Search

In this work, a two-step hydrothermal/solvothermal process was developed to generate highly fluorescent lawsone polymer dots (LPDs) utilizing an inexpensive and abundant starting material, 2-hydroxy-1,4-napththoquinone (lawsone). This hydrothermal/solvothermal process produces LPDs that have excitation independent emission with well-defined electronic transitions. This two-step protocol provides a straightforward approach to remove unwanted small molecular fluorescence, which has plagued carbon dot systems, without the need for advanced chromatographic purification methods or steps. A series of spectroscopic, electrochemical, and theoretical experiments suggest that this process proceeds via a sequential dehydration and dehydrogenation pathway to cross-link the lawsone into a carbon dot structure. This polymerization process helps to stabilize and favor certain electronic transitions inherently present in the lawsone monomer. The generation of the LPDs results in a 2 order of magnitude increase in the emission intensity and a quantum yield of 37%. This behavior is likely the result of the cross-linked structure shielding these electronic states from deactivation caused by nonradiative processes such as vibrational coupling and excited state quenching from thermal deactivation and solvent collisions. This finding is consistent with a cross-linked enhanced emission (CEE) mechanism, as previously observed for other similar systems. The LPDs were then incorporated into a TiO2 photoanode and utilized as a photosensitizer in a dye-sensitized solar cell (DSSC) which showed an enhancement in photocurrent density over pure TiO2. We also prepared a derivative of the LPDs utilizing a diethylene triamine additive (nitrogen-doped lawsone polymer dots (N-LPDs)) using the same two-step protocol and demonstrated its potential as a fluorescence microscopy dye for imaging MDA-MB-231 cancer cells. [ABSTRACT FROM AUTHOR]

The adsorption and UV photochemistry of 1,3-butadiene on highly oriented pyrolytic graphite [HOPG (0001)] is studied using temperature-programmed desorption (TPD) and electron energy loss spectroscopy (EELS). The temperature-programmed desorption suggests that butadiene is physisorbed on the HOBG surface with a monolayer desorption energy.

Electron energy loss spectroscopy, temperature-programmed desorption and X-ray photoelectron spectroscopy were used to investigate the adsorption and polymerization of formaldehyde on Cu(100).

The adsorption and photochemistry of CD3I adsorbed on TiO2(110) at ∼110 K has been studied by means of temperature programmed desorption (TPD) and x-ray photoelectron spectroscopy (XPS). Complex desorption behavior is observed in TPD suggesting the presence of several distinct coverage regimes. At submonolayer coverages there are two coexisting phases: one dominated by adsorbate–adsorbate interaction, the other dominated by adsorbate–substrate interactions. The first completed monolayer corresponds to (3.8±0.3)×1014 molecules cm-2 and shows only one desorption peak, although this is broad and extends asymmetrically to high temperature indicative of a changing desorption activation energy. With increasing coverage, a discrete, less tightly bound second layer is formed which slowly rearranges to produce three-dimensional clusters of methyl iodide, as indicated by a sharp reduction in the I (3d5/2)/Ti(2p) XPS intensity ratio. There is evidence that this rearrangement does not involve the first monolayer. Irradiation of 1 ML CD3I by 254 or 334 nm photons causes cleavage of the C–I bond and expulsion of I and C containing species into the vacuum. There is retention of ∼20% of the initial I atoms after irradiation at 254 nm. The photodissociation cross section, σ, of adsorbed CD3 I on TiO2(110) at 254 and 334 nm is calculated to be ∼1.1×10-18 cm2 and ∼1.3 ×10-20 cm2, respectively. At 254 nm, the adsorbate and gas phase σ are similar suggesting photodissociation is dominated by adsorbate excitation, but at 334 nm the adsorbate photodissociation cross section is almost an order of magnitude larger than its gas phase counterpart. This suggests that a second photoexcitation mechanism may be contributing to adsorbate photodissociation, possibly involving photogenerated substrate carriers. [ABSTRACT FROM AUTHOR]

The ultraviolet photodissociation and photodesorption of CD3I adsorbed on the TiO2(110) surface at ∼100 K has been investigated at 257, 275, 302, and 351 nm using modulated continuous-wave laser irradiation followed by resonantly enhanced multiphoton ionization of fragments expelled from the adsorbate layer. Photodissociation at these wavelengths produces CD3 radicals. Nonthermal photodesorption also contributes to removal of CD3I from the adsorbate layer, becoming a major mechanism at 351 nm. Similar processes are observed at both 1 and 25 monolayer (ML) coverages. The cross section for CD3I depletion from the monolayer is qualitatively similar to the gas phase CD3I absorption profile, decreasing by ∼3 orders of magnitude between 257 and 351 nm. Depletion cross sections, S(λ), for CD3I are 3±2×10-18 cm-2, 8±3×10-19 cm-2, 1±0.5×10-19 cm-2, and 3±1×10-21 cm-2 for 257, 275, 302, and 351 nm irradiation, respectively. The depletion cross section for 25 ML CD3I coverage is approximately an order of magnitude less than for 1 ML coverage with S(λ) calculated to be 3±2×10-19 cm-2, 1.5±0.7×10-19 cm-2, 1.5±0.7×10-20 cm-2, and 2±0.8×10-22 cm-2 for 257, 275, 302, and 351 nm radiation, respectively. We find no correlation between substrate absorption and the wavelength dependence of photodissociation or photodesorption suggesting that direct excitation of the adsorbate molecule is the dominant dissociation mechanism. The lack of substrate involvement may be due to poor coupling of the CD3I adsorbate and TiO2 substrate electronic structures. [ABSTRACT FROM AUTHOR]

The study was conducted to find whether the photochemistry of CF2Br2 is altered when it is adsorbed on a model carbonaceous aerosol surface. This implies that dissociative electron attachment does not significantly contribute to the adsorbate photochemistry.

The core level and valence band X-ray photoelectron spectra (XP spectra) of two arsenic sulfides, As4S4 (α-realgar) and As4S4 (pararealgar), are reported. Pararealgar is a polymorph of realgar created by irradiation of realgar with visible light. The core level spectra of the materials can be distinguished by small differences in core level binding energies (BEs). For example, the As 3d5/2 and S 2p3/2 peaks are at 43.1 and 162.8 eV BE, respectively, in realgar and 43.2 and 162.7 eV BE, respectively, in pararealgar.Density functional theory (DFT) calculations at the B3LYP/cc-pVDZ level were performed on single As4S4 clusters to determine the ground state orbital energies for realgar and pararealgar and electrostatic potential-derived atomic charges. The shifts in the core level BEs are qualitatively reproduced in the orbital energies and can be rationalized based on an increased average charge in pararealgar (S=−0.21, As=+0.21) versus realgar (S=−0.19, As=+0.19). A large variation in calculated charge between inequivalent As sites in pararealgar (from +0.09 to +0.31) broadens the observed arsenic XP spectra features. In addition, the four main features in the valence bands of these materials have been identified based on the DFT calculations. [Copyright &y& Elsevier]

Aims: The aim of this study was to define the levels of noise exposure for the surgeon, assistant, scrub nurse, and anesthetist during total hip and knee arthroplasty surgery. In addition, we sought to determine whether the noise exposure during these procedures reaches or exceeds the action values set out by the U.K. Noise at Work Regulations (2005)., Materials and Methods: Individual noise exposure during arthroplasty hip and knee surgery was recorded using a personal noise Dosemeter System model 22 (DM22) (Pulsar instruments, Filey, U.K.). Recordings were taken in real-time during five separate theater sessions. Each theater session included two arthroplasty procedures and lasted approximately 4 hrs. Personal noise exposure was expressed in terms of peak sound pressure and an average noise exposure over an 8-hour time-period to reflect the noise experienced by the ear over a working day., Results: In all three sessions involving total hip replacement surgery, the peak sound pressure, for the operating surgeon exceeded the exposure action values set out by the U.K. Noise at Work Regulations. Theater sessions involving total knee replacement surgery did not exceed any exposure action values for LCPeak or LEPd., Conclusion: Arthroplasty surgery is a working environment with significant noise exposure. We recommend any surgeon or theater member who is concerned about the noise generated in their theater to have noise levels formally assessed using appropriately positioned recording devices., (Copyright © 2020 Elsevier Inc. All rights reserved.)

It has been suggested that revision of the femoral component of hip resurfacing after femoral failure would be straightforward and have an outcome comparable to primary total hip arthroplasty (THA). We have compared the outcome of femoral side-only revision resurfacings to the results of primary modular large-bearing metal-on-metal THA. Fourteen consecutive patients underwent revision surgery of the failed femoral component, to a cemented tapered stem (CPT, Zimmer, Warsaw, Indiana) with a large modular metal head (Smith and Nephew Orthopaedics Ltd, Memphis, Tennessee, or Adept, Finsbury Orthopaedics, Surrey, England). The acetabular component was found to be well fixed, well orientated, and was left in situ. The 14 matched patients in the primary THA group received the same components. At a mean follow-up of 49 months (range, 30-60 months), clinical outcome measured using the Oxford and Harris Hip Scores showed no significant difference (P = .11, P = .45, respectively). Operative time and blood loss were comparable for both groups. We conclude that revision of the failed femoral resurfacing component gives excellent results., (Copyright © 2011 Elsevier Inc. All rights reserved.)

Background: Hodgkin's disease (HD) most commonly presents with progressive painless enlargement of peripheral lymph nodes, especially around the cervical region. A few children have systemic symptoms and weight loss. At the time of diagnosis, osseous involvement is uncommon, Case Presentation: A case is described of Primary Multifocal Osseous Hodgkin's Lymphoma in a seven-year-old boy. He presented with a painful swelling in the sternum, and further investigations revealed deposits in his L1 vertebra, the left sacro-iliac joint and the right acetabulum., Conclusion: The clinical, radiological and histological features of this disease can mimic other medical conditions, including Tuberculosis, making the diagnosis difficult and often leading to delays in treatment. This is a very rare condition and we believe this to be the youngest reported case in the literature.