Chemisorption and decomposition of nitric oxide on ruthenium

Nitric oxide, strongly chemisorbed on ruthenium, is desorbed almost completely as oxygen and nitrogen. Oxygen, nitrogen, and nitric oxide were observed singly on ruthenium with field emission microscopy. Thermal desorption spectroscopy from Ru(101̄0) showed that molecular nitrogen is only physisorbed but nitrogen from NO decomposition is strongly chemisorbed. Nitrogen from NO shows three binding states, the most strongly bound being present to only a small extent. NO shows three and two binding states when adsorbed at 120 K and 295 K respectively. Work function measurements gave Δφ = 1.3 eV for a monolayer of NO. NO is dissociatively adsorbed above 250 K but a lower temperature limit was not established. The decomposition of NO on $\text{Ru}\text{(10}\text{1}\text{0)}$ under high vacuum conditions is catalytic in that no oxides of ruthenium were observed to form in the process.     

NO气体的空间交叉CARS

采用具有高空间分辨率的空间交叉BOX CARS相位匹配方法,完成了对NO气休室温下、Q支(v=0→v=1)振转CARS谱的测量,研究了它与NO气体压强及激光线宽的关系.从CARS基本理论出发,考虑到激光线宽及不同线型,计算出理论曲线,与实验谱线进行了比较,洛伦兹线型的理论模拟和实验结果符合较好.     

Physical adsorption of nitric oxide on metal oxides

Adsorption isotherms have been measured at 77.5 K for nitric oxide and nitrogen on Al₂O₃, MgO, ZnO and NiO, and at 90.2 K. for nitric oxide on A1₂O₃ and NiO. Three isotherm measurements at 77.5 K were made on the Al₂O₃ sample for each adsorbate to examine the effect of different degrees of surface dehydroxylation. The latter was assessed by means of infrared absorption studies on an Al₂O₃ disc. Isosteric heats for NO adsorption on Al₂O₃ and NiO increase from ca. 8 kJ mol^?1 and 6 kJ mol^?1 (respectively) at half monolayer coverage to near the value of the enthalpy of sublimation (16.6 kJ mol^?1) at monolayer completion. These results are discussed in terms of adsorbate dimerisation. Anomalous adsorption-desorption behaviour for the NONiO system is discussed. Effective adsorbate molecular cross-sectional areas and results for N2 adsorption on preadsorbed NO do not support the existence of either localisation or micro-porosity.     

Chemisorption of nitric oxide by nickel

The adsorption of nitric oxide on clean and pre-oxidized nickel has been investigated by X-ray photoelectron spectroscopy. Three distinct states of chemisorption have been recognised at room temperature; one is dissociative while two involve molecularly adsorbed NO. Pre-exposing the nickel surface to oxygen enabled the activity of the surface to be controlled such that adsorption was confined to only one of the molecular states. The two molecular states are suggested to arise from “bent” and “linear” forms of NO.     

Plasticity of human dental pulp stromal cells with bioengineering platforms: A versatile tool for regenerative medicine

In recent years, human dental pulp stromal cells (DPSCs) have received growing attention due to their characteristics in common with other mesenchymal stem cells, in addition to the ease with which they can be harvested. In this study, we demonstrated that the isolation of DPSCs from third molar teeth of healthy individuals allowed the recovery of dental mesenchymal stem cells that showed self-renewal and multipotent differentiation capability. DPSCs resulted positive for CD73, CD90, CD105, STRO-1, negative for CD34, CD45, CD14 and were able to differentiate into osteogenic and chondrogenic cells. We also assayed the angiogenic potential of DPSCs, their capillary tube-like formation was assessed using an in vitro angiogenesis assay and the uptake of acetylated low-density lipoprotein was measured as a marker of endothelial function. Based on these results, DPSCs were capable of differentiating into cells with phenotypic and functional features of endothelial cells. Furthermore, this study investigated the growth and differentiation of human DPSCs under a variety of bioengineering platforms, such as low frequency ultrasounds, tissue engineering and nanomaterials. DPSCs showed an enhanced chondrogenic differentiation under ultrasound application. Moreover, DPSCs were tested on different scaffolds, poly(vinyl alcohol)/gelatin (PVA/G) sponges and human plasma clots. We showed that both PVA/G and human plasma clot are suitable scaffolds for adhesion, growth and differentiation of DPSCs toward osteoblastic lineages. Finally, we evaluated the interactions of DPSCs with a novel class of nanomaterials, namely boron nitride nanotubes (BNNTs). From our investigation, DPSCs have appeared as a highly versatile cellular tool to be employed in regenerative medicine.     

Formation of nitric oxide dimers on MgO-supported gold particles

We present density functional theory (DFT) calculations on the formation of nitric oxide dimers (N₂O₂) on Au atoms, dimers and trimers adsorbed on regular O^2 ? sites and neutral oxygen vacancies (F_s sites) of the MgO(100) surface. The study of the N₂O₂ species is of great interest since it has been detected in the NO reduction reaction as an intermediate towards the formation of N₂O. We found that the coupling of a NO molecule with a previously adsorbed one on Au/MgO is energetically favorable on Au₁ and Au₃, but unfavorable on Au₂. The stability of N₂O₂ is in direct relation with the amount of charge taken from the support. Furthermore, one of the N―O bonds can be activated as a result of the attraction between the negatively charged NO dimer and the ionic oxide surface. In fact, for Au₁ anchored on the F_s site a barrierless reaction occurs between N₂O₂ and a third NO molecule, forming adsorbed N₂O and NO₂.     

Adsorption and valence electronic states of nitric oxide on metal surfaces

Among fundamental diatomic molecules, the adsorption of carbon monoxide (CO) and nitric oxide (NO) on metal surfaces has been a subject of intensive research in the surface science community, partly owing to its relevance to heterogeneous catalysis used for environmental control. Compared to the rather well-defined adsorption mechanism of CO, that of NO is less understood because the adsorption results in much more complex reactions. The complexity is ascribed to the open-shell structure of valence electrons, making the molecule readily interact with the metal surface itself as well as with co-adsorbed molecules. Furthermore, the interaction crucially depends on the local structure of the surface. Therefore, to elucidate the interaction at the molecular scale, it is essential to study the valence state as well as the bonding geometry for individual NO molecules placed in a well-defined environment on the surface. Scanning tunneling microscopy (STM) is suitable for this purpose. In this review, we summarize the knowledge about the interaction of NO with metal surfaces, mainly focused on the valence electronic states, followed by recent studies using STM and atomic force microscopy (AFM) at the level of individual molecules.     

A study of nitric oxide adsorbed on nickel oxide,cobalt oxide,and graphite by X-ray photoelectron spectroscopy

The nitrogen 1s binding energy of nitric oxide adsorbed on nickel oxide, cobalt oxide and graphite was measured at several temperatures by X-ray photoelectron spectroscopy. For the oxides, a temperature dependent range of binding energies was observed, but for graphite the nitrogen 1s binding energy was independent of temperature. The values obtained suggest that significant back donation of electrons occurs from the oxides to the adsorbed nitric oxides, but no back donation occurs from graphite to adsorbed nitric oxide. However, adsorption did not cause changes in the binding energy of substrate core electrons. It is believed that unless the mean free path of electrons is short, the total photoelectron signal will not reveal changes in binding energy of electrons from substrate atoms at the surface.     

Heterodyne frequency measurements on the nitric oxide fundamental band

Heterodyne frequency measurements have been made on the fundamental band of nitric oxide from 1750 to 1931 cm⁻¹. Based on the analysis of these new measurements, minor changes are made in the band constants and an improved list of calculated energy levels for the v = 0 and v = 1 states is given.     

Infrared diode laser spectroscopy of nitric oxide

The lineshapes of the rotational-vibrational lines $\text{R(}\text{17}\text{2}\text{)}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{, R(}\text{19}\text{2}\text{)}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$, and $\text{R(}\text{19}\text{2}\text{)}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ of nitric oxide were measured using a PbS_0.61Se_0.39 diode laser. These lineshapes were measured for a NO/N₂ mixture and an NO/H₂O/N₂ mixture at atmospheric pressure. This is the first high resolution spectroscopic mearuement of the rotational-vibrational lineshape of NO broadened by H₂O. The effect of the H₂O is to broaden the lines, increasing the halfwidth by up to 30% for a 10% volume concentration of H₂O. For the case of NO broadened by N₂, the measured linestrengths for the $\text{R(}\text{19}\text{2}\text{)}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and $\text{R(}\text{17}\text{2}\text{)}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ lines are within 2% of previously published values.     

Quantitative in vivo1H-spectroscopy of healthy and tumorous human brain tissue at 4 tesla

In 35 healthy volunteers 79 hydrogen spectra were measured from the parietal lobe, parieto-occipital lobe, frontal lobe, temporal lobe, thalamus and insular region. Voxels were selected with a double spin-echo sequence at TE 71, 135 and 270 ms. The spectra were quantitatively evaluated by fitting a Lorentzian model to the resonances of the creatine pool at 3.02 ppm and the choline pool at 3.22 ppm. No differences were found in the intensities of either metabolite in the 6 investigated regions. Creatine and choline were equally distributed in these regions. The interindividual reproducibility of the spectra decreases with longer echo delays. The coefficients of variation of the areas of creatine and choline corrected for the number of acquisitions and the voxel size are ±13% at TE 71 ms, ±23% at TE 135 ms, ±43% at TE 270 ms. This is caused by an interindividual variation in T₂ by ±15%, which affects all resonances of a spectrum. Signal variations from the fit, the Q-factor of the RF-coil loaded with different subjects and variations in the flip angle are less than 10% at each echo delay. The intraindividual variation without repositioning of the subject was better than 10%. Using creatine as an internal reference the ratios of the amplitudes of N-acetyl-aspartate (NAA) at 2.01 ppm and γ-methylene protons of glutamic acid at 2.34 ppm were not specific for special regions of the brain. Only in the temporal lobe the ratio of NAA and creatine was reduced. A mean concentration ratio of 1.7 for NAA and Cre was measured as an average over all subjects and the investigated brain regions with the exception of the temporal lobe. Initial applications of the method to 7 patients with brain tumors are described.     

Adsorption and reaction of nitric oxide and oxygen on Rh(111)

Adsorption of NO and O₂ on Rh(111) has been studied by TPD and XPS. Both gases adsorb molecularly at 120 K. At low coverages (θ_NO < 0.3) NO dissociates completely upon heating to form N₂ and O₂ which have peak desorption temperatures at 710 and 1310 K., respectively. At higher NO coverages NO desorbs at 455 K and a new N₂ state obeying first order kinetics appears at 470 K. At saturation, 55% of the adsorbed NO decomposes. Preadsorbed oxygen inhibits NO decomposition and produces new N₂ and NO desorption states, both at 400 K. The saturation coverage of NO on Rh(111) is approximately 0.67 of the surface atom density. Oxygen on Rh(111) has two strongly bound states with peak temperatures of 840 and 1125 K with a saturation coverage ratio of 1:2. Desorption parameters for the 1125 peak vary strongly with coverage and, assuming second-order kinetics, yield an activation energy of $\text{85 ± 5}\text{kcal}\text{mol}$ and a pre-exponential factor of 2.0 cm² s^?1 in the limit of zero coverage. A molecular state desorbing at 150 K and the 840 K state fill concurrently. The saturation coverage of atomic oxygen on Rh(111) is approximately 0.83 times the surface atom density. The behavior of NO on Rh and Pt low index planes is compared.     

Surface structure effects in the adsorption and desorption of nitric oxide on rhodium

The adsorption, desorption and decomposition of NO on Rh surfaces have been investigated using field electron microscopy (FEM) and thermal desorption spectroscopy (TDS). At 77 K NO is molecularly adsorbed on all surfaces of Rh. At room temperature, however, about 30% of NO adsorbed on the rough surfaces is dissociated. The work function change Δφ due to NO adsorption increases as the surface becomes rougher. The results suggest the following order in Δφ: 0.93 eV = (100) < (111) < (511) < (410) < (331), (533) < (321) < (110) < (650) < (531), (210) = 1.4 eV. Upon heating the tip covered with molecular NO the FEM results suggest that the (321) surface is most active in the NO bond scission. The smooth surfaces are least effective in NO dissociation. The most likely interpretation of the FEM results is that the activity in NO bond scission increases in the following order: (111), (110) < (100), (511) < (650) < (410) < (210) < (331), (533) < (321). These results are discussed in relation to literature data concerning the dissociation of NO on the noble metals of Group VIII.     

Determination of optical properties of oxidative bleaching human dental tissue samples using optical coherence tomography

Oxidative bleaching changes of human teeth induced changes in the optical properties of dental tissue. We introduced 1310 nm wavelengths of optical coherence tomography (OCT) attenuation coefficient method which is a relatively novel and rarely reported methodology to measure the correlation coefficient during the teeth oxidative bleaching procedure. And the quantitative parameters of enamel optical thickness and disruption of the entrance signal (DES) were extracted from the OCT images. The attenuation coefficient of the bleached tissue is 6.2 mm⁻¹ which is significant (p < 0.001) higher than that unbleached sample is 1.4 mm⁻¹. But attenuation coefficient varied significantly (p < 0.001) between 5.9 and 1.5 mm⁻¹ in dentine which is downtrend. Furthermore, the persistence of bleaching oxidation in 35% hydrogen peroxide-induced optical thickness of enamel is similar with unbleached tissue which may indicate the refractive index of enamel is unchanged. Moreover, disruption of the entrance signal (DES) analysis showed that remarkable difference was appeared at enamel surface. The results indicate that optical properties of oxidative bleaching human dental tissue can be determined by attenuation coefficient using OCT system.     

Quinone-enhanced sonochemical production of nitric oxide from s-nitrosoglutathione

Sonolysis at 75 kHz of argon- and air-saturated aqueous solutions at pH 7.4 containing s-nitrosogluthathione (GSNO) enhances the production rate of nitric oxide (NO). The quinones, anthraquinone-2-sulfonate (AQ2S) and anthraquinone-2,7-disulfonate (AQ27S) further enhance the NO production over that produced in quinone-depleted sonicated solutions. In contrast, the hydrophobic quinones juglone (JQ) and 1,4-naphthoquinone (NQ) inhibit ultrasound-induced NO detection as compared to quinone-depleted solutions. Larger sonolytical decomposition of the hydrophobic quinones NQ and JQ, as compared to AQ2S and AQ27S, is detected which correlates with a larger production of pyrolysis-derived carbon-centered radicals. Reaction of those radicals with NO could explain NQ and JQ inhibition. This work suggests that sulfonated quinones could be used to enhance NO release from GSNO in tissues undergoing ultrasound irradiation.     

Sodium channel Na<Subscript>v</Subscript>1.7 immunoreactivity in painful human dental pulp and burning mouth syndrome

Background  

Voltage gated sodium channels Na_v1.7 are involved in nociceptor nerve action potentials and are known to affect pain sensitivity in clinical genetic disorders.     

Chemisorption and surface reactivity of nitric oxide on clean and sodium-dosed Ag(110)

The chemisorption of NO on clean and Na-dosed Ag(110) has been studied by LEED, Auger spectroscopy, and thermal desorption. On the clean surface, non-dissociative adsorption into the α-state occurs at 300 K with an initial sticking probability of ～0.1, and the surface is saturated at a coverage of about $\text{1}\text{25}$. Desorption occurs without decomposition, and is characterised by an enthalpy of E_d ～104 kJ mol^?1 — comparable with that for NO desorption from transition metals. Surface defects do not seem to play a significant role in the chemistry of NO on clean Ag, and the presence of surface Na inhibits the adsorption of αNO. However, in the presence of both surface and subsurface Na, both the strength and the extent of NO adsorption are markedly increased and a new state (β₁NO) with E_d ～121 kJ mol^?1 appears. Adsorption into this state occurs with destruction of the Ag(110)-(1 × 2)Na ordered phase. Desorption of β₁NO occurs with significant decomposition, N₂ and N₂O are observed as geseous products, and the system's behaviour towards NO resembles that of a transition metal. Incorporation of subsurface oxygen in addition to subsurface Na increases the desorption enthalpy (β₂NO), maximum coverage, and surface reactivity of NO still further: only about half the adsorbed layer desorbs without decomposition. The bonding of NO to Ag is discussed, and comparisons are made with the properties of α and βNO on Pt(110).