In situ deposition of flower-like ZnO on silk fibroin fibers

In this paper, a convenient biomineralization technique has been developed to form and assemble flower-like zinc oxide (ZnO) on silk fibroin fiber (SFF). Therein, SFF functions as supporting substrate and reactive sites for the in situ generation of ZnO particles. The photoluminescence (PL) of the resulting nanocomposite ZnO/SFF is investigated extensively. The PL peaks are mainly in the visible region (red), which is different from the usual ZnO region (green and violet). As-prepared ZnO/SFF nanocomposites could be useful in the medical field, photoelectron transfer devices, biomolecular detection, and antibacterial agents.     

In situ observation of cascade damage under heavy ion irradiation

Abstract

Collision cascades initiated from high energy PKAs produce defect clusters in crystalline solids irradiated with fast neutrons or energetic ions. They will affect not only an early stage of microstructural evolution but that at high fluence by changing free defect survival rate. To elucidate fundamental processes of cascade damage evolution, in situ observation of microstructure in FCC metals under heavy ion irradiation has been carried out using a combined facility of a 400 kV accelerator and a 200 kV transmission electron microscope installed in the University of Tokyo, Tokai. Defect clusters produced by individual energetic ions are observed during irradiation to examine subcascade formation, interaction of point-defects from cascade damage and related point-defect processes.     

Deep level emission of ZnO nanoparticles deposited inside UV opal

The temperature-dependent photoluminescence spectra of zinc oxide (ZnO) nanocrystals deposited inside the ultraviolet (UV) opal were studied. ZnO was grown in the voids between FCC packed SiO₂ spheres using spray pyrolysis under ultrasonic vibration in the solution containing a zinc nitrate precursor. The ZnO nanoparticles inside opal matrix with UV photonic band-gap exhibit suppression of the excitonic emission and enhancement of the deep level emission. Suppression of the excitonic lines is due to the inhibition of spontaneous emission, while enhancement and broadening of the DL emission in the green spectral region is due to Purcell effect. The infiltration of ZnO nanoparticles inside the photonic crystal may be a useful technique to increase its emission efficiency in the selected spectral region.     

In situ size measurement of Si nanoparticles and formation dynamics after laser ablation

We have developed a technique to detect Si nanoparticles selectively and to measure size in situ. Applying the technique, we have investigated formation process of Si nanoparticles after pulsed laser ablation of Si targets in Ar gas. Time-resolved photoluminescence (PL) spectroscopy revealed that PL only from Si nanoparticles is observed below 2.4 eV while PL from Si nanoparticles as well as defects in SiO₂ is observed above 2.4 eV. Therefore, Si nanoparticles can be detected selectively by excitation light with a photon energy below 2.4 eV. It is found that the onset of the PL from Si nanoparticles is delayed by approximately 0.3 ms from that of the defects and smaller Si nanoparticles. A size can be estimated by a band gap, which is roughly equal to the lowest photon energy at which Si nanoparticles can be excited. Thus, we estimated the sizes of growing Si nanoparticles. PACS 61.46.+w; 78.66.w; 07.60.Yi     

Deposition of silver nanoparticles on silica spheres via ultrasound irradiation

Silver-decorated silica spheres of submicrometer-sized silica spheres with a core-shell structure were obtained based on a seed-mediated growth process, where silver nanoparticles were firstly formed from reducing Ag⁺ to Ag⁰ in N,N-dimethylformamide (DMF) in the presence of poly(vinylpyrrolidone) (PVP) as protective agent under ultrasound irradiation, followed by the growth of silver shell served silver nanoparticles as nucleation sites and formaldehyde as reducer. The results revealed that the terms of PVP addition and ultrasonic surroundings had great influence on the fabrication of silver seeds.     

In situ TEM nanoindentation of nanoparticles

The deformation behavior of nanoparticles continues to be an exciting area for materials research. Typically, nanoparticles show a conspicuous lack of dislocations, even after significant deformation. Therefore, it has been suggested that dislocations cannot exist or/do not play a role on the deformation of nanoparticles. In situ TEM nanoindentation is a critical tool for addressing this issue because it allows for the deformation to be monitored in real time. In this article, we discuss some of the experimental needs and challenges for performing in situ nanoindentation TEM experiments on nanoparticles. In addition, we show both diffraction contrast and phase contrast in situ TEM nanoindentation experiments on silver nanoparticles with diameters below 50nm. Evidence of the presence of dislocations was observed during deformation, but upon unloading dislocations disappeared.     

Formation of silver iodide nanoparticles on silk fiber by means of ultrasonic irradiation

The growth of silver iodide nanoparticles on silk fiber was achieved by sequential dipping in an alternating bath of potassium iodide and silver nitrate under ultrasound irradiation. Some parameters such as effect of pH, concentration and numerous sequential dipping in growth of the nanocrystal have been studied. The samples were characterized with powder X-ray diffraction (XRD), scanning electron microscopy (SEM), ICP, TGA and solid state UV–vis spectroscopy.     

In situ observation of the ultrafast lattice dynamics of graphite under ion irradiation

We develop a pump-probe experiment system, in which vibrational dynamics of a solid sample under ion irradiation can be measured in real time. In situ observation enables us to monitor small changes induced by ion irradiation, without being influenced by the irreproducibility of the sample quality or the experimental configuration. We apply the experimental system to investigate the femtosecond dynamics of the coherent E_2g1 phonon of graphite under 5 keV He⁺ irradiation. A slight decrease in the dephasing rate of the phonon at the initial stage, as well as a downshift followed by an upshift of the phonon frequency, are clearly demonstrated, all of which were ambiguous in the ex situ experiment due to the poor reproducibility of the surface quality. This technique could also be applied to study femtosecond vibrational dynamics in real time during thermal annealing, film deposition with e.g. ablation and sputter, and molecular adsorption on substrates.     

Synthesis of oximes under ultrasound irradiation

The condensation of aldehydes and ketones with hydroxylamine hydrochloride results oximes in 50.7-98.7% yields in EtOH under ultrasound irradiation. Compared with conventional methods, the main advantages of the present procedure are milder conditions, shorter reaction time and higher yields.     

Radiation-induced formation of ZnO nanoparticles on the ZnSe single-crystal surface

The possible formation of ZnO nanocrystals was studied as a result of radiolysis of a ZnSe crystal surface exposed to zinc vapor and irradiated with gamma rays and in producing ZnSe-ZnO heterostructures. Under ⁶⁰Co gamma radiation in air, nanocrystals ～27 nm in size are formed from nanoscopic ZnO nuclei. Under a mixed flux of gamma rays and thermal-neutron radiation, a twin structure is formed in the host ZnSe lattice and ZnO is removed. The oxide layer is also destroyed under proton irradiation in vacuum. It is found that the growth of ZnO nanocrystallites causes a manyfold increase in the luminescence intensity in the ～600-nm band and in microhardness and also a decrease in the resistance and blocking and threshold voltages irrespective of polarity. Thus, gamma irradiation brings about the formation of light-emitting ZnSe-ZnO: Zn semiconductor structures with a p-n junction.     

Synthesis of alpha-oximinoketones under ultrasound irradiation

The reaction of 6-acylmethylphenanthridines with isoamyl nitrite results alpha-oximino-6-acylmethylphenanthridines in 73-95% yields in DMF under ultrasound irradiation. Compared with conventional methods, the main advantages of the present procedure are milder conditions, shorter reaction time and higher yields.     

Synthesis of N-alkoxyphthalimides under ultrasound irradiation

The alkylation of N-hydroxyphthalimide with alkyl halides in the presence of potassium carbonate results N-alkoxyphthalimides in 64-99% yields in DMSO under ultrasound irradiation. Compared with conventional methods, the main advantages of the present procedure are milder conditions, shorter reaction time and higher yields.     

In situ bioinspired synthesis of silver chloride nanocrystals on silk fibroin fibers

Silver chloride (AgCl) nanocrystals were formed and grown on silk fibroin fibers (SFFs) by a room-temperature process. Practically, the degummed SFFs were immersed into silver nitrate solution and sodium chloride solution in turn. The amino acids on the SFF surface were negatively charged in alkaline impregnant, providing locations to immobilize silver ions and form silver chloride seeds. AgCl nanocrystals can further grow into cubic AgCl nanocrystals with an edge of about 100 nm. The morphologies of the AgCl nanocrystals were mostly influenced by the concentration of sodium chloride solution and the special configurations of the SFFs. The target AgCl/SFF nanocomposites constructed by AgCl nanocrystals and substrate SFFs could be used as photocatalysts in water splitting and antibacterial agents. This work provides an important example in the introduction of natural biofibers to the synthesis of functional hybrid nanocomposites by a green and mild technique.     

Nanocomposite ZnO/Au formation by pulsed laser irradiation

The ZnO/Au nanocomposite formation involves synthesis of Au and ZnO colloidal solutions by 532 nm pulse laser ablation of metal targets in deionized water followed by laser irradiation of the mixed colloidal solution. The transmission electron microscope (TEM) and high-resolution transmission electron microscope (HRTEM) images show evolution of spherical particles into ZnO/Au nanonetworks with irradiation time. The formation mechanism of the nanonetwork can be explained on the basis of near resonance absorption of 532 nm irradiation by gold nanoparticles which can cause selective melting and fusion of gold nanoparticles to form network. The ZnO/Au nanocomposites show blue shift in the ZnO exciton absorption and red shift in the Au plasmon resonance absorption due to interfacial charge transfer.     

In situ SEM studies on strain sensing mechanisms of PPy-coated electrically conducting fabrics

This paper studies a flexible fabric strain sensor from PPy-coated fabrics prepared by a chemical vapor deposition method under low temperature, placing an emphasis on mechanisms of its strain sensing behavior. In situ tensile tests in a scanning electron microscope (SEM) were conducted for PPy-coated electrically conducting yarns, which were prepared by the same procedure as that for the PPy-coated fabrics, enabling it possible to observe in situ the phenomena that occurred on the fiber surface during fabric deformation. The investigation revealed that the PPy-coated nylon/polyurethane fabrics exhibited a high strain sensitivity of over 400 and very large workable strain range greater than 50%, which mainly attributes to the high conductivity and crack-opening and crack-closing mechanisms of PPy-coated polyurethane yarn, as well as the excellent properties of knitted fabric structure.     

Improved synthesis of chalcones under ultrasound irradiation

Claisen-Schmidt condensation of acetophenone with aromatic aldehydes catalyzed by pulverized KOH and KF-Al2O3 results chalcones in 52-97% and 83-98% yields respectively in alcoholic solvent under ultrasound irradiation.     

Dynamic processes in metal nanoparticles under irradiation

Dynamic processes occurring in a nanoscale metal object during the implantation of high-energy ions are studied in detail. It is shown that the elastic and thermoelastic lattice responses to irradiation form force factors considerably affecting the evolution of the defect-impurity system, which, in turn, leads to a decrease in the number of structural defects. Quantitative estimates of the spatial redistribution of defects resulting in their emergence on the surface are obtained. Such self-organization of nanoparticles under ionizing radiation forms a basis for the production of nanostructured radiation-resistant materials capable of sustaining a long-term intense radiation load.     

Dense coating of surface mounted CuBTC Metal-Organic Framework nanostructures on silk fibers, prepared by layer-by-layer method under ultrasound irradiation with antibacterial activity

The growth of Cu₃(BTC)₂ (BTC = 1,3,5-benzenetricarboxylate), also known as CuBTC and HKUST-1, Metal-Organic Framework (MOF) nanostructures on silk fibers were achieved by layer-by-layer technique in alternating bath of Cu(OAc)₂·2H₂O and H₃BTC solutions under ultrasound irradiation. The effect of pH, reaction time, ultrasound irradiation and sequential dipping steps in growth of the CuBTC Metal-Organic Framework nanostructures has been studied. These systems depicted a decrease in the size accompanying a decrease in the sequential dipping steps. In addition, dense coating of silk fibers with CuBTC MOF results in decrease the emission intensity of silk fibers. The silk fibers containing CuBTC Metal-Organic Framework exhibited high antibacterial activity against Escherichia coli and Staphylococcus aureus. The samples were characterized with powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) spectra and scanning electron microscopy (SEM). XRD analyses indicated that the prepared CuBTC MOF nanostructures on silk fibers were crystalline.     

Lysozyme crystallization in hydrogel media under ultrasound irradiation

Sonocrystallization implies the application of ultrasound radiation to control the nucleation and crystal growth depending on the actuation time and intensity. Its application allows to induce nucleation at lower supersaturations than required under standard conditions. Although extended in inorganic and organic crystallization, it has been scarcely explored in protein crystallization. Now, that industrial protein crystallization is gaining momentum, the interest on new ways to control protein nucleation and crystal growth is advancing. In this work we present the development of a novel ultrasound bioreactor to study its influence on protein crystallization in agarose gel. Gel media minimize convention currents and sedimentation, favoring a more homogeneous and stable conditions to study the effect of an externally generated low energy ultrasonic irradiation on protein crystallization avoiding other undesired effects such as temperature increase, introduction of surfaces which induce nucleation, destructive cavitation phenomena, etc. In-depth statistical analysis of the results has shown that the impact of ultrasound in gel media on crystal size populations are statistically significant and reproducible.