroprotectin D1 limits hippocampal hyperexcitability and seizure susceptibility in kindling epileptogenesis

Temporal lobe epilepsy, one of the most common epilepsy syndromes, is characterized by hippocampal hyperexcitability and progressive seizure susceptibility. Omega-3 fatty acids are involved in neuronal excitability and have anticonvulsant properties. We studied the effect of docosahexaenoic acid (DHA) or its derived lipid mediator, neuroprotectin D1 (NPD1, 10R,17S-dihydroxy-docosa-4Z,7Z,11E,13E,15Z,19Z-hexaenoic acid), in evoked seizures using a rapid kindling model of temporal lobe epilepsy. DHA or NPD1 was administered in rodents with or without kindling acquisition. Locomotor seizures and evoked epileptiform hippocampal activity immediately after hippocampal stimulations were analyzed. DHA or NPD1 limits hippocampal electrically induced hyperexcitability. Seizures induced by kindling triggered NPD1 synthesis in the hippocampus. Supplying its precursor, DHA, or direct injection of NPD1 into the third ventricle resulted in attenuation of kindling progression and hippocampal hyperexcitability. The significance of NPD1 in temporal lobe epilepsy could open new pathways for understanding the initiation and propagation of seizures and the role this lipid mediator plays in the neuronal network.

Investigations of solvents and various sulfur sources influence on the shape-controlled synthesis of CuInS2 nanocrystals

CuInS2 (CIS) nanocrystals were successfully synthesized through a hot-injection technique employing a reaction of copper (I) acetate and indium (III) acetate with tert-dodecanethiol as a source of sulfur, and trioctylphosphine oxide and 1-dodecanethiol were used as ligands. The reaction medium was a mixture of two solvents: oleylamine and 1-octadecene. Varying the ratio between both solvents leads to the formation of wurtzite CuInS2 particles with shapes ranging from triangular to rod-shaped with length up to 50 nm. Oleylamine turned out to influence the reaction condition in two opposite ways: by leading to monomer depletion before the injection of the sulfur precursor, and at the same time increasing the activity of the monomers remaining in solution. By changing the sulfur source from tert-dodecanethiol to sulfur dissolved in oleylamine, triangular particles with zinc blend structure and a smaller size (~5 nm) were synthesized. The final materials were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDX), and absorption spectroscopy (UV–Vis).

Photochemical loading of metal nanoparticles on reduced graphene oxide sheets using phosphotungstate

Well-dispersed reduced graphene oxide (r-GO) sheets loaded with metal nanoparticles were produced in dimethylformamide (DMF). The r-GO suspension was prepared through the photocatalytic reduction of graphene oxide (GO) using a phosphotungstate as a homogeneous photocatalyst under UV irradiation. Immediately after UV lamp was turned off, the injection of precursors of Ag, Au, and Pd caused the rapid nucleation because photoreduced phosphotungstates as well as electrons stored in r-GO directly reduced metal ions. Furthermore, the r-GO sheets not only provided the nucleation sites but also prohibited the metal nanoparticles from agglomeration. As a result, relatively uniform-sized metal nanoparticles were formed on the r-GO sheets. With phosphotungstates and UV light irradiation, both GO and metal ions can be reduced to form the hybrids of Ag, Au, and Pd/r-GO as a suspension in DMF or an isolated paper sheet without using any toxic reagents.

Continuous Transition from 3D to 1D Confinement Observed during the Formation of CdSe Nanoplatelets

We study the formation of colloidal CdSe nanoplatelets using both tansmission electron microscopy (TEM) and spectroscopic analysis. We show that the platelets form by continuous lateral extension of small (<2 nm) nanocrystal CdSe seeds. The nanoplatelet thickness is fixed by the seed dimension and remains constant during the platelet formation. The nanoplatelet lateral dimensions can be tuned using additional precursor injection. Absorption and fluorescence analysis of the CdSe nanoplatelets as they continuously extend laterally confirms a continuous transition from 3D to 1D confined nanoparticles. The formation of the CdSe platelets is found to be similar for different platelet thicknesses that we control with a precision of one CdSe monolayer.