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• 1. [Article] Towards p-Type Conductivity in SnO2Nanocrystals through Li Doping and Its Applications in Porous Diodes for Room Temperature Chlorine Gas Detection

  This work examined electrical transport properties and Li doping in SnO2synthesized by the sol–gel method. Solid-state 7Li-NMR line shapes revealed that Li ions occupy two distinct sites with differing ...

  Citation × Citation Citation Abstract Copy Title: Towards p-Type Conductivity in SnO2Nanocrystals through Li Doping and Its Applications in Porous Diodes for Room Temperature Chlorine Gas Detection Author: Chaparadza, Allen, Rananavare, Shankar Year: 2016 This work examined electrical transport properties and Li doping in SnO2synthesized by the sol–gel method. Solid-state 7Li-NMR line shapes revealed that Li ions occupy two distinct sites with differing dynamic mobilities. The chemical exchange rate between the two sites is, however, too slow for detection on the NMR timescale. Compressed nanoparticulate films of this doped semiconductor exhibited a positive Seebeck coefficient implying a p-type conductivity. A variable-temperature direct current conductivity, over a 25–350 °C temperature range, followed an Efros–Shklovskii variable range hopping (ES-VRH) conduction mechanism (ln(ρ) versus T−1/2) at temperatures below 100 °C with a crossover to 2D Mott variable range hopping (M-VRH) (ln(ρ) versus T−1/3) conduction at temperatures above 250 °C. In a transition region between these two limiting behaviors, direct current resistivity exhibited an anomalous temperature-independent plateau. We suggest that its origin may lie in a carrier inversion phenomenon wherein the majority carriers switch from holes to electrons due to Li ion expulsion from the crystalline core and creation of oxygen vacancies generated by loss of oxygen at elevated temperatures. Using a compression technique, porous diodes consisting of n-type (antimony doped SnO2) and the p-type (lithium-doped) nano-particulate films were prepared. Typical current-voltage curves of such devices resembled the behavior of a typical diode but for one key difference; owing to the porosity of the film, areas near the p-n interface and the p- and n-regions are accessible to gaseous analytes. This access is not possible in conventional diodes fabricated through contemporary planar technology. The gas sensing properties of the diodes were investigated by using Cl2, Br2, HCl, NO, NO2, CHCl3, NH3 and H2. Of all the gases tested, the sensor had very good sensitivity to Cl2 and had a response of 80 at 400 ppb of Cl2. The response time of the sensor was ~30 s at room temperature but the recovery time was temperature dependent. At room temperature the recovery time was 80s after 400 ppb chlorine exposure. The sensors were also found to recover quickly (~ 30 s) when the junctions were biased. Reverse biasing the diode provides a controllable band-bending at a p-n junction that could influence the electron-transfer rates from the adsorbates which create intra-band localized states. As a result reverse biasing can provide a means of desorbing the analyzed species. This approach eliminates the requirement to remove adsorbates by elevating the sensor temperature and hence improves on the energy efficiency of these types of sensors. Title: Towards p-Type Conductivity in SnO2Nanocrystals through Li Doping and Its Applications in Porous Diodes for Room Temperature Chlorine Gas Detection Author: Chaparadza, Allen, Rananavare, Shankar Year: 2016 This work examined electrical transport properties and Li doping in SnO2synthesized by the sol–gel method. Solid-state 7Li-NMR line shapes revealed that Li ions occupy two distinct sites with differing dynamic mobilities. The chemical exchange rate between the two sites is, however, too slow for detection on the NMR timescale. Compressed nanoparticulate films of this doped semiconductor exhibited a positive Seebeck coefficient implying a p-type conductivity. A variable-temperature direct current conductivity, over a 25–350 °C temperature range, followed an Efros–Shklovskii variable range hopping (ES-VRH) conduction mechanism (ln(ρ) versus T−1/2) at temperatures below 100 °C with a crossover to 2D Mott variable range hopping (M-VRH) (ln(ρ) versus T−1/3) conduction at temperatures above 250 °C. In a transition region between these two limiting behaviors, direct current resistivity exhibited an anomalous temperature-independent plateau. We suggest that its origin may lie in a carrier inversion phenomenon wherein the majority carriers switch from holes to electrons due to Li ion expulsion from the crystalline core and creation of oxygen vacancies generated by loss of oxygen at elevated temperatures. Using a compression technique, porous diodes consisting of n-type (antimony doped SnO2) and the p-type (lithium-doped) nano-particulate films were prepared. Typical current-voltage curves of such devices resembled the behavior of a typical diode but for one key difference; owing to the porosity of the film, areas near the p-n interface and the p- and n-regions are accessible to gaseous analytes. This access is not possible in conventional diodes fabricated through contemporary planar technology. The gas sensing properties of the diodes were investigated by using Cl2, Br2, HCl, NO, NO2, CHCl3, NH3 and H2. Of all the gases tested, the sensor had very good sensitivity to Cl2 and had a response of 80 at 400 ppb of Cl2. The response time of the sensor was ~30 s at room temperature but the recovery time was temperature dependent. At room temperature the recovery time was 80s after 400 ppb chlorine exposure. The sensors were also found to recover quickly (~ 30 s) when the junctions were biased. Reverse biasing the diode provides a controllable band-bending at a p-n junction that could influence the electron-transfer rates from the adsorbates which create intra-band localized states. As a result reverse biasing can provide a means of desorbing the analyzed species. This approach eliminates the requirement to remove adsorbates by elevating the sensor temperature and hence improves on the energy efficiency of these types of sensors. Close

• 2. [Article] Electrical Detection of the Temperature Induced Melting Transition of a DNA Hairpin Covalently Attached to Gold Interdigitated Microelectrodes

  The temperature induced melting transition of a self-complementary DNA strand covalently attached at the 5' end to the surface of a gold interdigitated microelectrode (GIME) was monitored in a novel, label-free, ...

  Citation × Citation Citation Abstract Copy Title: Electrical Detection of the Temperature Induced Melting Transition of a DNA Hairpin Covalently Attached to Gold Interdigitated Microelectrodes Author: Brewood, Greg P., Rangineni, Yaswanth, Fish, Daniel J., Bhandiwad, Ashwini, Evans, David R., Solanki, Raj, Benight, Albert S. Year: 2008 The temperature induced melting transition of a self-complementary DNA strand covalently attached at the 5' end to the surface of a gold interdigitated microelectrode (GIME) was monitored in a novel, label-free, manner. The structural state of the hairpin was assessed by measuring four different electronic properties of the GIME (capacitance, impedance, dissipation factor and phase angle) as a function of temperature from 25 degrees C to 80 degrees C. Consistent changes in all four electronic properties of the GIME were observed over this temperature range, and attributed to the transition of the attached single-stranded DNA (ssDNA) from an intramolecular, folded hairpin structure to a melted ssDNA. The melting curve of the self-complementary single strand was also measured in solution using differential scanning calorimetry (DSC) and UV absorbance spectroscopy. Temperature dependent electronic measurements on the surface and absorbance versus temperature values measured in solution experiments were analyzed assuming a two-state process. The model analysis provided estimates of the thermodynamic transition parameters of the hairpin on the surface. Two-state analyses of optical melting data and DSC measurements provided evaluations of the thermodynamic transition parameters of the hairpin in solution. Comparison of surface and solution measurements provided quantitative evaluation of the effect of the surface on the thermodynamics of the melting transition of the DNA hairpin. Title: Electrical Detection of the Temperature Induced Melting Transition of a DNA Hairpin Covalently Attached to Gold Interdigitated Microelectrodes Author: Brewood, Greg P., Rangineni, Yaswanth, Fish, Daniel J., Bhandiwad, Ashwini, Evans, David R., Solanki, Raj, Benight, Albert S. Year: 2008 The temperature induced melting transition of a self-complementary DNA strand covalently attached at the 5' end to the surface of a gold interdigitated microelectrode (GIME) was monitored in a novel, label-free, manner. The structural state of the hairpin was assessed by measuring four different electronic properties of the GIME (capacitance, impedance, dissipation factor and phase angle) as a function of temperature from 25 degrees C to 80 degrees C. Consistent changes in all four electronic properties of the GIME were observed over this temperature range, and attributed to the transition of the attached single-stranded DNA (ssDNA) from an intramolecular, folded hairpin structure to a melted ssDNA. The melting curve of the self-complementary single strand was also measured in solution using differential scanning calorimetry (DSC) and UV absorbance spectroscopy. Temperature dependent electronic measurements on the surface and absorbance versus temperature values measured in solution experiments were analyzed assuming a two-state process. The model analysis provided estimates of the thermodynamic transition parameters of the hairpin on the surface. Two-state analyses of optical melting data and DSC measurements provided evaluations of the thermodynamic transition parameters of the hairpin in solution. Comparison of surface and solution measurements provided quantitative evaluation of the effect of the surface on the thermodynamics of the melting transition of the DNA hairpin. Close

• 3. [Article] Nanosilver Rainbow: A Rapid and Facile Method to Tune Different Colours of Nanosilver Through the Controlled Synthesis of Stable Spherical Silver Nanoparticles

  A rapid and simple one-pot reaction to synthesize stable, spherically shaped silver nanoparticles (AgNps) of different sizes producing distinct optical properties in aqueous solution at ambient temperature ...

  Citation × Citation Citation Abstract Copy Title: Nanosilver Rainbow: A Rapid and Facile Method to Tune Different Colours of Nanosilver Through the Controlled Synthesis of Stable Spherical Silver Nanoparticles Author: Mendis, Pramujitha, de Silva, Rohini M., Nalin de Silva, K. M., Wijenayaka, Lahiru A., Jayawardana, Kalana, Yan, Mingdi Year: 2016 A rapid and simple one-pot reaction to synthesize stable, spherically shaped silver nanoparticles (AgNps) of different sizes producing distinct optical properties in aqueous solution at ambient temperature has been developed. Each system contains various sizes of silver nanoparticles showing rainbow colours with the peak wavelength of the absorption spectra ranging from 400 to 750 nm. Seven different colours of nano silver were developed through the controlled synthesis of spherical silver nanoparticles using silver nitrate as the metal precursor. Sodium borohydride was used as the main reducing agent and trisodium citrate and hydrazine sulphate were used as the stabilizing and auxiliary reducing agents respectively. The colour of the solution was controlled by varying the concentrations of reagents and the optimum conditions for all the colours are reported. Characterization of silver nanoparticles was carried out using UV-visible spectrophotometry and Transmission Electron Microscopy (TEM). Factors affecting the formation of different sizes of silver nanoparticles, such as silver nitrate concentration, reducing agent concentrations, reaction temperature and reaction pH are also reported. The stability of these coloured silver colloidal solutions was also investigated at different temperatures and the most stable temperature was found to be 4 °C, while the optimum pH to synthesize distinctively coloured silver nanoparticles was found to be in the range of 7–8. The outlined procedure provides a rapid, facile and reproducible synthetic route to spherical AgNps of varying size and ensuing optical properties. Thus, this method is certain to find value in the many applications where size tunability of AgNps is desired. Title: Nanosilver Rainbow: A Rapid and Facile Method to Tune Different Colours of Nanosilver Through the Controlled Synthesis of Stable Spherical Silver Nanoparticles Author: Mendis, Pramujitha, de Silva, Rohini M., Nalin de Silva, K. M., Wijenayaka, Lahiru A., Jayawardana, Kalana, Yan, Mingdi Year: 2016 A rapid and simple one-pot reaction to synthesize stable, spherically shaped silver nanoparticles (AgNps) of different sizes producing distinct optical properties in aqueous solution at ambient temperature has been developed. Each system contains various sizes of silver nanoparticles showing rainbow colours with the peak wavelength of the absorption spectra ranging from 400 to 750 nm. Seven different colours of nano silver were developed through the controlled synthesis of spherical silver nanoparticles using silver nitrate as the metal precursor. Sodium borohydride was used as the main reducing agent and trisodium citrate and hydrazine sulphate were used as the stabilizing and auxiliary reducing agents respectively. The colour of the solution was controlled by varying the concentrations of reagents and the optimum conditions for all the colours are reported. Characterization of silver nanoparticles was carried out using UV-visible spectrophotometry and Transmission Electron Microscopy (TEM). Factors affecting the formation of different sizes of silver nanoparticles, such as silver nitrate concentration, reducing agent concentrations, reaction temperature and reaction pH are also reported. The stability of these coloured silver colloidal solutions was also investigated at different temperatures and the most stable temperature was found to be 4 °C, while the optimum pH to synthesize distinctively coloured silver nanoparticles was found to be in the range of 7–8. The outlined procedure provides a rapid, facile and reproducible synthetic route to spherical AgNps of varying size and ensuing optical properties. Thus, this method is certain to find value in the many applications where size tunability of AgNps is desired. Close

• 4. [Article] Measurement of low vapor pressures : a kinetic approach

  A kinetic model was applied to vapor pressure data obtained by a variable flow method. The vapor pressures of benzoic acid, naphthalene, benzophenone, and phenylhydrazine were measured at temperatures ...

  Citation × Citation Citation Abstract Copy Title: Measurement of low vapor pressures : a kinetic approach Author: Bliden, Samuel Bernard Year: 1984 A kinetic model was applied to vapor pressure data obtained by a variable flow method. The vapor pressures of benzoic acid, naphthalene, benzophenone, and phenylhydrazine were measured at temperatures of 293K to 307K. The data are summarized in the data table on the following page. These data were obtained by passing air over a sample of the substance in a tube. The air stream was combusted, and a flame ionization detector was used to measure the mass of CO2 so obtained. Several different flow rates were used at each temperature with each substance. Title: Measurement of low vapor pressures : a kinetic approach Author: Bliden, Samuel Bernard Year: 1984 A kinetic model was applied to vapor pressure data obtained by a variable flow method. The vapor pressures of benzoic acid, naphthalene, benzophenone, and phenylhydrazine were measured at temperatures of 293K to 307K. The data are summarized in the data table on the following page. These data were obtained by passing air over a sample of the substance in a tube. The air stream was combusted, and a flame ionization detector was used to measure the mass of CO2 so obtained. Several different flow rates were used at each temperature with each substance. Close

• 5. [Article] Study of photolytic interference on HO measurements by LIF-FAGE

  For many years there has been a great interest among the scientific community in the study of the hydroxyl radical, HO. This interest stems from the fundamental role played by this molecule in the photochemistry ...

  Citation × Citation Citation Abstract Copy Title: Study of photolytic interference on HO measurements by LIF-FAGE Author: Martinez, Carmen Ivette Year: 1989 For many years there has been a great interest among the scientific community in the study of the hydroxyl radical, HO. This interest stems from the fundamental role played by this molecule in the photochemistry of the atmosphere, mainly as a cleansing agent of environmental pollutants. Knowing the concentration of the radical would enable scientists to corroborate current atmospheric models and to predict future trends in the atmosphere. Even though there is a great interest in the determination of atmospheric concentrations of this molecule, the task has been very difficult. This is mainly due to the lack of a method sensitive enough to detect concentrations around 106 molecules per cubic centimeter. The most accurate method presently available is the method of laser induced fluorescence using the fluorescence assay with gas expansion technique (LIF-FAGE). This method involves low pressure excitation of HO from its ground state to its lowest electronic excited state and observing the consequent fluorescence around 309 nm. The procedure is done at a pressure of 5 Torr to maximize the fluorescence lifetime of the radical and to minimize the interference of photolytic species. Background determination is achieved by chemical modulation using isobutane in a second channel of the same cell which removes the HO signal. In this study an assessment of the level of ozone interference in LIFF AGE has been done by calculating the relative population distribution of HO among its rotational levels and from this, determining its temperature. When the laser passes through the excitation detection cell it photolyses the ozone present producing in this way the highly reactive 0 1(D). When this molecule reacts with water or with isobutane it produces HO, and this is the source of interference in the actual measurements. In the determination of the relative population distributions of the different HO species, it was found that the naturally occurring HO has a thermal distribution with a temperature of about 300 K. The HO molecules produced from the reaction of 0 1(D) with isobutane also showed a thermal distribution with a temperature of about 230 K. On the other hand, the HO produced from the reaction of 0 1(D) with water did not show a thermal distribution. Two distinct temperatures were observed for this case: one around 200 K for values of K = 1 to 4, and the second one around 3000 K for values of K = 5 to 6. These values agree with previous experimental results for LIF methods by other authors except for the fact that the deviation from the first temperature determined by other authors starts at K = 6 or 7. Title: Study of photolytic interference on HO measurements by LIF-FAGE Author: Martinez, Carmen Ivette Year: 1989 For many years there has been a great interest among the scientific community in the study of the hydroxyl radical, HO. This interest stems from the fundamental role played by this molecule in the photochemistry of the atmosphere, mainly as a cleansing agent of environmental pollutants. Knowing the concentration of the radical would enable scientists to corroborate current atmospheric models and to predict future trends in the atmosphere. Even though there is a great interest in the determination of atmospheric concentrations of this molecule, the task has been very difficult. This is mainly due to the lack of a method sensitive enough to detect concentrations around 106 molecules per cubic centimeter. The most accurate method presently available is the method of laser induced fluorescence using the fluorescence assay with gas expansion technique (LIF-FAGE). This method involves low pressure excitation of HO from its ground state to its lowest electronic excited state and observing the consequent fluorescence around 309 nm. The procedure is done at a pressure of 5 Torr to maximize the fluorescence lifetime of the radical and to minimize the interference of photolytic species. Background determination is achieved by chemical modulation using isobutane in a second channel of the same cell which removes the HO signal. In this study an assessment of the level of ozone interference in LIFF AGE has been done by calculating the relative population distribution of HO among its rotational levels and from this, determining its temperature. When the laser passes through the excitation detection cell it photolyses the ozone present producing in this way the highly reactive 0 1(D). When this molecule reacts with water or with isobutane it produces HO, and this is the source of interference in the actual measurements. In the determination of the relative population distributions of the different HO species, it was found that the naturally occurring HO has a thermal distribution with a temperature of about 300 K. The HO molecules produced from the reaction of 0 1(D) with isobutane also showed a thermal distribution with a temperature of about 230 K. On the other hand, the HO produced from the reaction of 0 1(D) with water did not show a thermal distribution. Two distinct temperatures were observed for this case: one around 200 K for values of K = 1 to 4, and the second one around 3000 K for values of K = 5 to 6. These values agree with previous experimental results for LIF methods by other authors except for the fact that the deviation from the first temperature determined by other authors starts at K = 6 or 7. Close

• 6. [Article] Alumina-catalyzed Cope rearrangement

  The alumina-catalyzed Cope rearrangements of meso- and dl-3,4-diphenylhexa-1,5-diene were examined in detail, following up a preliminary observation by H. Berg at Portland State University. Commercial ...

  Citation × Citation Citation Abstract Copy Title: Alumina-catalyzed Cope rearrangement Author: Wang, Paul Jhy-Shing Year: 1974 The alumina-catalyzed Cope rearrangements of meso- and dl-3,4-diphenylhexa-1,5-diene were examined in detail, following up a preliminary observation by H. Berg at Portland State University. Commercial column-chromatography grade alumina was employed, and was further activated before use.by heating at 650-700° for four hours. Using a ratio of 20 mg of dl-3,4-diphenylhex-l,5-diene to 1 g of alumina in heptane, the Cope rearrangement was complete within 15 minutes at room temperature to give exclusively trans,trans-1,6-diphenylhexa-1,5-diene. This was identified.by melting point, infrared spectroscopy and vapor phase chromatography The catalyzed rearrangement of meso-3,4-diphenylhexa-l,5-diene was run using the same diene to alumina ratio. It was found that 31% of the meso-diene was converted to cis,trans- and trans,trans-l,6-diphenylhexa-1,5-diene at room temperature in four hours. Product iso-merization appeared to take place; the initial ratio of cis,trans-diene to trans,trans-diene was estimated to be 73:27. Another run was carried out at 60°, where the problem of isomerization of cis,trans-diene to trans,trans-diene was more pronounced. The rearrangement gave cis, trans-diene and trans,trans-diene in a ratio of 58:42, as estimated by extrapolation of the product ratio to zero time. Approximately 95% of meso-diene had reacted in one hour at this temperature. The extent of conversion of mes-diene was calculated by quantitative infrared spectroscopy, and the isomeric distribution of products was determined by vapor phase chromatography. The product distribution in the alumina-catalyzed rearrangements parallels that of the thermal Cope rearrangement, where dl-diene gives exclusively trans,trans-diene at 80° with a half-life of eight hours and meso-diene gives 63% cis,trans-diene and 27% trans,trans-diene at 120° with a half-life of 15 hours. Title: Alumina-catalyzed Cope rearrangement Author: Wang, Paul Jhy-Shing Year: 1974 The alumina-catalyzed Cope rearrangements of meso- and dl-3,4-diphenylhexa-1,5-diene were examined in detail, following up a preliminary observation by H. Berg at Portland State University. Commercial column-chromatography grade alumina was employed, and was further activated before use.by heating at 650-700° for four hours. Using a ratio of 20 mg of dl-3,4-diphenylhex-l,5-diene to 1 g of alumina in heptane, the Cope rearrangement was complete within 15 minutes at room temperature to give exclusively trans,trans-1,6-diphenylhexa-1,5-diene. This was identified.by melting point, infrared spectroscopy and vapor phase chromatography The catalyzed rearrangement of meso-3,4-diphenylhexa-l,5-diene was run using the same diene to alumina ratio. It was found that 31% of the meso-diene was converted to cis,trans- and trans,trans-l,6-diphenylhexa-1,5-diene at room temperature in four hours. Product iso-merization appeared to take place; the initial ratio of cis,trans-diene to trans,trans-diene was estimated to be 73:27. Another run was carried out at 60°, where the problem of isomerization of cis,trans-diene to trans,trans-diene was more pronounced. The rearrangement gave cis, trans-diene and trans,trans-diene in a ratio of 58:42, as estimated by extrapolation of the product ratio to zero time. Approximately 95% of meso-diene had reacted in one hour at this temperature. The extent of conversion of mes-diene was calculated by quantitative infrared spectroscopy, and the isomeric distribution of products was determined by vapor phase chromatography. The product distribution in the alumina-catalyzed rearrangements parallels that of the thermal Cope rearrangement, where dl-diene gives exclusively trans,trans-diene at 80° with a half-life of eight hours and meso-diene gives 63% cis,trans-diene and 27% trans,trans-diene at 120° with a half-life of 15 hours. Close

• 7. [Article] Structure and Phase Transitions of the 6, 6-Cyclopropane Isomer of C_ {61} H_ {2}

  We have used x-ray powder diffraction and differential scanning calorimetry to study the crystalline structures and thermal behavior of the 6,6-cyclopropane isomer of C61H2. At room temperature, the C61H2 ...

  Citation × Citation Citation Abstract Copy Title: Structure and Phase Transitions of the 6, 6-Cyclopropane Isomer of C_ {61} H_ {2} Author: Stetzer, M. R., Heiney, Paul A., Stephens, Peter W., Dinnebier, R. E., Zhu, Q., McGhie, Andrew R., Strongin, Robert M., Brandt, B. M., Smith, Amos B., III Year: 2000 We have used x-ray powder diffraction and differential scanning calorimetry to study the crystalline structures and thermal behavior of the 6,6-cyclopropane isomer of C61H2. At room temperature, the C61H2 cyclopropane molecules, like those of the 6,5-annulene isomer and C60O epoxide, are orientationally disordered and crystallize on a face-centered-cubic lattice such that their methylene groups are statistically disordered among the octahedral voids. Unlike 6,5−C61H2 and C60O, the low-temperature structure is not Pa3¯, but rather a low-symmetry orthorhombic lattice in which a≈b Title: Structure and Phase Transitions of the 6, 6-Cyclopropane Isomer of C_ {61} H_ {2} Author: Stetzer, M. R., Heiney, Paul A., Stephens, Peter W., Dinnebier, R. E., Zhu, Q., McGhie, Andrew R., Strongin, Robert M., Brandt, B. M., Smith, Amos B., III Year: 2000 We have used x-ray powder diffraction and differential scanning calorimetry to study the crystalline structures and thermal behavior of the 6,6-cyclopropane isomer of C61H2. At room temperature, the C61H2 cyclopropane molecules, like those of the 6,5-annulene isomer and C60O epoxide, are orientationally disordered and crystallize on a face-centered-cubic lattice such that their methylene groups are statistically disordered among the octahedral voids. Unlike 6,5−C61H2 and C60O, the low-temperature structure is not Pa3¯, but rather a low-symmetry orthorhombic lattice in which a≈b Close

• 8. [Article] An investigation of cadmium and sulfur reactions in dimethylsulfoxide

  The study of the reaction of cadmium and sulfur in dimethylsulfoxide (DMSO) is presented. Specifically, the reaction of dissolved molecular sulfur in DMSO at temperatures greater than 90°C with freshly ...

  Citation × Citation Citation Abstract Copy Title: An investigation of cadmium and sulfur reactions in dimethylsulfoxide Author: Hogle, Howard W. Year: 1982 The study of the reaction of cadmium and sulfur in dimethylsulfoxide (DMSO) is presented. Specifically, the reaction of dissolved molecular sulfur in DMSO at temperatures greater than 90°C with freshly precipitated metallic cadmium is followed by UV-visible spectrometry, atomic absorption spectrometry, and Raman spectrometry. Evidence for the formation of a new cadmium-sulfur species and S3- is discussed. In a second reaction, an equilibrium sodium polysulfide solution in DMSO is titrated with a solution of cadmium ion at room temperature and the reaction progress is followed by means of UV-visible spectrometry. A calculation of the average number of polysulfide charges reacting with each cadmium ion, n̄Q, was made using literature values of the molar absorptivities of the ions S3-, S8- 2, and S6- 2 and Beer's law. Likewise, the average number of sulfur atoms, n̄M, reacting with each cadmium ion was determined. A value of 4.8 polysulfide charges per cadmium ion was determined for n̄Q and a value of 18 sulfur atoms per cadmium ion was determined for n̄M. The significance of the possible formation of cadmium polysulfide complexes is discussed briefly in conjunction with the reaction mechanisms involved in the electrodeposition of CdS from a DMSO solution of CdCl2 and S8. Title: An investigation of cadmium and sulfur reactions in dimethylsulfoxide Author: Hogle, Howard W. Year: 1982 The study of the reaction of cadmium and sulfur in dimethylsulfoxide (DMSO) is presented. Specifically, the reaction of dissolved molecular sulfur in DMSO at temperatures greater than 90°C with freshly precipitated metallic cadmium is followed by UV-visible spectrometry, atomic absorption spectrometry, and Raman spectrometry. Evidence for the formation of a new cadmium-sulfur species and S3- is discussed. In a second reaction, an equilibrium sodium polysulfide solution in DMSO is titrated with a solution of cadmium ion at room temperature and the reaction progress is followed by means of UV-visible spectrometry. A calculation of the average number of polysulfide charges reacting with each cadmium ion, n̄Q, was made using literature values of the molar absorptivities of the ions S3-, S8- 2, and S6- 2 and Beer's law. Likewise, the average number of sulfur atoms, n̄M, reacting with each cadmium ion was determined. A value of 4.8 polysulfide charges per cadmium ion was determined for n̄Q and a value of 18 sulfur atoms per cadmium ion was determined for n̄M. The significance of the possible formation of cadmium polysulfide complexes is discussed briefly in conjunction with the reaction mechanisms involved in the electrodeposition of CdS from a DMSO solution of CdCl2 and S8. Close

• 9. [Article] Studies in transition metal chemistry

  The electronic and vibrational spectra of liquid chromium pentafluoride have been investigated. They were found to be consistent with a d1 system that is extensively fluorine-bridged at room temperature. ...

  Citation × Citation Citation Abstract Copy Title: Studies in transition metal chemistry Author: Brown, Steven David Year: 1975 The electronic and vibrational spectra of liquid chromium pentafluoride have been investigated. They were found to be consistent with a d1 system that is extensively fluorine-bridged at room temperature. The vibrational spectra were not consistent with C4v or D3h monomers. Title: Studies in transition metal chemistry Author: Brown, Steven David Year: 1975 The electronic and vibrational spectra of liquid chromium pentafluoride have been investigated. They were found to be consistent with a d1 system that is extensively fluorine-bridged at room temperature. The vibrational spectra were not consistent with C4v or D3h monomers. Close

• 10. [Article] The Discovery and Development of Metal-Free Arylation Reactions with Unsymmetrical Diaryliodonium Salts

  Functionalizing arenes and heteroarenes has been an active area of research since the 19th century, due to the presence of these molecular structures in many industrially important sectors. A tremendous ...

  Citation × Citation Citation Abstract Copy Title: The Discovery and Development of Metal-Free Arylation Reactions with Unsymmetrical Diaryliodonium Salts Author: Sundalam, Sunil Kumar Year: 2017 Functionalizing arenes and heteroarenes has been an active area of research since the 19th century, due to the presence of these molecular structures in many industrially important sectors. A tremendous amount of research has been published in achieving these chemical transformations using stoichiometric reagents and transition metal-catalyzed reactions. However, challenges still remain. An alternative and comparable methodology to metal-catalyzed reactions to overcome the drawbacks will advance this particular area of research is desirable. Hypervalent iodine compounds offer a promising approach to metal-free arylation reactions. These mild, air and moisture stable compounds have showed significant success as non-toxic and metal-free reagents for the arylation reactions. In particular, unsymmetrical diaryliodonium salts offer functionalization of complex arene structure in an efficient and sustainable pathway. A base-mediated coupling reaction for the metal-free synthesis of alkyl-aryl ethers by using unsymmetrical diaryliodonium salts and aliphatic alcohols is described. This method shows broad substrate scope with respect to both of the coupling partners to produce industrially useful alkyl-aryl ethers in moderate to excellent yields. The reaction is operationally simple, proceeds at mild temperature, and is atom-economical. Sustainability and synthetic utility of this reaction is demonstrated by the use of unsymmetrical aryl(mesityl)iodonium salts as the arylating agents. A limitation of poor reactivity of electron rich unsymmetrical diaryliodonium salts was overcome by designing 2nd generation conditions and using trimethoxy benzene (TMP) as the auxiliary group. Additionally discovery and development of an efficient method to access highly functionalized arynes from unsymmetrical aryl(mesityl)iodonium tosylate salts is presented. The aryne intermediates are generated by ortho C-H deprotonation of aryl(mesityl)iodonium salt with an amide base and subsequently trapped in a cycloaddition reaction with furan in moderate to good yields. Selective iodonium moiety elimination is discussed and the effect of auxiliary and temperature to reduce the regioisomeric ratio is demonstrated. Finally, additional coupling partner including benzyl azide and aliphatic amines are presented to show further utility of this methodology. Also, mechanistic investigations leading to the moderate reactivity of some electron rich unsymmetrical diaryliodonium salts is discussed. Title: The Discovery and Development of Metal-Free Arylation Reactions with Unsymmetrical Diaryliodonium Salts Author: Sundalam, Sunil Kumar Year: 2017 Functionalizing arenes and heteroarenes has been an active area of research since the 19th century, due to the presence of these molecular structures in many industrially important sectors. A tremendous amount of research has been published in achieving these chemical transformations using stoichiometric reagents and transition metal-catalyzed reactions. However, challenges still remain. An alternative and comparable methodology to metal-catalyzed reactions to overcome the drawbacks will advance this particular area of research is desirable. Hypervalent iodine compounds offer a promising approach to metal-free arylation reactions. These mild, air and moisture stable compounds have showed significant success as non-toxic and metal-free reagents for the arylation reactions. In particular, unsymmetrical diaryliodonium salts offer functionalization of complex arene structure in an efficient and sustainable pathway. A base-mediated coupling reaction for the metal-free synthesis of alkyl-aryl ethers by using unsymmetrical diaryliodonium salts and aliphatic alcohols is described. This method shows broad substrate scope with respect to both of the coupling partners to produce industrially useful alkyl-aryl ethers in moderate to excellent yields. The reaction is operationally simple, proceeds at mild temperature, and is atom-economical. Sustainability and synthetic utility of this reaction is demonstrated by the use of unsymmetrical aryl(mesityl)iodonium salts as the arylating agents. A limitation of poor reactivity of electron rich unsymmetrical diaryliodonium salts was overcome by designing 2nd generation conditions and using trimethoxy benzene (TMP) as the auxiliary group. Additionally discovery and development of an efficient method to access highly functionalized arynes from unsymmetrical aryl(mesityl)iodonium tosylate salts is presented. The aryne intermediates are generated by ortho C-H deprotonation of aryl(mesityl)iodonium salt with an amide base and subsequently trapped in a cycloaddition reaction with furan in moderate to good yields. Selective iodonium moiety elimination is discussed and the effect of auxiliary and temperature to reduce the regioisomeric ratio is demonstrated. Finally, additional coupling partner including benzyl azide and aliphatic amines are presented to show further utility of this methodology. Also, mechanistic investigations leading to the moderate reactivity of some electron rich unsymmetrical diaryliodonium salts is discussed. Close