Non-Catalytic Benefits of Ni(II) Binding to an Si(111)-PNP Construct for Photoelectrochemical Hydrogen Evolution Reaction: Metal Ion Induced Flat Band Potential Modulation.

We report here the remarkable and non-catalytic beneficial effects of a Ni(II) ion binding to a Si|PNP type surface as a result of significant thermodynamic band bending induced by ligand attachment and Ni(II) binding. We unambiguously deconvolute the thermodynamic flat band potentials (VFB) from the kinetic onset potentials (Von) by synthesizing a specialized bis-PNP macrochelate that enables one-step Ni(II) binding to a p-Si(111) substrate. XPS analysis and rigorous control experiments confirm covalent attachment of the designed ligand and its resulting Ni(II) complex. Illuminated J-V measurements under catalytic conditions show that the Si|BisPNP-Ni substrate exhibits the most positive onset potential for the hydrogen evolution reaction (HER) (-0.55 V vs Fc/Fc+) compared to other substrates herein. Thermodynamic flat band potential measurements in the dark reveal that Si|BisPNP-Ni also exhibits the most positive VFB value (-0.02 V vs Fc/Fc+) by a wide margin. Electrochemical impedance spectroscopy data generated under illuminated, catalytic conditions demonstrate a surprising lack of correlation evident between Von and equivalent circuit element parameters commonly associated with HER. Overall, the resulting paradigm comprises a system wherein the extent of band bending induced by metal ion binding is the primary driver of photoelectrochemical (PEC)-HER benefits, while the kinetic (catalytic) effects of the PNP-Ni(II) are minimal. This suggests that dipole and band-edge engineering must be a primary design consideration (not secondary to catalyst) in semiconductor|catalyst hybrids for PEC-HER.

Liposomes Containing Nickel-Bis(dithiolene) Complexes for Photothermal Theranostics.

New thermosensitive liposomes with a phase transition at 42 °C, containing nickel-bis(dithiolene) complexes as efficient and stable photothermal agents, have been formulated and characterized. These liposomes are highly stable and keep their contents at 37 °C for more than 30 days. On the contrary, the mild hyperthermia generated by the nickel-bis(dithiolene) complex under 940 nm NIR irradiation allows for the fine controlled release of the liposome contents, making such liposomes highly suitable for on-demand drug delivery in the human body under NIR laser irradiation. These liposomes can also be directly used, as shown here, as nanoagents for photothermal therapy. In fact, strong cell death can be generated under laser irradiation in the presence of these photothermally active nanocargos containing less than 10% w/w of metal complex. We also demonstrate, for the first time, that nickel-bis(dithiolene) complexes are good photoacoustic agents, generating easily detectable ultrasonic signals directly proportional to the concentration of complexes and the used laser power.

Enhanced photocatalytic removal of Safranin-T dye under sunlight within minute time intervals using heulandite/polyaniline@ nickel oxide composite as a novel photocatalyst.

Natural zeolite heulandite/polyaniline composite (Hu/PANI) was synthesized for the first time as catalyst support for nickel oxide photocatalyst (Hu/PANI@Ni2O3). The structural, chemical, morphological, textural and optical properties were investigated using different techniques. The synthetic Ni2O3 crystals showed well developed flaky habits with diameter range 200-400 nm and length range 1-4 µm. The estimated band gap energies of Hu/PANI composite and Hu/PANI@Ni2O3 composite are 1.8 eV and 1.46 eV, respectively, which are remarkably smaller than the recorded value for pure nickel oxide. The photocatalytic properties of Hu/PANI@Ni2O3 composite for efficient degradation of safranin-T dye were evaluated under sunlight as a function of irradiation time, initial dye concentration, catalyst mass, solution pH, and the catalyst stability. Hu/PANI@Ni2O3 composite exhibits amazing photocatalytic degradation efficiency for safranin dye, whereas 80%, 98%, and ~ 100% of 5 mg/l dye were removed after only 1 min of solar irradiation using 0.025, 0.03, and 0.035 g of Hu/PANI@Ni2O3, respectively. The higher concentrations of the dye (10-50 mg/L) can be fully removed within minutes by increasing the solution pH or using higher doses from the Hu/PANI@Ni2O3 catalyst. The removal percentage achieved the maximum value at the alkaline conditions. Also, the Hu/PANI@Ni2O3 displayed high stability and remain 84.5% of the initial photocatalytic efficiency after 5 runs. Additionally, the composite can be used effectively in the removal of different types of dyes and mixed dyes within the same time intervals. Thus, loading of nickel oxide onto hybrid Hu/PANI composite as a catalyst support achieved amazing photocatalytic degradation capacity.

Effect of mobile phone use on metal ion release from fixed orthodontic appliances.

INTRODUCTION: The aim of this study was to evaluate the effect of exposure to radiofrequency electromagnetic fields emitted by mobile phones on the level of nickel in saliva. METHODS: Fifty healthy patients with fixed orthodontic appliances were asked not to use their cell phones for a week, and their saliva samples were taken at the end of the week (control group). The patients recorded their time of mobile phone usage during the next week and returned for a second saliva collection (experimental group). Samples at both times were taken between 8:00 and 10:00 pm, and the nickel levels were measured. Two-tailed paired-samples t test, linear regression, independent t test, and 1-way analysis of variance were used for data analysis. RESULTS: The 2-tailed paired-samples t test showed significant differences between the levels of nickel in the control and experimental groups (t [49] = 9.967; P <0.001). The linear regression test showed a significant relationship between mobile phone usage time and the nickel release (F [1, 48] = 60.263; P <0.001; R(2) = 0.577). CONCLUSIONS: Mobile phone usage has a time-dependent influence on the concentration of nickel in the saliva of patients with orthodontic appliances.

Molecular symmetry determines the mechanism of a very efficient ultrafast excitation-to-heat conversion in Ni-substituted chlorophylls.

In the Ni-substituted chlorophylls, an ultrafast (<60 fs) deactivation channel is created, which is not present in Ni-porphyrins. This observation prompted us to investigate in detail the mechanism of excitation-to-heat conversion in Ni-substituted chlorophylls, experimentally, using time-resolved laser-induced optoacoustic spectroscopy, and theoretically, using group theory approach. The Ni-substituted chlorophylls show exceptional photostability and the optoacoustic measurements confirm the prompt and very efficient (100%) excitation-into-heat conversion in these complexes. Considering their excellent spectral properties and the loss-free excitation-into-heat conversion they are likely to become a new class of versatile photocalorimetric references. The curious features of the Ni-substituted chlorophylls originate from the symmetry of a ligand field created in the central cavity. The central N-Ni(2+) bonds, formed via the donation of two electrons from each of the sp(2) orbitals of two central nitrogens to an empty [Formula: see text] hybrid centered on Ni(2+), have a considerable covalent character. The extreme rate of excited state relaxation is then not due to a ladder of the metal centered d-states, often invoked in metalloporphyrins, but seems to result from a peculiar topology of the potential energy surface (a saddle-shaped crossing) due to the covalent character of the N-Ni(2+) bonds. This is confirmed by a strong 0→0 character of electronic transitions in these complexes indicating a similarity of their equilibrium geometries in the ground (S(0)) and the excited states (both Q(X) and Q(Y)). The excitation energy is very efficiently converted into molecular vibrations and dissipated as heat, involving the central Ni(2+). These Ni-substituted pigments pose a fine exemplification of symmetry control over properties of excited states of transition metal complexes.

Effect of surface modification by nitrogen ion implantation on the electrochemical and cellular behaviors of super-elastic NiTi shape memory alloy.

The aim of this investigation was to enhance the biological behavior of NiTi shape memory alloy while preserving its super-elastic behavior in order to facilitate its compatibility for application in human body. The surfaces of NiTi samples were bombarded by three different nitrogen doses. Small-angle X-ray diffraction was employed for evaluating the generated phases on the bombarded surfaces. The electrochemical behaviors of the bare and surface-modified NiTi samples were studied in simulated body fluid (SBF) using electrochemical impedance and potentio-dynamic polarization tests. Ni ion release during a 2-month period of service in the SBF environment was evaluated using atomic absorption spectrometry. The cellular behavior of nitrogen-modified samples was studied using fibroblast cells. Furthermore, the effect of surface modification on super-elasticity was investigated by tensile test. The results showed the improvement of both corrosion and biological behaviors of the modified NiTi samples. However, no significant change in the super-elasticity was observed. Samples modified at 1.4E18 ion cm(-2) showed the highest corrosion resistance and the lowest Ni ion release.

Formation of multiscale surface structures on nickel via above surface growth and below surface growth mechanisms using femtosecond laser pulses.

The formation of self-organized micro- and nano-structured surfaces on nickel via both above surface growth (ASG) and below surface growth (BSG) mechanisms using femtosecond laser pulse illumination is reported. Detailed stepped growth experiments demonstrate that conical mound-shaped surface structure development is characterized by a balance of growth mechanisms including scattering from surface structures and geometric effects causing preferential ablation of the valleys, flow of the surface melt, and redeposition of ablated material; all of which are influenced by the laser fluence and the number of laser shots on the sample. BSG-mound formation is dominated by scattering, while ASG-mound formation is dominated by material flow and redeposition. This is the first demonstration to our knowledge of the use of femtosecond laser pulses to fabricate metallic surface structures that rise above the original surface. These results are useful in understanding the details of multi-pulse femtosecond laser interaction with metals.

Nickel titanates hollow shells: nanosphere, nanorod, and their photocatalytic properties.

Two kinds of hollow shell structured nickel titanates (nanosphere, nanorod) were prepared by the microwave-assisted hydrothermal method using carbon material as the template. Their phase structure, morphology, and optical properties were well characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and UV-vis diffuse reflectance spectroscopy (DRS). Comparing with the template-free NiTiO3 (NiTiO3-TF), the two kinds of hollow shell structured NiTiO3 have larger Brunauer-Emmet-Teller (BET) surface areas. Both NiTiO3 nanosphere (NiTiO3-NS) and nanorod (NiTiO3-NR) showed remarkably photocatalytic H2 evolution from the methanol aqueous solution under full-arc lamp and visible light. Additional, their photocatalytic activities were also determined by photo-degradation of methyl blue (MB), and the degradation yield reached nearly 100% within 100 min on NiTiO3-NR under visible light. Whatever in photocatalytic H2 evolution or MB degradation, their photocatalytic activities all followed the order: NiTiO3-NR > NiTiO3-NS > NiTiO3-TF. The higher photocatalytic activities of the hollow shelled NiTiO3 should be due to their larger BET surface areas and more utilization of the incident light.

Fabrication process and electromagnetic wave absorption characterization of a CNT/Ni/epoxy nanocomposite.

Since carbon nanotube (CNT) was first discovered in 1991, it has been considered as a viable type of conductive filler for electromagnetic wave absorption materials in the GHz range. In this paper, pearl-necklace-structure CNT/Ni nano-powders were fabricated by a polyol process as conductive fillers. Compared to synthesized CNT, pearl-necklace Ni-decorated CNT increased the electrical conductivity by an order of 1 due to the enhancement of the Ni-conductive network. Moreover, the decorated Ni particles prevented the agglomeration of CNTs by counterbalancing the Van der Walls interaction between the CNTs. A CNT/Ni nanocomposite showed a homogeneous dispersion in an epoxy-based matrix. This enhanced physical morphology and electrical properties lead to an increase in the loss tangent and reflection loss in the CNT/Ni/Epoxy nanocomposite compared to these characteristics of a CNT/Epoxy nanocomposite in range of 8-12 GHz. The electromagnetic wave absorption properties of CNT/Ni/epoxy nanocomposites will provide enormous opportunities for electronic applications where lightweight EMI shielding or electro-magnetic wave absorption properties are necessary.

Assembly of Ni(OH)2 nanoparticle films on aqueous surfaces induced by small amounts of toluene, and the study of their unmediated electrocatalytic oxidation toward some small biomolecules.

A simple strategy for the preparation of a Ni(OH)2 nanoparticle film is described. Ni(OH)2 nanoparticles were synthesized in an aqueous solution of Ni2+ and tert-butylamine in the presence of small amounts of toluene, which induced the nanoparticles to assemble a thin film on the aqueous surface. The obtained Ni(OH)2 nanoparticle film was easily transferred onto the electrode surfaces and exhibited stable electrochemical performance. The electrochemical behavior of various small biomolecules, including cysteine, homocysteine, glutathione, histidine, glycine, cystine, methionine, lysine, aspartic acid, glutamic acid, phenylalanine, ascorbic acid, uric acid and dopamine, were studied at the Ni(OH)2 nanoparticle-film-modified electrode. The Ni(OH)2 nanoparticle film exhibits excellent direct, unmediated electrocatalysis toward the oxidation of cysteine, homocysteine and ascorbic acid in a pH 7.4 buffer solution with a low onset potential and a high oxidation signal. This behavior differs from many reports in which small organic molecules are electrocatalyzed indirectly by the Ni(OH)2/NiOOH redox couple in a strongly alkaline solution.

Effect on the grain size of single-mode microwave sintered NiCuZn ferrite and zinc titanate dielectric resonator ceramics.

Microwave sintering of materials significantly depends on dielectric, magnetic and conductive Losses. Samples with high dielectric and magnetic loss such as ferrites could be sintered easily. But low dielectric loss material such as dielectric resonators (paraelectrics) finds difficulty in generation of heat during microwave interaction. Microwave sintering of materials of these two classes helps in understanding the variation in dielectric and magnetic characteristics with respect to the change in grain size. High-energy ball milled Ni0.6Cu0.2Zn0.2Fe1.98O4-delta and ZnTiO3 are sintered in conventional and microwave methods and characterized for respective dielectric and magnetic characteristics. The grain size variation with higher copper content is also observed with conventional and microwave sintering. The grain size in microwave sintered Ni0.6Cu0.2Zn0.2Fe1.98O4-delta is found to be much small and uniform in comparison with conventional sintered sample. However, the grain size of microwave sintered sample is almost equal to that of conventional sintered sample of Ni0.3Cu0.5Zn0.2Fe1.98O4-delta. In contrast to these high dielectric and magnetic loss ferrites, the paraelectric materials are observed to sinter in presence of microwaves. Although microwave sintered zinc titanate sample showed finer and uniform grains with respect to conventional samples, the dielectric characteristics of microwave sintered sample are found to be less than that of conventional sample. Low dielectric constant is attributed to the low density. Smaller grain size is found to be responsible for low quality factor and the presence of small percentage of TiO2 is observed to achieve the temperature stable resonant frequency.

Effect of heating mode on sinterability of Fe-Ni steels.

The present study examines the effect of heating mode on the densification, microstructure, and mechanical properties of iron-nickel steel with graphite and phosphorus addition. The compacts were sintered in conventional (radiatively-heated) and microwave (2.45 GHz, multimode) furnaces at 1120 degrees C for 1 hour in forming gas (dissociated ammonia atmosphere, 95% N2-5% H2). The experimental results show that microwave sintered alloy has better properties compared with the conventionally sintered counterparts. Detailed analyses by using optical microscopy and scanning electron microscopy (SEM) reveal that microwave sintered sample has finer microstructure. SEM examination of the fractured surfaces indicate that a mixed mode fracture containing both, ductile and brittle types, is present in microwave sintered alloy, in contrast with the brittle fracture only in conventional sintered counterpart.

Photocatalytic reduction of Cr(VI) and Ni(II) in aqueous solution by synthesized nanoparticle ZnO under ultraviolet light irradiation: a kinetic study.

Photocatalytic removal of Cr(VI) and Ni(II) from aqueous solution using synthesized nanoparticle ZnO under ultraviolet (UV) light irradiation was studied in this work. Firstly, nanoparticle ZnO was prepared by the chemical method with an organic chemical inhibitor. Then removal efficiency of Cr(VI) and Ni(II) by nanoparticle ZnO was investigated with variation of the solution pH, ZnO dosage, contact time and initial Cr(VI) and Ni(II) concentration. Maximum removal of Cr(VI) and Ni(II) was observed at near-neutral pH because the reduced photocatalytic activity of ZnO at exceedingly low and high pH values originates from either acidic/photochemical corrosion of the catalyst and/or surface passivation with Zn(OH)2. As the ZnO dosage increased, the removal efficiency of Cr(VI) and Ni(II) was continuously enhanced, but was gradually decreased above 1.25 g/l due to the increased blockage of the incident UV light used for the photocatalytic reaction. The optimum ZnO dosage was determined as 1 g/l. Removal efficiencies of Cr(VI) and Ni(II) decreased as initial Cr(VI) and Ni(II) concentration increased, due to an increased inhibition effect on the surface of ZnO resulting from the decreased reaction sites on the surface of ZnO required for the further photocatalytic reaction.

NIR-Driven Intracellular Photocatalytic O2 Evolution on Z-Scheme Ni3S2/Cu1.8S@HA for Hypoxic Tumor Therapy.

Hypoxia in a tumor microenvironment (TME) has inhibited the photodynamic therapy (PDT) efficacy. Here, Ni3S2/Cu1.8S nanoheterostructures were synthesized as a new photosensitizer, which also realizes the intracellular photocatalytic O2 evolution to relieve hypoxia in TME and enhance PDT as well. With the narrow band gap (below 1.5 eV), the near infrared (NIR) (808 nm) can stimulate their separation of the electron-hole. The novel Z-scheme nanoheterostructures, testified by experimental data and density functional theory (DFT) calculation, possess a higher redox ability, endowing the photoexited holes with sufficient potential to oxide H2O into O2, directly. Meanwhile, the photostimulated electrons can capture the dissolved O2 to form a toxic reactive oxygen species (ROS). Moreover, Ni3S2/Cu1.8S nanocomposites also possess the catalase-/peroxidase-like activity to convert the endogenous H2O2 into ·OH and O2, which not only cause chemodynamic therapy (CDT) but also alleviate hypoxia to assist the PDT as well. In addition, owing to the narrow band gap, they possess a high NIR harvest and great photothermal conversion efficiency (49.5%). It is noted that the nanocomposites also exhibit novel biodegradation and can be metabolized and eliminated via feces and urine within 2 weeks. The present single electrons in Ni/Cu ions induce the magnetic resonance imaging (MRI) ability for Ni3S2/Cu1.8S. To make sure that the cancer cells were specifically targeted, hyaluronic acid (HA) was grafted outside and Ni3S2/Cu1.8S@HA integrated photodynamic therapy (PDT), chemodynamic therapy (CDT), and photothermal therapy (PTT) to exhibit the great anticancer efficiency for hypoxic tumor elimination.

A distance-triggered signaling on-off mechanism by plasmonic Au nanoparticles: toward advanced photocathodic DNA bioanalysis.

An efficient signaling on-off mechanism was first proposed by integrating exciton-plasmon coupling and exciton energy transfer into cathodic PEC bioassays. This signaling on-off mechanism has endowed the cathodic PEC biosensor with powerful capability for ultrasensitive and specific detection of target DNA.

Defect-engineered transition metal hydroxide nanosheets realizing tumor-microenvironment-responsive multimodal-imaging-guided NIR-II photothermal therapy.

Exploiting two-dimensional nanomaterials as photo-based theranostic agents is promising for the highly efficient ablation of deep-tissue-buried tumors. However, they are limited by their poor absorption in the second near-infrared-light (NIR-II) bio-window (1000-1300 nm) and intrinsic nonbiodegradability. Herein, defect-rich sulfur-doped Ni(OH)2 (S-Ni(OH)2) nanosheets decorated with bovine serum albumin (BSA) as a novel theranostic agent is developed, which can accomplish multimodal-imaging-guided photothermal ablation of mouse cancers in the NIR-II bio-window. Sulfur doping extends the absorption spectra of Ni(OH)2 nanosheets from the visible to NIR-II bio-window, affording highly efficient photothermal conversion (58.20% for 1064 nm), entailing it to become an excellent contrast agent for photoacoustic imaging. Further, because of their intrinsic paramagnetic property, they can be applied for magnetic resonance imaging. Owing to the abundant defective sites in S-Ni(OH)2 nanosheets, they exhibit response to the tumor microenvironment, resulting in effective biodegradation and excretion from the body. In vivo toxicity experiments indicated that S-Ni(OH)2-BSA NSs delivered no appreciable toxicity and good biocompatibility. This work provides an avenue for the rational design of effective theranostics agents.

Ultra-broadband enhanced absorption of metal surfaces structured by femtosecond laser pulses.

We investigate the enhanced absorption properties in a wavelength range of 0.2-25 microm for NiTi alloy targets structured by femtosecond laser pulses in air. Three different types of surface structures are produced with varying laser fluences. Measured reflectances through integrating sphere technique show that their couplings of incident electromagnetic irradiations are improved greatly over the broadband wavelength range. In particular, for coral-like micro-structures on the metal surfaces, approximate 90% absorption can be achieved from ultraviolet to mid-infrared region. Cut-off wavelengths of the enhanced absorption for the varied dimensional surface structures are determined experimentally. Chemical analysis by X-ray photoelectron spectroscopy indicates that blackness of metal surfaces is not attributed to the change in elemental composition. The physics of such remarkable absorption for the structured metal surfaces are discussed as well.

Effects of the external magnetic field and chemical combination on Kbeta/Kalpha X-ray intensity ratios of some nickel and cobalt compounds.

A systematic study of X-ray intensity ratios of the K-series lines was made on compounds of nickel and cobalt to examine the influence of chemical state and 0.6 and 1.2 T external magnetic fields on energy-dispersive X-ray fluorescence analysis. The samples were excited by 22.69 keV X-rays emitted from a Cd-109 radioisotope source and characteristic K X-rays emitted from the samples were counted by means of an Si(Li) detector. For B=0, the present experimental results were compared with the experimental and theoretical data in literature. The results demonstrate a clear dependence of the Kbeta/Kalpha intensity ratios on the chemical state of the element in the sample and values of external magnetic field.

Excitation function for 63Cu(n,p)63Ni reaction in neutron energy range up to 15 MeV.

The excitation function for the (63)Cu(n,p)(63)Ni reaction has been measured by activation method using the 4.5 MV Dynamitron accelerator of the Fast Neutron Laboratory of Tohoku University. Copper plates and hollow spherical copper shells were irradiated by neutrons of various energy up to 14.9 MeV produced by the T(p,n), D(d,n), and T(d,n) reactions. The (63)Ni produced in the irradiated copper target was chemically separated. The beta-rays emitted from the extracted (63)Ni were measured by a liquid scintillation method. The cross sections obtained were compared with the evaluated data files of JENDL-3.3, ENDF/B-VI and FENDL/A-2.0. Consequently, it is found that FENDL/A-2.0 is consistent with our experimental data in the energy range studied in this work. The effect of proton shell appeared in the excitation function obtained is also discussed.

Effect of radiofrequency electromagnetic fields (RF-EMFS) from mobile phones on nickel release from orthodontic brackets: An in vitro study.

BACKGROUND: The worldwide dramatic increase in the use of cell phones has generated great concerns about their potential adverse health effects. OBJECTIVE: The aim of the present study was to evaluate the effects of radiofrequency electromagnetic fields (RF-EMFs) emitted from mobile phones on the level of nickel release from orthodontic brackets. METHODS: Twenty stainless steel brackets were divided randomly into experimental and control groups (n=10). Brackets were immersed in artificial saliva at 37°C for 6 months. Experimental group were exposed to GSM 900MHz RF-EMFs emitted from a mobile phone stimulator for 4hours. The specific absorption rate (SAR) was 2.287W/kg. The concentration of nickel in the artificial saliva in both groups was evaluated by using the cold-vapour atomic absorption spectrometry. The Mann-Whitney test was used to assess significant differences in nickel release between the exposed and non-exposed groups. RESULTS: The mean nickel levels in the exposed and non-exposed groups were 11.95 and 2.89µg/l, respectively. This difference between the concentrations of nickel in the artificial saliva of these groups was statistically significant (P=0.001). CONCLUSION: Exposure to RF-EMFs emitted from mobile phones can lead to human exposure to higher levels of nickel in saliva in patients with orthodontic appliances. As nickel exposure can lead to allergic reaction in humans and considering this point that about 10-20% of the population can be hypersensitive to nickel, further studies are needed to evaluate the effects of radiofrequency electromagnetic fields (RF-EMFs) emitted from common devices such as mobile phones or Wi-Fi routers on the level of nickel release from orthodontic brackets.