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Sample records for diamondoid thiols attached

  1. Near-Edge X-ray Absorption Fine Structure Spectroscopy of Diamondoid Thiol Monolayers on Gold

    SciTech Connect

    Willey, T M; Fabbri, J; Lee, J I; Schreiner, P; Fokin, A A; Tkachenko, B A; Fokina, N A; Dahl, J; Carlson, B; Vance, A L; Yang, W; Terminello, L J; van Buuren, T; Melosh, N

    2007-11-27

    Diamondoids, hydrocarbon molecules with cubic-diamond-cage structures, have unique properties with potential value for nanotechnology. The availability and ability to selectively functionalize this special class of nanodiamond materials opens new possibilities for surface-modification, for high-efficiency field emitters in molecular electronics, as seed crystals for diamond growth, or as robust mechanical coatings. The properties of self-assembled monolayers (SAMs) of diamondoids are thus of fundamental interest for a variety of emerging applications. This paper presents the effects of thiol substitution position and polymantane order on diamondoid SAMs on gold using near-edge X-ray absorption fine structure spectroscopy (NEXAFS) and X-ray photoelectron spectroscopy (XPS). A framework to determine both molecular tilt and twist through NEXAFS is presented and reveals highly ordered diamondoid SAMs, with the molecular orientation controlled by the thiol location. C 1s and S 2p binding energies are lower in adamantane thiol than alkane thiols on gold by 0.67 {+-} 0.05 eV and 0.16 {+-} 0.04 eV respectively. These binding energies vary with diamondoid monolayer structure and thiol substitution position, consistent with different amounts of steric strain and electronic interaction with the substrate. This work demonstrates control over the assembly, in particular the orientational and electronic structure, providing a flexible design of surface properties with this exciting new class of diamond clusters.

  2. Covalent attachment of diamondoid phosphonic acid dichlorides to tungsten oxide surfaces.

    PubMed

    Li, Fei Hua; Fabbri, Jason D; Yurchenko, Raisa I; Mileshkin, Alexander N; Hohman, J Nathan; Yan, Hao; Yuan, Hongyuan; Tran, Ich C; Willey, Trevor M; Bagge-Hansen, Michael; Dahl, Jeremy E P; Carlson, Robert M K; Fokin, Andrey A; Schreiner, Peter R; Shen, Zhi-Xun; Melosh, Nicolas A

    2013-08-06

    Diamondoids (nanometer-sized diamond-like hydrocarbons) are a novel class of carbon nanomaterials that exhibit negative electron affinity (NEA) and strong electron-phonon scattering. Surface-bound diamondoid monolayers exhibit monochromatic photoemission, a unique property that makes them ideal electron sources for electron-beam lithography and high-resolution electron microscopy. However, these applications are limited by the stability of the chemical bonding of diamondoids on surfaces. Here we demonstrate the stable covalent attachment of diamantane phosphonic dichloride on tungsten/tungsten oxide surfaces. X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared (FTIR) spectroscopy revealed that diamondoid-functionalized tungsten oxide films were stable up to 300-350 °C, a substantial improvement over conventional diamondoid thiolate monolayers on gold, which dissociate at 100-200 °C. Extreme ultraviolet (EUV) light stimulated photoemission from these diamondoid phosphonate monolayers exhibited a characteristic monochromatic NEA peak with 0.2 eV full width at half-maximum (fwhm) at room temperature, showing that the unique monochromatization property of diamondoids remained intact after attachment. Our results demonstrate that phosphonic dichloride functionality is a promising approach for forming stable diamondoid monolayers for elevated temperature and high-current applications such as electron emission and coatings in micro/nano electromechanical systems (MEMS/NEMS).

  3. Tunnel magnetoresistance of diamondoids

    NASA Astrophysics Data System (ADS)

    Matsuura, Yukihito

    2016-10-01

    Tunnel magnetoresistance (TMR) of diamondoids has been predicted by first principles density functional theory. Diamantane was used as a basic molecular proxy for diamondoids because hydrogen atoms in the apical position are easily substituted for a thiol group. The pristine diamantane exhibited a low TMR ratio of 7%, and boron-substitution considerably decreased the TMR ratio. Conversely, nitrogen-substitution enhanced the TMR ratio by up to 20%. Heteroatom-substitution changes the tunneling probabilities by varying the molecular bond lengths. Furthermore, when the spins of the electrodes are parallel, the heteroatoms resulted in transmittance probabilities at an energy range near the Fermi level. Consequently, heteroatom-substitution can control the TMR ratios of diamondoids very well.

  4. Investigation of diamondoid and functionalized diamondoid molecules under extreme conditions

    NASA Astrophysics Data System (ADS)

    Yang, F.; Lin, Y.; Mao, W. L.

    2013-12-01

    As the fourth most abundant element in the universe and an important energy carrier, carbon based materials have long been of considerable interests in research. Diamondoids are cage-like, ultra-stable, saturated hydrocarbons, with carbon-carbon frameworks superimposed on the diamond lattice and originally found in petroleum. The exceptional electron photoemission from thin film of diamondoids has excited interests in using these unique materials as functional elements to regulate energy flow at the nanoscale. Selective chemical functionalization further changes the electronic properties of the system and brings many more possible applications. Pressure (P), together with temperature (T), could lead to formation of novel phases of pure diamondoids and provide alternative routes for potentially synthesizing higher diamondoids. In addition, the electronic properties of functionalized diamondoids may also be enhanced with P. We have compressed pure diamondoids: the [121] tetramantane up to 20 GPa and observed a phase transition at high pressure from powder x-ray diffraction (XRD). This phase transition took place at approximately 13 GPa and completed within a short pressure range. Meanwhile, we observed only continuous changes in the CCC bending and CC stretching regions from Raman spectroscopy, suggesting that the carbon framework of the diamondoid molecules remains intact with pressure. The phase transition observed in XRD is probably due to the molecular packing rearrangement. We also discovered interesting pressure-induced electronic properties changes in newly synthesized functionalized diamondoids, particularly the Ag-adamantane-thiol, from Raman spectroscopy. First, there is an abrupt emergence of photoluminescence with ~700 nm peak emission when the crystals are compressed to 2-3 GPa, suggesting an indirect to direct band gap transition. Second, the phonon modes in the Raman spectra begin to diminish, accompanied by an increase of the baseline slope, when the

  5. Monochromatic electron photoemission from diamondoid monolayers

    SciTech Connect

    Yang, Wanli; Yang, Wanli L.; Fabbri, J.D.; Willey, T.M.; Lee, J.R.I.; Dahl, J.E.; Carlson, R.M.K.; Schreiner, P.R.; Fokin, A.A.; Tkachenko, B.A.; Fokina, N.A.; Meevasana, W.; Mannella, N.; Tanaka, K.; Zhou, X.J.; van Buuren, T.; Kelly, M.A.; Hussain, Z.; Melosh, N.A.; Shen, Z.-X.

    2007-02-27

    We found monochromatic electron photoemission from large-area self-assembled monolayers of a functionalized diamondoid, [121]tetramantane-6-thiol. Photoelectron spectra of the diamondoid monolayers exhibited a peak at the low-kinetic energy threshold; up to 68percent of all emitted electrons were emitted within this single energy peak. The intensity of the emission peak is indicative of diamondoids being negative electron affinity materials. With an energy distribution width of less than 0.5 electron volts, this source of monochromatic electrons may find application in technologies such as electron microscopy, electron beam lithography, and field-emission flatpanel displays.

  6. Monochromatic Electron Photoemission from DiamondoidMonolayers

    SciTech Connect

    Yang, W.L.

    2010-04-15

    We found monochromatic electron photoemission from large-area self-assembled monolayers of a functionalized diamondoid, [121]tetramantane-6-thiol. Photoelectron spectra of the diamondoid monolayers exhibited a peak at the low-kinetic energy threshold; up to 68% of all emitted electrons were emitted within this single energy peak. The intensity of the emission peak is indicative of diamondoids being negative electron affinity materials. With an energy distribution width of less than 0.5 electron volts, this source of monochromatic electrons may find application in technologies such as electron microscopy, electron beam lithography, and field-emission flat-panel displays.

  7. Diamondoid monolayers as electron emitters

    DOEpatents

    Yang, Wanli; Fabbri, Jason D.; Melosh, Nicholas A.; Hussain, Zahid; Shen, Zhi-Xun

    2013-10-29

    Provided are electron emitters based upon diamondoid monolayers, preferably self-assembled higher diamondoid monolayers. High intensity electron emission has been demonstrated employing such diamondoid monolayers, particularly when the monolayers are comprised of higher diamondoids. The application of such diamondoid monolayers can alter the band structure of substrates, as well as emit monochromatic electrons, and the high intensity electron emissions can also greatly improve the efficiency of field-effect electron emitters as applied to industrial and commercial applications.

  8. Diamondoid monolayers as electron emitters

    DOEpatents

    Yang, Wanli [El Cerrito, CA; Fabbri, Jason D [San Francisco, CA; Melosh, Nicholas A [Menlo Park, CA; Hussain, Zahid [Orinda, CA; Shen, Zhi-Xun [Stanford, CA

    2012-04-10

    Provided are electron emitters based upon diamondoid monolayers, preferably self-assembled higher diamondoid monolayers. High intensity electron emission has been demonstrated employing such diamondoid monolayers, particularly when the monolayers are comprised of higher diamondoids. The application of such diamondoid monolayers can alter the band structure of substrates, as well as emit monochromatic electrons, and the high intensity electron emissions can also greatly improve the efficiency of field-effect electron emitters as applied to industrial and commercial applications.

  9. Oriented attachment kinetics for ligand capped nanocrystals: coarsening of thiol-PbS nanoparticles.

    PubMed

    Zhang, Jing; Wang, Yonghao; Zheng, Jinsheng; Huang, Feng; Chen, Dagui; Lan, Youzhao; Ren, Guoqiang; Lin, Zhang; Wang, Chen

    2007-02-15

    In this work, the growth kinetics of thiol-capped PbS nanoparticles was studied. Two-stage growth process was observed, which was controlled first by oriented attachment (OA) mechanism and then by the hybrid Ostwald ripening (OR) and OA mechanism. Different from the NaOH-ZnS system, where OA will occur between any two multilevel nanoparticles, an OA kinetic model only considering the attachment related to original particles was fitted well with the experimental results. Analysis reveals that this model may be a universal one to describe the OA crystal growth process of nanocrystals capped with easily destroyed ligands, such as thiol-ZnS in the previous report. The OA crystal growth characteristics determined by the surface agent were discussed and compared. We propose that with stronger surface capping, the OR growth of nanocrystals is hindered, which facilitates the size controlling via OA kinetics during nanosynthesis.

  10. Diamondoid-based molecular junctions: a computational study

    NASA Astrophysics Data System (ADS)

    Adhikari, Bibek; Sivaraman, Ganesh; Fyta, Maria

    2016-12-01

    In this work, we deal with the computational investigation of diamondoid-based molecular conductance junctions and their electronic transport properties. A small diamondoid is placed between the two gold electrodes of the nanogap and is covalently bonded to the gold electrodes through two different molecules, a thiol group and a N-heterocyclic carbene molecule. We have shown that the thiol linker is more efficient as it introduces additional electron paths for transport at lower energies. The influence of doping the diamondoid on the properties of the molecular junctions has been investigated. We find that using a nitrogen atom to dope the diamondoids leads to a considerable increase of the zero bias conductance. For the N-doped system we show an asymmetric feature of the I-V curve of the junctions resulting in rectification within a very small range of bias voltages. The rectifying nature is the result of the characteristic shift in the bias-dependent highest occupied molecular orbital state. In all cases, the efficiency of the device is manifested and is discussed in view of novel nanotechnological applications.

  11. Photoluminescence of Diamondoid Crystals

    SciTech Connect

    Clay, William; Sasagawa, Takao; Iwasa, Akio; Liu, Zhi; Dahl, Jeremy E.; Carlson, Robert M.K.; Kelly, Michael; Melos, Nicholas; Shen, Zhi-Xun; /Stanford U., Phys. Dept. /Stanford U., Appl. Phys. Dept. /Stanford U., Geballe Lab. /SIMES, Stanford

    2012-04-03

    The photoluminescence of diamondoids in the solid state is examined. All of the diamondoids are found to photoluminesce readily with initial excitation wavelengths ranging from 233 nm to 240 nm (5.3 eV). These excitation energies are more than 1 eV lower than any previously studied saturated hydrocarbon material. The emission is found to be heavily shifted from the absorption, with emission wavelengths of roughly 295 nm (4.2 eV) in all cases. In the dissolved state, however, no uorescence is observed for excitation wavelengths as short as 200 nm. We also discuss predictions and measurements of the quantum yield. Our predictions indicate that the maximum yield may be as high as 25%. Our measurement of one species, diamantane, gives a yield of 11%, the highest ever reported for a saturated hydrocarbon, even though it was likely not at the optimal excitation wavelength.

  12. Ultralow effective work function surfaces using diamondoid monolayers

    NASA Astrophysics Data System (ADS)

    Narasimha, Karthik Thimmavajjula; Ge, Chenhao; Fabbri, Jason D.; Clay, William; Tkachenko, Boryslav A.; Fokin, Andrey A.; Schreiner, Peter R.; Dahl, Jeremy E.; Carlson, Robert M. K.; Shen, Z. X.; Melosh, Nicholas A.

    2016-03-01

    Electron emission is critical for a host of modern fabrication and analysis applications including mass spectrometry, electron imaging and nanopatterning. Here, we report that monolayers of diamondoids effectively confer dramatically enhanced field emission properties to metal surfaces. We attribute the improved emission to a significant reduction of the work function rather than a geometric enhancement. This effect depends on the particular diamondoid isomer, with [121]tetramantane-2-thiol reducing gold's work function from ∼5.1 eV to 1.60 ± 0.3 eV, corresponding to an increase in current by a factor of over 13,000. This reduction in work function is the largest reported for any organic species and also the largest for any air-stable compound. This effect was not observed for sp3-hybridized alkanes, nor for smaller diamondoid molecules. The magnitude of the enhancement, molecule specificity and elimination of gold metal rearrangement precludes geometric factors as the dominant contribution. Instead, we attribute this effect to the stable radical cation of diamondoids. Our computed enhancement due to a positively charged radical cation was in agreement with the measured work functions to within ±0.3 eV, suggesting a new paradigm for low-work-function coatings based on the design of nanoparticles with stable radical cations.

  13. Making Silicone Rubber Highly Resistant to Bacterial Attachment Using Thiol-ene Grafting

    PubMed Central

    2016-01-01

    Biomedical devices are indispensable in modern medicine yet offer surfaces that promote bacterial attachment and biofilm formation, resulting in acute and chronic healthcare-associated infections. We have developed a simple method to graft acrylates to silicone rubber, polydimethylsiloxane (PDMS), a commonly used device material that is often colonized by bacteria. We demonstrate a novel method whereby nontoxic bacteria attachment-resistant polymers can be readily grafted from and grafted to the surface using thiol-ene chemistry, substantially reducing bacterial colonization. With use of this approach, bacterial biofilm coverage can be reduced by 99% compared with standard PDMS in an in vitro assay. This grafting approach offers significant advantages over commonly used physisorbed coatings, especially in areas of high shear or mechanical stress. Furthermore, the approach is versatile such that the grafted material properties can be tailored for the desired final application. PMID:27775316

  14. The fate of diamondoids in coals and sedimentary rocks

    SciTech Connect

    Wei, Z.; Moldowan, J.M.; Jarvie, D.M.; Hill, R.

    2006-12-15

    Diamondoids were detected in the extracts of a series of coals and rocks varying in maturity, lithology, source input, and depositional environment. At the same maturity level, diamondoids are generally about a magnitude more abundant in source rocks than in coals. The concentrations of diamondoids are maturity dependent. However, while diamondoids become more abundant with the increasing thermal maturity, a diminution in diamondoid concentrations is observed at the maturity value of about R{sub o} = 4.0% in both coals and rocks. The occurrence of diamantane destruction at 550{sup o}C during pyrolysis suggests that diamondoids may be eventually destroyed at high temperatures in the Earth. Here we propose three main phases of diamondoid life in nature: diamondoid generation (phase I, R{sub o} < 1.1%), diamondoid generation and enrichment (phase II, 1.1% {le} R{sub o} {le}4.0%), and diamondoid destruction (phase III, R{sub o} > 4.0%).

  15. The fate of diamondoids in coals and sedimentary rocks

    USGS Publications Warehouse

    Wei, Z.; Moldowan, J.M.; Jarvie, D.M.; Hill, R.

    2006-01-01

    Diamondoids were detected in the extracts of a series of coals and rocks varying in maturity, lithology, source input, and depositional environment. At the same maturity level, diamondoids are generally about a magnitude more abundant in source rocks than in coals. The concentrations of diamondoids are maturity dependent. However, while diamondoids become more abundant with the increasing thermal maturity, a diminution in diamondoid concentrations is observed at the maturity value of about Ro = 4.0% in both coals and rocks. The occurrence of diamantane destruction at 550 ??C during pyrolysis suggests that diamondoids may be eventually destroyed at high temperatures in the Earth. Here we propose three main phases of diamondoid life in nature: diamondoid generation (phase I, Ro 4.0%). ?? 2006 Geological Society of America.

  16. Chemically modified diamondoids as biosensors for DNA

    NASA Astrophysics Data System (ADS)

    Sivaraman, Ganesh; Fyta, Maria

    2014-03-01

    Understanding the interaction of biological molecules with materials is essential in view of the novel potential applications arising when these two are combined. To this end, we investigate the interaction of DNA with diamondoids, a broad family of tiny hydrogen-terminated diamond clusters with high technological potential. We model this interaction through quantum-mechanical computer simulations and focus on the hydrogen bonding possibilities of the different DNA nucleobases to the lower amine-modified diamondoids with respect to their relative distance and orientation. Our aim is to promote the binding between these two units, and probe this through the association energy, the electronic structure of the nucleobase-diamondoid system, and the specific role of their frontier orbitals. We discuss the relevance of our results in view of biosensing applications and specifically nanopore sequencing of DNA.

  17. Attachment site cysteine thiol pKa is a key driver for site-dependent stability of THIOMAB(TM) antibody-drug conjugates.

    PubMed

    Vollmar, Breanna S; Wei, Binqing; Ohri, Rachana; Zhou, Jianhui; He, Jintang; Yu, Shang-Fan; Leipold, Douglas; Cosino, Ely; Yee, Sharon; Fourie-O'Donohue, Aimee; Li, Guangmin; Lewis Phillips, Gail D; Kozak, Katherine Ruth; Kamath, Amrita; Xu, Keyang; Lee, Genee; Lazar, Greg A; Erickson, Hans K

    2017-09-08

    Incorporation of cysteines into antibodies by mutagenesis allows for the direct conjugation of small molecules to specific sites on the antibody via disulfide bonds. The stability of the disulfide bond linkage between the small molecule and the antibody is highly dependent on the location of the engineered cysteine in either the heavy chain (HC) or light chain (LC) of the antibody. Here, we explore the basis for this site-dependent stability. We evaluated the in vivo efficacy and pharmacokinetics of five different cysteine mutants of trastuzumab conjugated to a pyrrolobenzodiazepine (PBD) via disulfide bonds. A significant correlation was observed between disulfide stability and efficacy for the conjugates. We hypothesized that the observed site-dependent stability of the disulfide-linked conjugates could be due to differences in the attachment site cysteine thiol pKa. We measured the cysteine thiol pKa using isothermal titration calorimetry (ITC) and found that the variants with the highest thiol pKa (LC K149C and HC A140C) were found to yield the conjugates with the greatest in vivo stability. Guided by homology modeling, we identified several mutations adjacent to LC K149C which reduced the cysteine thiol pKa and thus decreased the in vivo stability of the disulfide-linked PBD conjugated to LC K149C. We also present results suggesting that the high thiol pKa of LC K149C is responsible for the sustained circulation stability of LC K149C TDCs utilizing a maleimide-based linker. Taken together, our results provide evidence that the site-dependent stability of cys-engineered antibody-drug conjugates may be explained by interactions between the engineered cysteine and the local protein environment that serve to modulate the side chain thiol pKa. The influence of cysteine thiol pKa on stability & efficacy offers a new parameter for the optimization of ADCs that utilize cysteine-engineering.

  18. Enhanced oscillatory rectification and negative differential resistance in pentamantane diamondoid-cumulene systems

    NASA Astrophysics Data System (ADS)

    Tawfik, Sherif Abdulkader; Cui, X. Y.; Ringer, S. P.; Stampfl, C.

    2016-02-01

    We propose a new functionality for diamondoids in nanoelectronics. Based on the nonequilibrium Green's function formalism and density functional theory, we reveal that when attached to gold electrodes, the pentamantane-cumulene molecular junction exhibits large and oscillatory rectification and negative differential resistance (NDR) - depending on the number of carbon atoms in cumulene (Cn). When n is odd rectification is greatly enhanced where the rectification ratio can reach ~180 and a large negative differential resistance peak current of ~3 μA. This oscillatory behavior is well rationalised in terms of the occupancy of the carbon 2p states in Cn. Interestingly, different layers of C atoms in the pentamantane molecule have different contributions to transmission. The first and third layers of C atoms in pentamantane have a slight contribution to rectification, and the fifth and sixth layers have a stronger contribution to both rectification and NDR. Thus, our results suggest potential avenues for controlling their functions by chemically manipulating various parts of the diamondoid molecule, thus extending the applications of diamondoids in nanoscale integrated circuits.

  19. Ordered phases of encapsulated diamondoids into carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Legoas, S. B.; dos Santos, R. P. B.; Troche, K. S.; Coluci, V. R.; Galvão, D. S.

    2011-08-01

    Diamondoids are hydrogen-terminated nanosized diamond fragments that are present in petroleum crude oil at low concentrations. These fragments are found as oligomers of the smallest diamondoid, adamantane (C10H16). Due to their small size, diamondoids can be encapsulated into carbon nanotubes to form linear arrangements. We have investigated the encapsulation of diamondoids into single walled carbon nanotubes with diameters between 1.0 and 2.2 nm using fully atomistic simulations. We performed classical molecular dynamics and energy minimizations calculations to determine the most stable configurations. We observed molecular ordered phases (e.g. double, triple, 4- and 5-stranded helices) for the encapsulation of adamantane, diamantane, and dihydroxy diamantane. Our results also indicate that the functionalization of diamantane with hydroxyl groups can lead to an improvement on the molecular packing factor when compared to non-functionalized compounds. Comparisons to hard-sphere models revealed differences, especially when more asymmetrical diamondoids were considered. For larger diamondoids (i.e., adamantane tetramers), we have not observed long-range ordering but only a tendency to form incomplete helical structures. Our calculations predict that thermally stable (at least up to room temperature) complex ordered phases of diamondoids can be formed through encapsulation into carbon nanotubes.

  20. Diamonds are a chemist's best friend: diamondoid chemistry beyond adamantane.

    PubMed

    Schwertfeger, Hartmut; Fokin, Andrey A; Schreiner, Peter R

    2008-01-01

    Marilyn Monroe knew that "diamonds are a girl's best friend" but, in the meantime, many chemists have realized that they are also extremely attractive objects in contemporary chemistry. The chemist's diamonds are usually quite small (herein: nanometer-sized "diamondoids") and as a result of their unique structure are unusual chemical building blocks. Since lower diamondoids (up to triamantane) have recently become available in large amounts from petroleum and higher diamondoids (starting from tetramantane) are now also accessible from crude oil new research involving them has begun to emerge. Having well-defined structures makes these cage compounds so special compared to other nanometer-scale diamonds. Selective and high-yielding synthetic approaches to the functionalization of diamondoids gives derivatives that can find applications in, for example, polymers, coating materials, drugs, and molecular electronics.

  1. Building of an immunosensor: how can the composition and structure of the thiol attachment layer affect the immunosensor efficiency?

    PubMed

    Briand, Elisabeth; Salmain, Michèle; Herry, Jean-Marie; Perrot, Hubert; Compère, Chantal; Pradier, Claire-Marie

    2006-09-15

    Immunosensors, based on the immobilization of a model rabbit antibody on mixed self-assembled monolayers and Protein A as a linking agent on gold transducers, were elaborated and characterized at each step by modulated polarization-infrared spectroscopy (PM-IRRAS) and occasionally by atomic force microscopy (AFM) and quartz crystal microbalance (QCM). By testing two different mixed SAMs comprising 11-mercaptoundecanoic acid (MUA), together with either decanethiol (C9CH3) or mercaptohexanol (C6OH), the role of the chemical composition and structure of the antibody attachment layer upon the sensor performance was demonstrated.

  2. Laser-induced fluorescence of free diamondoid molecules.

    PubMed

    Richter, Robert; Röhr, Merle I S; Zimmermann, Tobias; Petersen, Jens; Heidrich, Christoph; Rahner, Ramon; Möller, Thomas; Dahl, Jeremy E; Carlson, Robert M K; Mitric, Roland; Rander, Torbjörn; Merli, Andrea

    2015-02-14

    We observe the fluorescence of pristine diamondoids in the gas phase, excited using narrow band ultraviolet laser light. The emission spectra show well-defined features, which can be attributed to transitions from the excited electronic state into different vibrational modes of the electronic ground state. We assign the normal modes responsible for the vibrational bands, and determine the geometry of the excited states. Calculations indicate that for large diamondoids, the spectral bands do not result from progressions of single modes, but rather from combination bands composed of a large number of Δv = 1 transitions. The vibrational modes determining the spectral envelope can mainly be assigned to wagging and twisting modes of the surface atoms. We conclude that our theoretical approach accurately describes the photophysics in diamondoids and possibly other hydrocarbons in general.

  3. Quantum nuclear dynamics in the photophysics of diamondoids

    NASA Astrophysics Data System (ADS)

    Patrick, Christopher E.; Giustino, Feliciano

    2013-06-01

    The unusual electronic properties of diamondoids, the nanoscale relatives of diamond, make them attractive for applications ranging from drug delivery to field emission displays. Identifying the fundamental origin of these properties has proven highly challenging, with even the most advanced quantum many-body calculations unable to reproduce measurements of a quantity as ubiquitous as the optical gap. Here, by combining first-principles calculations and Importance Sampling Monte Carlo methods, we show that the quantum dynamics of carbon nuclei is key to understanding the electronic and optical properties of diamondoids. Quantum nuclear effects dramatically modify the absorption lineshapes and renormalize the optical gaps. These findings allow us to formulate a complete theory of optical absorption in diamondoids, and establish the universal role of quantum nuclear dynamics in nanodiamond across the length scales.

  4. Deliberate design of an acentric diamondoid metal-organic network

    SciTech Connect

    Yang Caiqin; Wang Jing; Wang Wei; Zhan Wenhong

    2011-09-15

    Reaction of 2.5-dicarboxy-1-methylpyridinium (DCMP) chloride and Zn(NO{sub 3}){sub 2}.6H{sub 2}O in the presence of NaHCO{sub 3} in water gave an expected acentric diamondoid network [Zn(DCMP){sub 2}] with a three-fold interpenetration. With long Zn-Zn separations, very large cavities are formed within each diamondoid network with high propensity to interpenetration, which makes it show a promising non-linear optical property with SHG efficiency approximately 7 times higher than that of potassium dihydrogen phosphate (KDP). The design strategy of ligand through methylation of the corresponding pyrdinecarboxylic acid can be extended to other widely used carboxylic acids, more importantly, to lead to an unsymmetric bifunctional bridging ligand, which is essential for generating polar solids. - Graphical Abstract: Reaction of Zn(NO{sub 3}){sub 2}.6H{sub 2}O with a deliberately designed unsymmetrical ligand 2.5-dicarboxy-1-methylpyridinium (DCMP) chloride and in the presence of NaHCO{sub 3} gave an expected noncentric diamondoid network [Zn(DCMP){sub 2}], which has its SHG response approximately 7 times higher than that of potassium dihydrogen phosphate (KDP). Highlights: > DCMP as an unsymmetrical organic ligand to design metal organic framework. > Long Zn-Zn separations and very large cavities formed. > Diamondoid network with high propensity to interpenetration formed. > Bifunctional bridging ligand was used to generate polar solids with large SHG response.

  5. The abundance and distribution of diamondoids in biodegraded oils from the San Joaquin Valley: Implications for biodegradation of diamondoids in petroleum reservoirs

    USGS Publications Warehouse

    Wei, Z.; Moldowan, J.M.; Peters, K.E.; Wang, Y.; Xiang, W.

    2007-01-01

    The biodegradability of diamondoids was investigated using a collection of crude oil samples from the San Joaquin Valley, California, that had been biodegraded to varying extent in the reservoir. Our results show that diamondoids are subjected to biodegradation, which is selective as well as stepwise. Adamantanes are generally more susceptible to biodegradation than other diamondoids, such as diamantanes and triamantanes. We report a possible pathway for the microbial degradation of adamantane. This cage hydrocarbon possibly breaks down to a metabolic intermediate through the action of microbes at higher levels of biodegradation in petroleum reservoirs. Microbial alteration has only a minor effect on diamondoid abundance in oil at low levels of biodegradation. Our results suggest that most diamondoids (with the exception of adamantane) are resistant to biodegradation, like the polycyclic terpanes (e.g. C19-C24 tricyclic terpanes, hopanes, gammacerane, oleananes, Ts, Tm, C29 Ts), steranes and diasteranes. Microbial alteration of diamondoids has a negligible impact on the quantification of oil cracking achieved using the diamondoid-biomarker method. ?? 2007 Elsevier Ltd. All rights reserved.

  6. Vibrational properties of cagelike diamondoid nitrogen at high pressure

    NASA Astrophysics Data System (ADS)

    Wang, Hui

    2013-08-01

    Under high pressure, a cagelike diamondoid nitrogen structure was lately discovered by first-principles structure researches. This newly proposed structure is very unique and has not been observed in any other element. Using density-functional calculations, we study the pressure effect on its vibrational properties. The Born effective charges are calculated, and the resulting LO—TO splittings of certain infrared active modes are beyond 20 cm-1. We depict the Γ-point vibrational modes and find the breathing mode, rotational mode, and shearing mode. Frequencies of all the optical modes increase with pressure increasing. Moreover, the relation between the breathing mode frequency and the nitrogen cage diameter is discussed in detail. Our calculation results give a deeper insight into the vibrational properties of the cagelike diamondoid nitrogen.

  7. Ab initio structural and vibrational properties of GaAs diamondoids and nanocrystals

    SciTech Connect

    Abdulsattar, Mudar Ahmed; Hussein, Mohammed T.; Hameed, Hadeel Ali

    2014-12-15

    Gallium arsenide diamondoids structural and vibrational properties are investigated using density functional theory at the PBE/6-31(d) level and basis including polarization functions. Variation of energy gap as these diamondoids increase in size is seen to follow confinement theory for diamondoids having nearly equiaxed dimensions. Density of energy states transforms from nearly single levels to band structure as we reach larger diamondoids. Bonds of surface hydrogen with As atoms are relatively localized and shorter than that bonded to Ga atoms. Ga-As bonds have a distribution range of values due to surface reconstruction and effect of bonding to hydrogen atoms. Experimental bulk Ga-As bond length (2.45 Å) is within this distribution range. Tetrahedral and dihedral angles approach values of bulk as we go to higher diamondoids. Optical-phonon energy of larger diamondoids stabilizes at 0.037 eV (297 cm{sup -1}) compared to experimental 0.035 eV (285.2 cm{sup -1}). Ga-As force constant reaches 1.7 mDyne/Å which is comparable to Ga-Ge force constant (1.74 mDyne/Å). Hydrogen related vibrations are nearly constant and serve as a fingerprint of GaAs diamondoids while Ga-As vibrations vary with size of diamondoids.

  8. Catalytic Generation Of Nanometer-sized Diamondoids From Thermal Decomposition Of Organic Matter In Modern Sediments

    NASA Astrophysics Data System (ADS)

    Wei, Z.; Moldowan, M. J.; Paytan, A.

    2005-12-01

    Diamondoids are nanoparticles naturally occurring in petroleum and not known to be natural products. Experimental work of artificial maturation on modern sediments was completed to determine if diamondoids can be created from biosynthetic precursors (e.g., n-alkenes, fatty acids, highly branched isoprenoids, sterols, etc.) present in modern sediments. Addition of mineral catalysts (montmorillonite K10, acidic aluminosilicate and calcium carbonate) with distinctive properties to pyrolysis experiments conducted using organic-rich modern sediments can provide information on which type of catalyst is active and effective in the production of diamondoids. Trace amounts of diamondoids were detected in San Francisco Bay, Santa Barbara Basin, and Elkhorn Slough muds. These might have been contributed by slight contamination with unknown oil spills or oil seeps, as supported by the presence of both geological epimers (22S) and biological epimers (22R) for C31-C35 homohopanes in mud extracts. However, diamondoids were not detectable or possibly absent in Celestun Lagoon carbonate which is rich in microfossils. Various quantities of diamondoids were generated from the thermal alteration of organic matter in several modern sediments in the presence and absence of catalysts. It is likely that the formation of diamondoids is coincident with the occurrence of n-alkanes and other biomarkers since the thermal maturation of modern sediments produces a certain amount of diamondoids. Clay minerals usually behave as acidic catalysts in the transformation of organic matter to hydrocarbons. As expected, montmorillonite K10 and acidic aluminosilicate greatly facilitate the formation of diamondoids in modern sediments at 340°C. Rearrangements of certain strained polycyclic carbonium-ion intermediates at Lewis super-acid sites may be responsible for the relatively high abundance of diamondoids upon thermal stress in the presence of montmorillonite K10 or acidic aluminosilicate. In contrast

  9. UV resonance Raman analysis of trishomocubane and diamondoid dimers

    NASA Astrophysics Data System (ADS)

    Meinke, Reinhard; Richter, Robert; Merli, Andrea; Fokin, Andrey A.; Koso, Tetyana V.; Rodionov, Vladimir N.; Schreiner, Peter R.; Thomsen, Christian; Maultzsch, Janina

    2014-01-01

    We present resonance Raman measurements of crystalline trishomocubane and diamantane dimers containing a C=C double bond. Raman spectra were recorded with excitation energies between 2.33 eV and 5.42 eV. The strongest enhancement is observed for the C=C stretch vibration and a bending mode involving the two carbon atoms of the C=C bond, corresponding to the B2g wagging mode of ethylene. This is associated with the localization of the π-HOMO and LUMO and the elongation of the C=C bond length and a pyramidalization of the two sp2-hybridized carbon atoms at the optical excitation. The observed Raman resonance energies of the trishomocubane and diamantane dimers are significantly lower than the HOMO-LUMO gaps of the corresponding unmodified diamondoids.

  10. UV resonance Raman analysis of trishomocubane and diamondoid dimers

    SciTech Connect

    Meinke, Reinhard Thomsen, Christian; Maultzsch, Janina; Richter, Robert; Merli, Andrea; Fokin, Andrey A.; Koso, Tetyana V.; Schreiner, Peter R.; Rodionov, Vladimir N.

    2014-01-21

    We present resonance Raman measurements of crystalline trishomocubane and diamantane dimers containing a C=C double bond. Raman spectra were recorded with excitation energies between 2.33 eV and 5.42 eV. The strongest enhancement is observed for the C=C stretch vibration and a bending mode involving the two carbon atoms of the C=C bond, corresponding to the B{sub 2g} wagging mode of ethylene. This is associated with the localization of the π-HOMO and LUMO and the elongation of the C=C bond length and a pyramidalization of the two sp{sup 2}-hybridized carbon atoms at the optical excitation. The observed Raman resonance energies of the trishomocubane and diamantane dimers are significantly lower than the HOMO-LUMO gaps of the corresponding unmodified diamondoids.

  11. UV resonance Raman analysis of trishomocubane and diamondoid dimers.

    PubMed

    Meinke, Reinhard; Richter, Robert; Merli, Andrea; Fokin, Andrey A; Koso, Tetyana V; Rodionov, Vladimir N; Schreiner, Peter R; Thomsen, Christian; Maultzsch, Janina

    2014-01-21

    We present resonance Raman measurements of crystalline trishomocubane and diamantane dimers containing a C=C double bond. Raman spectra were recorded with excitation energies between 2.33 eV and 5.42 eV. The strongest enhancement is observed for the C=C stretch vibration and a bending mode involving the two carbon atoms of the C=C bond, corresponding to the B2g wagging mode of ethylene. This is associated with the localization of the π-HOMO and LUMO and the elongation of the C=C bond length and a pyramidalization of the two sp(2)-hybridized carbon atoms at the optical excitation. The observed Raman resonance energies of the trishomocubane and diamantane dimers are significantly lower than the HOMO-LUMO gaps of the corresponding unmodified diamondoids.

  12. Effects of molecular geometry on the properties of compressed diamondoid crystals

    DOE PAGES

    Yang, Fan; Lin, Yu; Baldini, Maria; ...

    2016-11-01

    Diamondoids are an intriguing group of carbon-based nanomaterials, which combine desired properties of inorganic nanomaterials and small hydrocarbon molecules with atomic-level uniformity. In this Letter, we report the first comparative study on the effect of pressure on a series of diamondoid crystals with systematically varying molecular geometries and shapes, including zero-dimensional (0D) adamantane; one-dimensional (1D) diamantane, [121]tetramantane, [123]tetramantane, and [1212]pentamantane; two-dimensional (2D) [12312]hexamantane; and three-dimensional (3D) triamantane and [1(2,3)4]pentamantane. We find the bulk moduli of these diamondoid crystals are strongly dependent on the diamondoids’ molecular geometry with 3D [1(2,3)4]pentamantane being the least compressible and 0D adamantane being the most compressible.more » These diamondoid crystals possess excellent structural rigidity and are able to sustain large volume deformation without structural failure even after repetitive pressure loading cycles. These properties are desirable for constructing cushioning devices. Furthermore, we also demonstrate that lower diamondoids outperform the conventional cushioning materials in both the working pressure range and energy absorption density.« less

  13. Effects of molecular geometry on the properties of compressed diamondoid crystals

    SciTech Connect

    Yang, Fan; Lin, Yu; Baldini, Maria; Dahl, Jeremy E. P.; Carlson, Robert M. K.; Mao, Wendy L.

    2016-11-01

    Diamondoids are an intriguing group of carbon-based nanomaterials, which combine desired properties of inorganic nanomaterials and small hydrocarbon molecules with atomic-level uniformity. In this Letter, we report the first comparative study on the effect of pressure on a series of diamondoid crystals with systematically varying molecular geometries and shapes, including zero-dimensional (0D) adamantane; one-dimensional (1D) diamantane, [121]tetramantane, [123]tetramantane, and [1212]pentamantane; two-dimensional (2D) [12312]hexamantane; and three-dimensional (3D) triamantane and [1(2,3)4]pentamantane. We find the bulk moduli of these diamondoid crystals are strongly dependent on the diamondoids’ molecular geometry with 3D [1(2,3)4]pentamantane being the least compressible and 0D adamantane being the most compressible. These diamondoid crystals possess excellent structural rigidity and are able to sustain large volume deformation without structural failure even after repetitive pressure loading cycles. These properties are desirable for constructing cushioning devices. Furthermore, we also demonstrate that lower diamondoids outperform the conventional cushioning materials in both the working pressure range and energy absorption density.

  14. Generation of plasmas in supercritical xenon inside microcapillaries for synthesis of diamondoid

    NASA Astrophysics Data System (ADS)

    Oshima, Fumito; Ishii, Chikako; Stauss, Sven; Terashima, Kazuo

    2012-10-01

    Diamondoids are series of sp^3 hybridized carbon nanomaterials that could be applied in various fields such as pharmacy and optoelectronics. In our previous studies, higher order diamondoids were synthesized in supercritical fluid (SCF) plasmas in a batch-type reactor using adamantane (C10H16), the smallest diamondoid, as a precursor and seed. However the yield was low and the selectivity was difficult to control. We have developed a continuous flow SCF microplasma reactor that allows discharge volume and residence time to be adjusted. The electrodes consist of a tungsten wire inserted into a fused silica capillary and a sputtered silver outside of the capillary. We dissolved adamantane in supercritical xenon near critical point, and then generated DBDs inside the capillary using a nominal constant xenon flow rate of 0˜2.3 mL min-1. Micro-Raman spectra of the synthesized products show peaks that are characteristic of hydrocarbons possessing sp^3 hybridized bonds while gas-chromatography/mass spectrometry spectra indicate the synthesis of diamantane (C14H20) and possibly isomers of diamondoids consisting of up to nine cages, nonamantane. It is suggested that this type of SCF microplasma reactor might be effective not only for synthesis of diamondoids, but also other nanomaterials.

  15. Benchmark investigation of diamondoid-functionalized electrodes for nanopore DNA sequencing

    NASA Astrophysics Data System (ADS)

    Sivaraman, Ganesh; Amorim, Rodrigo G.; Scheicher, Ralph H.; Fyta, Maria

    2016-10-01

    Small diamond-like particles, diamondoids, have been shown to effectively functionalize gold electrodes in order to sense DNA units passing between the nanopore-embedded electrodes. In this work, we present a comparative study of Au(111) electrodes functionalized with different derivatives of lower diamondoids. Focus is put on the electronic and transport properties of such electrodes for different DNA nucleotides placed within the electrode gap. The functionalization promotes a specific binding to DNA leading to different properties for the system, which provides a tool set to systematically improve the signal-to-noise ratio of the electronic measurements across the electrodes. Using quantum transport calculations, we compare the effectiveness of the different functionalized electrodes in distinguishing the four DNA nucleotides. Our results point to the most effective diamondoid functionalization of gold electrodes in view of biosensing applications.

  16. Size and shape dependent photoluminescence and excited state decay rates of diamondoids.

    PubMed

    Richter, Robert; Wolter, David; Zimmermann, Tobias; Landt, Lasse; Knecht, Andre; Heidrich, Christoph; Merli, Andrea; Dopfer, Otto; Reiss, Philipp; Ehresmann, Arno; Petersen, Jens; Dahl, Jeremy E; Carlson, Robert M K; Bostedt, Christoph; Möller, Thomas; Mitric, Roland; Rander, Torbjörn

    2014-02-21

    We present photoluminescence spectra and excited state decay rates of a series of diamondoids, which represent molecular structural analogues to hydrogen-passivated bulk diamond. Specific isomers of the five smallest diamondoids (adamantane-pentamantane) have been brought into the gas phase and irradiated with synchrotron radiation. All investigated compounds show intrinsic photoluminescence in the ultraviolet spectral region. The emission spectra exhibit pronounced vibrational fine structure which is analyzed using quantum chemical calculations. We show that the geometrical relaxation of the first excited state of adamantane, exhibiting Rydberg character, leads to the loss of Td symmetry. The luminescence of adamantane is attributed to a transition from the delocalized first excited state into different vibrational modes of the electronic ground state. Similar geometrical changes of the excited state structure have also been identified in the other investigated diamondoids. The excited state decay rates show a clear dependence on the size of the diamondoid, but are independent of the particle geometry, further indicating a loss of particle symmetry upon electronic excitation.

  17. Diamondoid-functionalized gold nanogaps as sensors for natural, mutated, and epigenetically modified DNA nucleotides.

    PubMed

    Sivaraman, Ganesh; Amorim, Rodrigo G; Scheicher, Ralph H; Fyta, Maria

    2016-05-21

    Modified tiny hydrogen-terminated diamond structures, known as diamondoids, show a high efficiency in sensing DNA molecules. These diamond cages, as recently proposed, could offer functionalization possibilities for gold junction electrodes. In this investigation, we report on diamondoid-functionalized electrodes, showing that such a device would have a high potential in sensing and sequencing DNA. The smallest diamondoid including an amine modification was chosen for the functionalization. Here, we report on the quantum tunneling signals across diamondoid-functionalized Au(111) electrodes. Our work is based on quantum-transport calculations and predicts the expected signals arising from different DNA units within the break junctions. Different gating voltages are proposed in order to tune the sensitivity of the functionalized electrodes with respect to specific nucleotides. The relation of this sensitivity to the coupling or decoupling of the electrodes is discussed. Our results also shed light on the sensing capability of such a device in distinguishing the DNA nucleotides, in their natural and mutated forms.

  18. Diamondoid synthesis by nanosecond pulsed microplasmas generated in He at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Stauss, Sven; Shizuno, Tomoki; Oshima, Fumito; Pai, David Z.; Terashima, Kazuo

    2012-10-01

    Diamondoids are sp^3 hybridized carbon nanomaterials that possess interesting properties making them attractive for biotechnology, medicine, and opto- and nanoelectronics. So far, larger diamondoids have been synthesized using the smallest diamondoid (adamantane) as a precursor. For this electric discharges and pulsed laser plasmas generated in supercritical fluids, and hot filament chemical vapor deposition have been used, but these methods are difficult to realize or very time-consuming. We have developed a more convenient approach where diamondoids are synthesized by high-voltage nanosecond pulsed microplasmas (voltage 15 kVp-p, frequency 1 Hz, pulse width 10 ns) generated in He at atmospheric pressure using point-to-plane tungsten electrodes. Adamantane was used as a precursor, and synthesis was conducted for 10^5 pulses at gas temperatures of 297, 373 and 473 K. Energy dispersive X-ray and micro-Raman spectroscopy were conducted to determine the composition of the products, and gas chromatography - mass spectra indicated the formation of diamantane. It was found that synthesis is more efficient at room temperature than at higher temperatures, and time-resolved optical emission spectroscopy suggest that the chemical reactions take place in the afterglow.

  19. Non Covalent Interactions in Large Diamondoid Dimers in the Gas Phase - a Microwave Study

    NASA Astrophysics Data System (ADS)

    Perez, Cristobal; Sekutor, Marina; Fokin, Andrey A.; Blomeyer, Sebastian; Vishnevskiy, Yury V.; Mitzel, Norbert W.; Schreiner, Peter R.; Schnell, Melanie

    2017-06-01

    Accurate structure determination of large molecules still represents an ambitious challenge. Interesting benchmark systems for structure determination are large diamondoid dimers, whose structures are governed by strong intramolecular interactions. Recently, diamondoid dimers with unusually long central C-C bonds (up to 1.71 Å) were synthesized. This long central C-C bond was rationalized by numerous CH...HC-type dispersion attractions between the two halves of the molecule. The thermodynamic stabilization of molecules equipped with bulky groups has provided a conceptually new rationale, since until then it had been assumed that such molecules are highly unstable. We performed a broadband CP-FTMW spectroscopy study in the 2-8 GHz frequency range on oxygen-substituted diamondoid dimers (C_{26}H_{34}O_2, 28 heavy atoms) as well as diadamantyl ether to provide further insight into their structures. The experimental data are compared with results from quantum-chemical calculations and gas-phase electron diffraction. For the ether, we even obtained ^{13}C and ^{18}O isotopologues to generate the full heavy-atom substitution structure.

  20. Thiol biochemistry of prokaryotes

    NASA Technical Reports Server (NTRS)

    Fahey, Robert C.

    1986-01-01

    The present studies have shown that GSH metabolism arose in the purple bacteria and cyanobacteria where it functions to protect against oxygen toxicity. Evidence was obtained indicating that GSH metabolism was incorporated into eucaryotes via the endosymbiosis giving rise to mitochrondria and chloroplasts. Aerobic bacteria lacking GSH utilize other thiols for apparently similar functions, the thiol being coenzyme A in Gram positive bacteria and chi-glutamylcysteine in the halobacteria. The thiol biochemistry of prokaryotes is thus seen to be much more highly diversified than that of eucaryotes and much remains to be learned about this subject.

  1. Rapid photochemical surface patterning of proteins in thiol-ene based microfluidic devices.

    PubMed

    Lafleur, Josiane P; Kwapiszewski, Radoslaw; Jensen, Thomas G; Kutter, Jörg P

    2013-02-21

    The suitable optical properties of thiol-ene polymers combined with the ease of modifying their surface for the attachment of recognition molecules make them ideal candidates in many biochip applications. This paper reports the rapid one-step photochemical surface patterning of biomolecules in microfluidic thiol-ene chips. This work focuses on thiol-ene substrates featuring an excess of thiol groups at their surface. The thiol-ene stoichiometric composition can be varied to precisely control the number of surface thiol groups available for surface modification up to an average surface density of 136 ± 17 SH nm(-2). Biotin alkyne was patterned directly inside thiol-ene microchannels prior to conjugation with fluorescently labelled streptavidin. The surface bound conjugates were detected by evanescent wave-induced fluorescence (EWIF), demonstrating the success of the grafting procedure and its potential for biochip applications.

  2. Improved Performance of DNA Microarray Multiplex Hybridization Using Probes Anchored at Several Points by Thiol-Ene or Thiol-Yne Coupling Chemistry.

    PubMed

    Bañuls, Maria-Jose; Jiménez-Meneses, Pilar; Meyer, Albert; Vasseur, Jean-Jacques; Morvan, François; Escorihuela, Jorge; Puchades, Rosa; Maquieira, Ángel

    2017-02-15

    Nucleic acid microarray-based assay technology has shown lacks in reproducibility, reliability, and analytical sensitivity. Here, a new strategy of probe attachment modes for silicon-based materials is built up. Thus, hybridization ability is enhanced by combining thiol-ene or thiol-yne click chemistry reactions with a multipoint attachment of polythiolated probes. The viability and performance of this approach was demonstrated by specifically determining Salmonella PCR products up to a 20 pM sensitivity level.

  3. Hybrid metal–organic chalcogenide nanowires with electrically conductive inorganic core through diamondoid-directed assembly

    SciTech Connect

    Yan, Hao; Hohman, J. Nathan; Li, Fei Hua; Jia, Chunjing; Solis-Ibarra, Diego; Wu, Bin; Dahl, Jeremy E. P.; Carlson, Robert M. K.; Tkachenko, Boryslav A.; Fokin, Andrey A.; Schreiner, Peter R.; Vailionis, Arturas; Kim, Taeho Roy; Devereaux, Thomas P.; Shen, Zhi -Xun; Melosh, Nicholas A.

    2016-12-26

    Controlling inorganic structure and dimensionality through structure-directing agents is a versatile approach for new materials synthesis that has been used extensively for metal–organic frameworks and coordination polymers. However, the lack of ‘solid’ inorganic cores requires charge transport through single-atom chains and/or organic groups, limiting their electronic properties. Here, we report that strongly interacting diamondoid structure-directing agents guide the growth of hybrid metal–organic chalcogenide nanowires with solid inorganic cores having three-atom cross-sections, representing the smallest possible nanowires. The strong van der Waals attraction between diamondoids overcomes steric repulsion leading to a cis configuration at the active growth front, enabling face-on addition of precursors for nanowire elongation. These nanowires have band-like electronic properties, low effective carrier masses and three orders-of-magnitude conductivity modulation by hole doping. Furthermore, this discovery highlights a previously unexplored regime of structure-directing agents compared with traditional surfactant, block copolymer or metal–organic framework linkers.

  4. Results from VUV Spectroscopy of Neutral Diamondoid Molecules and IR Spectroscopy of the Cationic Species

    NASA Astrophysics Data System (ADS)

    Pirali, Olivier; Boyé-Peronne, Séverine; Douin, Stéphane; Galue, Hector Alvaro; Oomens, Jos; Garcia, Gustavo; Nahon, Laurent; Vervloet, Michel

    2009-06-01

    Due to their stability, diamond materials are expected to be present in different environments of the interstellar medium. Indeed, nanometer size diamond cristals have been extracted from carbonaceous chondrites and two emission features (observed at 3.43 μm and 3.53 μm) in the spectra of HD 97048 and Elias1 have been assigned to these species. Despite high astrophysical relevance, very few is known about the structural properties and dynamics of the molecular building blocks of larger species : the diamondoid molecules. These molecules consist of sp3 hybridized carbon cages where dangling bonds are terminated by hydrogen atoms. The infrared spectra of neutral molecules conforted the assignment of the 3.43 μm and 3.53 μm emission features to nanometer size diamondoid systems. In order to improve the understanding of the possible process leading to the IR emission features, we recorded the IR spectra of the deshydrogenated cationic species of adamantane, diamantane and triamantane (using Infrared Multi Photon Dissociation technique with the free electron laser FELIX) as well as the VUV spectra of adamantane and diamantane (obtained thanks to the Threshold Photo Electron Photo Ion Coincidence technique at the DESIRS beamline of the synchrotron SOLEIL). We will show the results of these spectra and the preliminary analysis. Saslaw and Gaustad, Nature, 221, 160 (1969) Lewis et al., Nature, 326, 160 (1987) van Kerckhoven et al., Astronomy and Astrophysic, 384, 568 (2002) Pirali et al., The Astrophysical Journal, 661, 919 (2007)

  5. Hybrid metal-organic chalcogenide nanowires with electrically conductive inorganic core through diamondoid-directed assembly

    NASA Astrophysics Data System (ADS)

    Yan, Hao; Hohman, J. Nathan; Li, Fei Hua; Jia, Chunjing; Solis-Ibarra, Diego; Wu, Bin; Dahl, Jeremy E. P.; Carlson, Robert M. K.; Tkachenko, Boryslav A.; Fokin, Andrey A.; Schreiner, Peter R.; Vailionis, Arturas; Kim, Taeho Roy; Devereaux, Thomas P.; Shen, Zhi-Xun; Melosh, Nicholas A.

    2016-12-01

    Controlling inorganic structure and dimensionality through structure-directing agents is a versatile approach for new materials synthesis that has been used extensively for metal-organic frameworks and coordination polymers. However, the lack of `solid’ inorganic cores requires charge transport through single-atom chains and/or organic groups, limiting their electronic properties. Here, we report that strongly interacting diamondoid structure-directing agents guide the growth of hybrid metal-organic chalcogenide nanowires with solid inorganic cores having three-atom cross-sections, representing the smallest possible nanowires. The strong van der Waals attraction between diamondoids overcomes steric repulsion leading to a cis configuration at the active growth front, enabling face-on addition of precursors for nanowire elongation. These nanowires have band-like electronic properties, low effective carrier masses and three orders-of-magnitude conductivity modulation by hole doping. This discovery highlights a previously unexplored regime of structure-directing agents compared with traditional surfactant, block copolymer or metal-organic framework linkers.

  6. Unconventional molecule-resolved current rectification in diamondoid-fullerene hybrids

    NASA Astrophysics Data System (ADS)

    Randel, Jason C.; Niestemski, Francis C.; Botello-Mendez, Andrés R.; Mar, Warren; Ndabashimiye, Georges; Melinte, Sorin; Dahl, Jeremy E. P.; Carlson, Robert M. K.; Butova, Ekaterina D.; Fokin, Andrey A.; Schreiner, Peter R.; Charlier, Jean-Christophe; Manoharan, Hari C.

    2014-09-01

    The unimolecular rectifier is a fundamental building block of molecular electronics. Rectification in single molecules can arise from electron transfer between molecular orbitals displaying asymmetric spatial charge distributions, akin to p-n junction diodes in semiconductors. Here we report a novel all-hydrocarbon molecular rectifier consisting of a diamantane-C60 conjugate. By linking both sp3 (diamondoid) and sp2 (fullerene) carbon allotropes, this hybrid molecule opposingly pairs negative and positive electron affinities. The single-molecule conductances of self-assembled domains on Au(111), probed by low-temperature scanning tunnelling microscopy and spectroscopy, reveal a large rectifying response of the molecular constructs. This specific electronic behaviour is postulated to originate from the electrostatic repulsion of diamantane-C60 molecules due to positively charged terminal hydrogen atoms on the diamondoid interacting with the top electrode (scanning tip) at various bias voltages. Density functional theory computations scrutinize the electronic and vibrational spectroscopic fingerprints of this unique molecular structure and corroborate the unconventional rectification mechanism.

  7. Synthesis of higher diamondoids by pulsed laser ablation plasmas in supercritical CO{sub 2}

    SciTech Connect

    Nakahara, Sho; Stauss, Sven; Kato, Toru; Terashima, Kazuo; Sasaki, Takehiko

    2011-06-15

    Pulsed laser ablation (wavelength 532 nm; fluence 18 J/cm{sup 2}; pulse width 7 ns; repetition rate 10 Hz) of highly oriented pyrolytic graphite was conducted in adamantane-dissolved supercritical CO{sub 2} with and without cyclohexane as a cosolvent. Micro-Raman spectroscopy of the products revealed the presence of hydrocarbons possessing sp{sup 3}-hybridized carbons similar to diamond structures. The synthesis of diamantane and other possible diamondoids consisting of up to 12 cages was confirmed by gas chromatography-mass spectrometry. Furthermore, gas chromatography-mass spectrometry measurements of samples before and after pyrolysis treatment indicate the synthesis of the most compact decamantane, namely, superadamantane. It is thought that oxidant species originating from CO{sub 2} during pulsed laser ablation might lead to the selective dissociation of C-H bonds, enabling the synthesis of low H/C ratio molecules. Therefore, laser ablation in supercritical CO{sub 2} is proposed as a practical method for synthesizing diamondoids.

  8. Hybrid metal-organic chalcogenide nanowires with electrically conductive inorganic core through diamondoid-directed assembly.

    PubMed

    Yan, Hao; Hohman, J Nathan; Li, Fei Hua; Jia, Chunjing; Solis-Ibarra, Diego; Wu, Bin; Dahl, Jeremy E P; Carlson, Robert M K; Tkachenko, Boryslav A; Fokin, Andrey A; Schreiner, Peter R; Vailionis, Arturas; Kim, Taeho Roy; Devereaux, Thomas P; Shen, Zhi-Xun; Melosh, Nicholas A

    2017-03-01

    Controlling inorganic structure and dimensionality through structure-directing agents is a versatile approach for new materials synthesis that has been used extensively for metal-organic frameworks and coordination polymers. However, the lack of 'solid' inorganic cores requires charge transport through single-atom chains and/or organic groups, limiting their electronic properties. Here, we report that strongly interacting diamondoid structure-directing agents guide the growth of hybrid metal-organic chalcogenide nanowires with solid inorganic cores having three-atom cross-sections, representing the smallest possible nanowires. The strong van der Waals attraction between diamondoids overcomes steric repulsion leading to a cis configuration at the active growth front, enabling face-on addition of precursors for nanowire elongation. These nanowires have band-like electronic properties, low effective carrier masses and three orders-of-magnitude conductivity modulation by hole doping. This discovery highlights a previously unexplored regime of structure-directing agents compared with traditional surfactant, block copolymer or metal-organic framework linkers.

  9. Hybrid metal–organic chalcogenide nanowires with electrically conductive inorganic core through diamondoid-directed assembly

    DOE PAGES

    Yan, Hao; Hohman, J. Nathan; Li, Fei Hua; ...

    2016-12-26

    Controlling inorganic structure and dimensionality through structure-directing agents is a versatile approach for new materials synthesis that has been used extensively for metal–organic frameworks and coordination polymers. However, the lack of ‘solid’ inorganic cores requires charge transport through single-atom chains and/or organic groups, limiting their electronic properties. Here, we report that strongly interacting diamondoid structure-directing agents guide the growth of hybrid metal–organic chalcogenide nanowires with solid inorganic cores having three-atom cross-sections, representing the smallest possible nanowires. The strong van der Waals attraction between diamondoids overcomes steric repulsion leading to a cis configuration at the active growth front, enabling face-on additionmore » of precursors for nanowire elongation. These nanowires have band-like electronic properties, low effective carrier masses and three orders-of-magnitude conductivity modulation by hole doping. Furthermore, this discovery highlights a previously unexplored regime of structure-directing agents compared with traditional surfactant, block copolymer or metal–organic framework linkers.« less

  10. Hybrid metal-organic chalcogenide nanowires with electrically conductive inorganic core through diamondoid-directed assembly

    NASA Astrophysics Data System (ADS)

    Yan, Hao; Hohman, J. Nathan; Li, Fei Hua; Jia, Chunjing; Solis-Ibarra, Diego; Wu, Bin; Dahl, Jeremy E. P.; Carlson, Robert M. K.; Tkachenko, Boryslav A.; Fokin, Andrey A.; Schreiner, Peter R.; Vailionis, Arturas; Kim, Taeho Roy; Devereaux, Thomas P.; Shen, Zhi-Xun; Melosh, Nicholas A.

    2017-03-01

    Controlling inorganic structure and dimensionality through structure-directing agents is a versatile approach for new materials synthesis that has been used extensively for metal-organic frameworks and coordination polymers. However, the lack of `solid’ inorganic cores requires charge transport through single-atom chains and/or organic groups, limiting their electronic properties. Here, we report that strongly interacting diamondoid structure-directing agents guide the growth of hybrid metal-organic chalcogenide nanowires with solid inorganic cores having three-atom cross-sections, representing the smallest possible nanowires. The strong van der Waals attraction between diamondoids overcomes steric repulsion leading to a cis configuration at the active growth front, enabling face-on addition of precursors for nanowire elongation. These nanowires have band-like electronic properties, low effective carrier masses and three orders-of-magnitude conductivity modulation by hole doping. This discovery highlights a previously unexplored regime of structure-directing agents compared with traditional surfactant, block copolymer or metal-organic framework linkers.

  11. Diamondoid hydrocarbons as a molecular proxy for thermal maturity and oil cracking: Geochemical models from hydrous pyrolysis

    USGS Publications Warehouse

    Wei, Z.; Moldowan, J.M.; Zhang, S.; Hill, R.; Jarvie, D.M.; Wang, Hongfang; Song, F.; Fago, F.

    2007-01-01

    A series of isothermal hydrous pyrolysis experiments was performed on immature sedimentary rocks and peats of different lithology and organic source input to explore the generation of diamondoids during the thermal maturation of sediments. Oil generation curves indicate that peak oil yields occur between 340 and 360 ??C, followed by intense oil cracking in different samples. The biomarker maturity parameters appear to be insensitive to thermal maturation as most of the isomerization ratios of molecular biomarkers in the pyrolysates have reached their equilibrium values. Diamondoids are absent from immature peat extracts, but exist in immature sedimentary rocks in various amounts. This implies that they are not products of biosynthesis and that they may be generated during diagenesis, not just catagenesis and cracking. Most importantly, the concentrations of diamondoids are observed to increase with thermal stress, suggesting that they can be used as a molecular proxy for thermal maturity of source rocks and crude oils. Their abundance is most sensitive to thermal exposure above temperatures of 360-370 ??C (R0 = 1.3-1.5%) for the studied samples, which corresponds to the onset of intense cracking of other less stable components. Below these temperatures, diamondoids increase gradually due to competing processes of generation and dilution. Calibrations were developed between their concentrations and measured vitrinite reflectance through hydrous pyrolysis maturation of different types of rocks and peats. The geochemical models obtained from these methods may provide an alterative approach for determining thermal maturity of source rocks and crude oils, particularly in mature to highly mature Paleozoic carbonates. In addition, the extent of oil cracking was quantified using the concentrations of diamondoids in hydrous pyrolysates of rocks and peats, verifying that these hydrocarbons are valuable indicators of oil cracking in nature. ?? 2006 Elsevier Ltd. All rights

  12. Thiol-addition reactions and their applications in thiol recognition.

    PubMed

    Yin, Caixia; Huo, Fangjun; Zhang, Jingjing; Martínez-Máñez, Ramón; Yang, Yutao; Lv, Haigang; Li, Sidian

    2013-07-21

    Because of the biological importance of thiols, the development of probes for thiols has been an active research area in recent years. In this review, we summarize the results of recent exciting reports regarding thiol-addition reactions and their applications in thiol recognition. The examples reported can be classified into four reaction types including 1,1, 1,2, 1,3, 1,4 addition reactions, according to their addition mechanisms, based on different Michael acceptors. In all cases, the reactions are coupled to color and/or emission changes, although some examples dealing with electrochemical recognition have also been included. The use of thiol-addition reactions is a very simple and straightforward procedure for the preparation of thiol-sensing probes.

  13. Electron–vibration coupling induced renormalization in the photoemission spectrum of diamondoids

    PubMed Central

    Gali, Adam; Demján, Tamás; Vörös, Márton; Thiering, Gergő; Cannuccia, Elena; Marini, Andrea

    2016-01-01

    The development of theories and methods devoted to the accurate calculation of the electronic quasi-particle states and levels of molecules, clusters and solids is of prime importance to interpret the experimental data. These quantum systems are often modelled by using the Born–Oppenheimer approximation where the coupling between the electrons and vibrational modes is not fully taken into account, and the electrons are treated as pure quasi-particles. Here, we show that in small diamond cages, called diamondoids, the electron–vibration coupling leads to the breakdown of the electron quasi-particle picture. More importantly, we demonstrate that the strong electron–vibration coupling is essential to properly describe the overall lineshape of the experimental photoemission spectrum. This cannot be obtained by methods within Born–Oppenheimer approximation. Moreover, we deduce a link between the vibronic states found by our many-body perturbation theory approach and the well-known Jahn–Teller effect. PMID:27103340

  14. Electron–vibration coupling induced renormalization in the photoemission spectrum of diamondoids

    SciTech Connect

    Gali, Adam; Demján, Tamás; Vörös, Márton; Thiering, Gergő; Cannuccia, Elena; Marini, Andrea

    2016-04-22

    The development of theories and methods devoted to the accurate calculation of the electronic quasi-particle states and levels of molecules, clusters and solids is of prime importance to interpret the experimental data. These quantum systems are often modelled by using the Born–Oppenheimer approximation where the coupling between the electrons and vibrational modes is not fully taken into account, and the electrons are treated as pure quasi-particles. Here, we show that in small diamond cages, called diamondoids, the electron–vibration coupling leads to the breakdown of the electron quasi-particle picture. More importantly, we demonstrate that the strong electron–vibration coupling is essential to properly describe the overall lineshape of the experimental photoemission spectrum. This cannot be obtained by methods within Born–Oppenheimer approximation. Furthermore, we deduce a link between the vibronic states found by our many-body perturbation theory approach and the well-known Jahn–Teller effect.

  15. Electroanalysis of Plant Thiols

    PubMed Central

    Supalkova, Veronika; Huska, Dalibor; Diopan, Vaclav; Hanustiak, Pavel; Zitka, Ondrej; Stejskal, Karel; Baloun, Jiri; Pikula, Jiri; Havel, Ladislav; Zehnalek, Josef; Adam, Vojtech; Trnkova, Libuse; Beklova, Miroslava; Kizek, Rene

    2007-01-01

    Due to unique physico-chemical properties of –SH moiety thiols comprise wide group of biologically important compounds. A review devoted to biological functions of glutathione and phytochelatins with literature survey of methods used to analysis of these compounds and their interactions with cadmium(II) ions and Murashige-Skoog medium is presented. For these purposes electrochemical techniques are used. Moreover, we revealed the effect of three different cadmium concentrations (0, 10 and 100 μM) on cadmium uptake and thiols content in maize plants during 192 hours long experiments using differential pulse anodic stripping voltammetry to detect cadmium(II) ions and high performance liquid chromatography with electrochemical detection to determine glutathione. Cadmium concentration determined in tissues of the plants cultivated in nutrient solution containing 10 μM Cd was very low up to 96 hours long exposition and then the concentration of Cd markedly increased. On the contrary, the addition of 100 μM Cd caused an immediate sharp increase in all maize plant parts to 96 hours Cd exposition but subsequently the Cd concentration increased more slowly. A high performance liquid chromatography with electrochemical detection was used for glutathione determination in treated maize plants after 96 and 192 hours of treatment. The highest total content of glutathione per one plant was 6 μg (96 h, 10 μM Cd) in comparison with non-treated plant (control) where glutathione content was 1.5 μg. It can be concluded that electrochemical techniques have proved to be useful to analyse plant thiols.

  16. Electrical conduction measurement of thiol modified DNA molecules

    NASA Astrophysics Data System (ADS)

    Hwang, J. S.; Hwang, S. W.; Ahn, D.

    2003-09-01

    We present a novel transport measurement of 60 base pairs of poly(dG)-poly(dC) DNA molecules. Thiol-terminated DNA molecules are chemically anchored at the surface of a Au nanoparticle and this DNA attached Au nanoparticle is self-trapped in between Au nanoelectrodes to make an electrical conduction channel. It provides an automatic electrical conduction channel consisting of electrode-DNA-nanoparticle-DNA-electrode. Due to robust bonding of thiol and Au, this transport channel is stable and reliable. The current-voltage characteristics measured from our device show a nonlinear behavior with voltage gaps comparable to previous experiment using the same molecules.

  17. Rapid and thiol-specific high-throughput assay for simultaneous relative quantification of total thiols, protein thiols, and nonprotein thiols in cells.

    PubMed

    Yang, Yang; Guan, Xiangming

    2015-01-06

    Thiol groups in biological molecules play a significant role in various physiological functions and pathological conditions. Thiols are divided into two major groups: protein thiols and nonprotein thiols. Numerous methods have been reported for thiol assays. Most of these methods have been developed for glutathione, the principal nonprotein thiol, despite the fact that cellular protein thiols are more abundant than glutathione. Further, these methods usually involve a process of biological sample preparation followed by a separation method, and they are time-consuming. We reported previously a series of thiol-specific fluorogenic benzofurazan sulfides. These nonfluorescent benzofurazan sulfides react rapidly and specifically with a thiol to form a strong fluorescent thiol adduct. The rapid reaction, thiol-specific and fluorogenic nature of the sulfides successfully yielded an application of one of the sulfides for relative quantitation of total thiols in live cells through fluorescence microscopy. In this work, we employed the same compound to develop the first high-throughput method for simultaneous monitoring of protein thiols, nonprotein thiols, and total thiols in cells in a 96-well plate on a fluorescence microplate reader at λ(ex) = 430 nm and λ(em) = 520 nm, respectively. The method is rapid and sensitive, and has been validated by an HPLC thiol assay method. The method can detect thiols with cell concentrations as low as 500 cells/well. We also demonstrated that the method can readily monitor changes in cellular thiol levels. Although the method cannot provide an absolute quantification for thiols because fluorescence intensity of different thiol adducts varies, it provides an accurate measurement of relative quantification, relative to the control. The method will be a valuable tool in thiol-related biomedical/pharmaceutical research.

  18. Synthesis of diamondoid lanthanide-polyoxometalate solids as tunable photoluminescent materials.

    PubMed

    Zhao, Wen-Feng; Zou, Chao; Shi, Lian-Xu; Yu, Jian-Can; Qian, Guo-Dong; Wu, Chuan-De

    2012-09-07

    The reaction between polyoxometalate (POM) [TBA](12)[WZn{Zn(H(2)O)}(2)(ZnW(9)O(34))(2)] (TBA = tetrabutyl ammonium) and lanthanide (Ln) nitrate (Ln = La, Eu and Tb) in a mixed solvent of CH(3)CN and DMF yielded three noncentrosymmetric diamondoid Ln-POM solid materials, {[Ln(2)(DMF)(8)(H(2)O)(6)][ZnW(12)O(40)]}·4DMF (Ln-POM; Ln = La, Eu and Tb). In these compounds, the {ZnW(12)O(40)} unit, transferred from the metastable [WZn{Zn(H(2)O)}(2)(ZnW(9)O(34))(2)] cluster, acts as a tetradentate ligand to connect with four Ln nodes, while the Ln ion links up two {ZnW(12)O(40)} units. These compounds generated interesting luminescence emissions that are dependent on the Ln ions and their ratios. White light emission was obtained by a doped approach with a rational ratio of the Eu(3+) and Tb(3+) ions.

  19. Synthesis, crystal structure, and magnetic properties of a two-fold interpenetrated diamondoid open framework

    NASA Astrophysics Data System (ADS)

    Wu, Jing-Yun; Cheng, Fu-Yin; Chiang, Ming-Hsi

    2016-10-01

    Self-assembly of an enlarged angular pyridinecarboxylate ligand and cobalt(II) acetate under mild conditions afforded a three-dimensional open-framework coordination polymer, [Co2(μ-H2O)(pyca-43)4]n (1, Hpyca-43=(E)-3-((pyridin-4-yl)methyleneamino)benzoic acid). The molecular structure of 1 has rationalized to be a porous two-fold interpenetrated diamondoid-like network, with dinuclear Co2(μ-H2O)(O2C)4N4 clusters as tetrahedral secondary building units (SBUs), possessing highly solvent accessible volume of approximately 53.0%. Least-squares fit of the magnetic susceptibility data (20-300 K) of 1 yields Curie constant C=6.15 cm3 mol-1 K and Weiss constant θ=-11.6 K. Every Co2 subunit within the network is magnetically insulated to other dimers. The magnetic exchange parameter between Co(II) centers is estimated to -0.72 cm-1, suggesting a weak antiferromagnetic interaction. The gav value of 4.65 from fitting to the Lines model indicates that the decrease of the χMT value upon cooling is dominated by depopulation of the excited Kramer's states to the effective ground singlet. In addition, the thermal stability and adsorption properties of 1 are also reported.

  20. Electron–vibration coupling induced renormalization in the photoemission spectrum of diamondoids

    DOE PAGES

    Gali, Adam; Demján, Tamás; Vörös, Márton; ...

    2016-04-22

    The development of theories and methods devoted to the accurate calculation of the electronic quasi-particle states and levels of molecules, clusters and solids is of prime importance to interpret the experimental data. These quantum systems are often modelled by using the Born–Oppenheimer approximation where the coupling between the electrons and vibrational modes is not fully taken into account, and the electrons are treated as pure quasi-particles. Here, we show that in small diamond cages, called diamondoids, the electron–vibration coupling leads to the breakdown of the electron quasi-particle picture. More importantly, we demonstrate that the strong electron–vibration coupling is essential tomore » properly describe the overall lineshape of the experimental photoemission spectrum. This cannot be obtained by methods within Born–Oppenheimer approximation. Furthermore, we deduce a link between the vibronic states found by our many-body perturbation theory approach and the well-known Jahn–Teller effect.« less

  1. Quantification of Thiols and Disulfides

    PubMed Central

    Winther, Jakob R.; Thorpe, Colin

    2013-01-01

    Background Disulfide bond formation is a key posttranslational modification, with implications for structure, function and stability of numerous proteins. While disulfide bond formation is a necessary and essential process for many proteins, it is deleterious and disruptive for others. Cells go to great lengths to regulate thiol-disulfide bond homeostasis, typically with several, apparently redundant, systems working in parallel. Dissecting the extent of oxidation and reduction of disulfides is an ongoing challenge due, in part, to the facility of thiol/disulfide exchange reactions. Scope of the review In the present account, we briefly survey the toolbox available to the experimentalist for the chemical determination of thiols and disulfides. We have chosen to focus on the key chemical aspects of current methodology, together with identifying potential difficulties inherent in their experimental implementation. Major conclusions While many reagents have been described for the measurement and manipulation of the redox status of thiols and disulfides, a number of these methods remain underutilized. The ability to effectively quantify changes in redox conditions in living cells presents a continuing challenge. General Significance Many unresolved questions in the metabolic interconversion of thiols and disulfides remain. For example, while pool sizes of redox pairs and their intracellular distribution are being uncovered, very little is known about the flux in thiol-disulfide exchange pathways. New tools are needed to address this important aspect of cellular metabolism. PMID:23567800

  2. Diamondoid diacids ('O4' species) in oil sands process-affected water.

    PubMed

    Lengger, Sabine K; Scarlett, Alan G; West, Charles E; Rowland, Steven J

    2013-12-15

    As a by-product of oil sands extraction, large volumes of oil sands process water (OSPW) are generated, which are contaminated with a large range of water-soluble organic compounds. The acids are thought to be derived from hydrocarbons via natural biodegradation pathways such as α- and β-oxidation of alkyl substituents, which could produce mono- and diacids, for example. However, while several monoacids ('O2' species) have been identified, the presence of diacids (i.e. 'O4' species) has only been deduced from results obtained via Fourier transform infrared (FTIR) spectroscopy, Fourier transform ion cyclotron resonance high-resolution mass spectrometry (FTICR-HRMS) and nuclear magnetic resonance ((1)H-NMR) spectroscopy and the structures have never been confirmed. An extract of an OSPW from a Canadian tailings pond was analysed and the retention times and the electron ionization mass spectra of some analytes were compared with those of bis-methyl esters of authentic diacids by gas chromatography × gas chromatography/time-of-flight mass spectrometry (GCxGC/TOFMS) in nominal and accurate mass configurations. Two diamondoid diacids (3-carboxymethyladamantane-1-carboxylic acid and adamantane-1,3-dicarboxylic acid) were firmly identified as their bis-methyl esters by retention time and mass spectral matching and several other structural isomers were more tentatively assigned. Diacids have substantially increased polarity over the hydrocarbon and monoacid species from which they probably derive: as late members of biodegradation processes they may be useful indicators of weathering and ageing, not only of OSPW, but potentially of crude oil residues more generally. Structures of O4 species in OSPW have been identified. This confirms pathways of microbial biodegradation, which were only postulated previously, and may be a further indication that remediation of OSPW toxicity can occur by natural microbial action. The presence and abundance of these diacids might

  3. Diamondoid Structure in a Metal-Organic Framework of Fe4 Single-Molecule Magnets.

    PubMed

    Rigamonti, Luca; Cotton, Carri; Nava, Andrea; Lang, Heinrich; Rüffer, Tobias; Perfetti, Mauro; Sorace, Lorenzo; Barra, Anne-Laure; Lan, Yanhua; Wernsdorfer, Wolfgang; Sessoli, Roberta; Cornia, Andrea

    2016-09-12

    A 3D metal-organic framework (MOF) having single-molecule magnet (SMM) linkers was prepared in crystalline form by using a tetrairon(III) complex functionalised with two divergent pyridyl groups, namely [Fe4 (pPy)2 (dpm)6 ] (1; H3 pPy=2-(hydroxymethyl)-2-(pyridin-4-yl)propane-1,3-diol, Hdpm=dipivaloylmethane). Reaction of 1 with silver(I) perchlorate afforded {[Fe4 (pPy)2 (dpm)6 ]2 Ag}ClO4 (2), which crystallises in a cubic face-centred lattice and exhibits two interlocked diamondoid networks. In 2, the SMMs act as linear ditopic synthons, and silver(I) ions as tetrahedral nodes coordinated by four pyridyl nitrogen atoms. The magnetic properties of 1 (S=5 and D≈-0.4 cm(-1) in the ground spin state) are largely preserved in 2, which shows slow magnetic relaxation with an anisotropy barrier of Ueff /kB =11.46(10) K in zero field and 14.25(8) K in an applied field of 1 kOe. However, crystal symmetry triggers highly noncollinear magnetic anisotropy contributions oriented at 109.47° from each other along the threefold axes of AgN4 tetrahedra, a unique scenario fully confirmed by a single-crystal cantilever torque magnetometry investigation. Magnetisation curves down to 0.03 K demonstrated the occurrence of a wide hysteresis loop when the magnetic field was swept along one of the four Ag-N bonds. By symmetry, the crystalline compound can then be persistently magnetised parallel or antiparallel to the four main diagonals of the unit cell, although the crystals have no overall second-order anisotropy. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Determination of diamondoids in crude oils using gas purge microsyringe extraction with comprehensive two dimensional gas chromatography-time-of-flight mass spectrometry.

    PubMed

    Zhang, Wanfeng; Zhu, Shukui; Pang, Liling; Gao, Xuanbo; Zhu, Gang-Tian; Li, Donghao

    2016-12-23

    Based on a homemade device, gas purge microsyringe extraction (GP-MSE) of crude oil samples was developed for the first time. As a simple, fast, low-cost, sensitive and solvent-saving technique, GP-MSE provides some outstanding advantages over the widely used sample preparation methods for crude oils such as column chromatography (ASTM D2549). Several parameters affecting extraction efficiency were optimized, including extraction temperature, extraction time, extraction solvent, condensing temperature and purge gas flow rate. With the optimized GP-MSE conditions, several real crude oil samples were extracted, and trace diamondoids were determined using comprehensive two dimensional gas chromatography-time-of-flight mass spectrometry (GC×GC-TOFMS). In total, more than 100 diamondoids were detected and 27 marker compounds were identified and quantified accurately. The limits of detection (LODs, S/N=3) were less than 0.08μg/L for all diamondoids. The relative standard deviation (RSD) was below 8%, ranging from 1.1 to 7.6%. The linearity of the developed method was in the range of 0.5-100.0μg/L with correlation coefficients (R(2)) more than 0.996. The recoveries obtained at spiking 50μg/L were between 81 and 108% for diamondoids in crude oil samples. The developed method can also be extended to the analysis of other components in crude oils and other complex matrices. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. Di-heterometalation of thiol-functionalized peptide nucleic acids

    PubMed Central

    Joshi, Tanmaya; Patra, Malay; Spiccia, Leone; Gasser, Gilles

    2013-01-01

    As a proof-of-principle, two hetero-bimetallic PNA oligomers containing a ruthenium(II) polypyridyl and a cyclopentadienyl manganese tricarbonyl complex have been prepared by serial combination of solid-phase peptide coupling and in-solution thiol chemistry. Solid-phase N-terminus attachment of Ru(II)-polypyridyl carboxylic acid derivative, C1, onto the thiol-functionalized PNA backbone (H-a-a-g-t-c-t-g-c-linker-cys-NH2) has been performed by standard peptide coupling method. As two parallel approaches, the strong affinity of thiols for maleimide and haloacetyl group has been exploited for subsequent post-SPPS addition of cymantrene-based organometallic cores, C2 and C3. Michael-like addition and thioether ligation of thiol functionalized PNA1 (H-gly-a-a-g-t-c-t-g-c-linker-cys-NH2) and PNA2 (C1-a-a-g-t-c-t-g-c-linker-cys-NH2) to cymantrene maleimide and chloroacetyl derivatives, C2 and C3, respectively, has been performed. The synthesized ruthenium(II)-cymantrenyl PNA oligomers have been characterized by mass spectrometry (ESI-MS) and IR spectroscopy. The distinct Mn-CO vibrational IR stretches, between 1,924–2,074 cm−1, have been used as markers to confirm the presence of cymantrenyl units in the PNA sequences and the purity of the HPLC-purified PNA thioethers assessed using LC-MS. PMID:23422249

  6. Putting the squeeze on CH4 and CO2 through control over interpenetration in diamondoid nets.

    PubMed

    Elsaidi, Sameh K; Mohamed, Mona H; Wojtas, Lukasz; Chanthapally, Anjana; Pham, Tony; Space, Brian; Vittal, Jagadese J; Zaworotko, Michael J

    2014-04-02

    We report the synthesis, structure, and sorption properties of a family of eight diamondoid (dia) metal-organic materials (MOMs) that are sustained by Co(II) or Zn(II) cations linked by one of three rigid ligands: 4-(2-(4-pyridyl)ethenyl)benzoate (1), 4-(pyridin-4-yl)benzoate (2), and 4-(pyridin-4-yl)acrylate (3). Pore size control in this family of dia nets was exerted by two approaches: changing the length of the linker ligand from 1 to 3, and using solvent as a template to control the level of interpenetration in nets based upon 1 and 3. The resulting MOMs, dia-8i-1, dia-5i-3, dia-7i-1-Zn, dia-7i-1-Co, dia-4i-3-a, dia-4i-3-b, dia-4i-2, and dia-4i-1, exhibit 1D channels with pore limiting diameters (PLDs) of 1.64, 2.90, 5.06, 5.28, 8.57, 8.83, 11.86, and 18.25 Å, respectively. We selected dia nets for this study for the following reasons: their 1D channels facilitate study of the impact of pore size on gas sorption parameters in situations where pore chemistry is similar (pyridyl benzoate-type linkers) or identical (in the case of polymorphs), and their saturated metal centers eliminate open metal sites from dominating sorbent-solvate interactions and possibly masking the effect of pore size. Our data reveal that smaller pore sizes offer stronger interactions, as determined by the isosteric heat of adsorption (Qst) and the steepness of the adsorption isotherm in the low-pressure region. The porous MOM with the smallest PLD suitable for physisorption, dia-7i-1-Co, was thereby found to exhibit the highest Qst values for CO2 and CH4. Indeed, dia-7i-1-Co exhibits a Qst for CH4 of 26.7 kJ/mol, which was validated through grand canonical Monte Carlo simulation studies of CH4 adsorption. This Qst value is considerably higher than those found in covalent organic frameworks and other MOMs with unsaturated metal centers. These results therefore further validate the critical role that PLD plays in gas adsorption by porous MOMs.

  7. Thiol-Based Redox Switches

    PubMed Central

    Groitl, Bastian; Jakob, Ursula

    2014-01-01

    Regulation of protein function through thiol-based redox switches plays an important role in the response and adaptation to local and global changes in the cellular levels of reactive oxygen species (ROS). Redox regulation is used by first responder proteins, such as ROS-specific transcriptional regulators, chaperones or metabolic enzymes to protect cells against mounting levels of oxidants, repair the damage and restore redox homeostasis. Redox regulation of phosphatases and kinases is used to control the activity of select eukaryotic signaling pathways, making reactive oxygen species important second messengers that regulate growth, development and differentiation. In this review we will compare different types of reversible protein thiol modifications, elaborate on their structural and functional consequences and discuss their role in oxidative stress response and ROS adaptation. PMID:24657586

  8. Thiols in a Connecticut Stratified Freshwater Lake

    NASA Astrophysics Data System (ADS)

    Hu, H.; Mylon, S. E.; Benoit, G.

    2003-12-01

    Thiols are an important class of dissolved reduced sulfur (DRS) species in aquatic environments. They are generally formed from biological processes or during diagenesis of biogenic matter. Thiols can affect the biogeochemistry of B-type metals as they form strong complexes that influence trace metal speciation, bioavailability and toxicity. While current literature focuses on the biogeochemistry of thiols in marine systems, little is known about the biogeochemistry of thiols in oxic freshwaters. We chose to study thiols in Linsley Pond a stratified freshwater lake that has been extensively studied by Hutchinson. Our goals were to identify and quantify the range of thiols present throughout this small lake. Additionally, we hoped to discern the environmental factors that influence the production and distribution of thiols in the water column, and to evaluate importance of thiols in trace metal speciation. To identify and quantify various thiols in freshwaters, we adopted a sensitive and selective analytical method, which involves precolumn fluorometric labeling coupled to high performance liquid chromatography and sensitive fluorescence detection. Using this method, our analytical detection limit is below one nanomolar. Among others, two thiol species were observed in Linsley Pond: 3-mercaptopropionic acid (3-MPA) and glutathione (GSH). 3-MPA exists in both oxic and anoxic water layers at nanomolar levels, and increases from surface to bottom. GSH is only detected in subsurface layer and co-varies with Chl a, indicating possible biological sources of GSH in these layers. There is a third, unidentified thiol species which is currently under investigation. The unidentified thiol species appears only in anoxic lake waters, and tests indicate that it is not PC2 (phytochelatin with 2 glutamic acid-cysteine units). Throughout the water column, concentrations of all three thiols are greater in whole water samples than in the dissolved phase (0.45 um).

  9. Thiol/disulfide homeostasis in postmenopausal osteoporosis.

    PubMed

    Korkmaz, V; Kurdoglu, Z; Alisik, M; Turgut, E; Sezgın, O O; Korkmaz, H; Ergun, Y; Erel, O

    2017-04-01

    To evaluate the impact of postmenopausal osteoporosis on thiol/disulfide homeostasis. A total of 75 participants were divided into two groups: Group 1 (n = 40) was composed of healthy postmenopausal women, and group 2 (n = 35) was composed of women with postmenopausal osteoporosis. Clinical findings and thiol/disulfide homeostasis were compared between the two groups. The disulfide/native thiol ratio was 8.6% ± 3.6 in group 1 and 12.7% ± 8.4 in group 2 (p = 0.04). The disulfide/native thiol percent ratio was significantly higher in group 2 after adjustment for the years since menopause and age (p < 0.05). The native thiol/total thiol percent ratio was 85.6% ± 4.8 in group 1 and 73.8% ± 24.9 in group 2 (p = 0.01). The native thiol/total thiol percent ratio was significantly lower in group 2 after adjustment for the years since menopause and age (p < 0.05). Thiol/disulfide homeostasis shifted to the disulfide side independent of age and years since menopause in postmenopausal osteoporosis.

  10. High-Tg Thiol-Click Thermoset Networks via the Thiol-Maleimide Michael Addition.

    PubMed

    Parker, Shelbi; Reit, Radu; Abitz, Haley; Ellson, Gregory; Yang, Kejia; Lund, Benjamin; Voit, Walter E

    2016-07-01

    Thiol-click reactions lead to polymeric materials with a wide range of interesting mechanical, electrical, and optical properties. However, this reaction mechanism typically results in bulk materials with a low glass transition temperature (Tg ) due to rotational flexibility around the thioether linkages found in networks such as thiol-ene, thiol-epoxy, and thiol-acrylate systems. This report explores the thiol-maleimide reaction utilized for the first time as a solvent-free reaction system to synthesize high-Tg thermosetting networks. Through thermomechanical characterization via dynamic mechanical analysis, the homogeneity and Tg s of thiol-maleimide networks are compared to similarly structured thiol-ene and thiol-epoxy networks. While preliminary data show more heterogeneous networks for thiol-maleimide systems, bulk materials exhibit Tg s 80 °C higher than other thiol-click systems explored herein. Finally, hollow tubes are synthesized using each thiol-click reaction mechanism and employed in low- and high-temperature environments, demonstrating the ability to withstand a compressive radial 100 N deformation at 100 °C wherein other thiol-click systems fail mechanically. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Diamond surface functionalization with biomimicry - Amine surface tether and thiol moiety for electrochemical sensors

    NASA Astrophysics Data System (ADS)

    Sund, James B.; Causey, Corey P.; Wolter, Scott D.; Parker, Charles B.; Stoner, Brian R.; Toone, Eric J.; Glass, Jeffrey T.

    2014-05-01

    The surface of conducting diamond was functionalized with a terminal thiol group that is capable of binding and detecting nitrogen-oxygen species. The functionalization process employed multiple steps starting with doped diamond films grown by plasma enhanced chemical vapor deposition followed by hydrogen termination and photochemical attachment of a chemically protected amine alkene. The surface tether was deprotected to reveal the amine functionality, which enabled the tether to be extended with surface chemistry to add a terminal thiol moiety for electrochemical sensing applications. Each step of the process was validated using X-ray photoelectron spectroscopy analysis.

  12. A versatile approach to high-throughput microarrays using thiol-ene chemistry

    NASA Astrophysics Data System (ADS)

    Gupta, Nalini; Lin, Brian F.; Campos, Luis M.; Dimitriou, Michael D.; Hikita, Sherry T.; Treat, Neil D.; Tirrell, Matthew V.; Clegg, Dennis O.; Kramer, Edward J.; Hawker, Craig J.

    2010-02-01

    Microarray technology has become extremely useful in expediting the investigation of large libraries of materials in a variety of biomedical applications, such as in DNA chips, protein and cellular microarrays. In the development of cellular microarrays, traditional high-throughput printing strategies on stiff, glass substrates and non-covalent attachment methods are limiting. We have developed a facile strategy to fabricate multifunctional high-throughput microarrays embedded at the surface of a hydrogel substrate using thiol-ene chemistry. This user-friendly method provides a platform for the immobilization of a combination of bioactive and diagnostic molecules, such as peptides and dyes, at the surface of poly(ethylene glycol)-based hydrogels. The robust and orthogonal nature of thiol-ene chemistry allows for a range of covalent attachment strategies in a fast and reliable manner, and two complementary strategies for the attachment of active molecules are demonstrated.

  13. Attachment Disorganization.

    ERIC Educational Resources Information Center

    Solomon, Judith, Ed.; George, Carol, Ed.

    Disorganized attachment relationships were first formally identified on the basis of the anomalous behavior of some infants during laboratory separations and reunions with the parent. This book presents new research and theory on the topic of attachment disorganization, an area of investigation that is of increasing importance in the study of…

  14. Attachment Disorganization.

    ERIC Educational Resources Information Center

    Solomon, Judith, Ed.; George, Carol, Ed.

    Disorganized attachment relationships were first formally identified on the basis of the anomalous behavior of some infants during laboratory separations and reunions with the parent. This book presents new research and theory on the topic of attachment disorganization, an area of investigation that is of increasing importance in the study of…

  15. Asymmetric synthesis of tertiary thiols and thioethers

    PubMed Central

    MacLellan, Paul

    2011-01-01

    Summary Enantiomerically pure tertiary thiols provide a major synthetic challenge, and despite the importance of chiral sulfur-containing compounds in biological and medicinal chemistry, surprisingly few effective methods are suitable for the asymmetric synthesis of tertiary thiols. This review details the most practical of the methods available. PMID:21647256

  16. Inactivation of Penicillins by Thiol Broth

    PubMed Central

    Murray, Patrick R.; Niles, Ann C.

    1982-01-01

    Thiol broth with sodium polyanetholesulfonate inactivated penicillin G, carbenicillin, nafcillin, oxacillin, and gentamicin, but had no effect on cephalothin, cefoxitin, clindamycin, chloramphenicol, erythromycin, and tetracycline. Only Thiol broth was capable of this inactivation, which was not influenced by the presence of blood. PMID:7153352

  17. Thiol/disulfide homeostasis in asphalt workers.

    PubMed

    Yilmaz, Ömer Hınç; Bal, Ceylan; Neşelioglu, Salim; Büyükşekerci, Murat; Gündüzöz, Meşide; Eren, Funda; Tutkun, Lutfiye; Yilmaz, Fatma Meric

    2016-09-02

    The aim of this study was to investigate thiol/disulfide homeostasis in asphalt workers who are exposed to polycyclic aromatic hydrocarbons occupationally. The study was carried out in 34 nonsmoker asphalt workers. Additionally, 35 healthy nonsmoker volunteers were recruited as control group. Thiol and disulfide concentrations were determined using the novel automated measurement method. Levels of urinary 1-OH-pyrene were analyzed by liquid chromatography. Disulfide/thiol ratio was significantly higher in exposed group (p = .034). Also, a positive correlation was detected between disulfide/thiol ratio and 1-OH-pyrene values (r = .249, p = .036). Thiol/disulfide homeostasis was found to be disturbed in asphalt workers. The novel test used in this study may be useful for evaluating the oxidative status in polycyclic aromatic hydrocarbon (PAH) exposure.

  18. Photoreduction of Hg(II) and photodemethylation of methylmercury: the key role of thiol sites on dissolved organic matter

    USGS Publications Warehouse

    Jeremiason, Jeffrey D.; Portner, Joshua C.; Aiken, George R.; Hiranaka, Amber J.; Dvorak, Michelle T.; Tran, Khuyen T.; Latch, Douglas E.

    2015-01-01

    This study examined the kinetics of photoreduction of Hg(II) and photodemethylation of methylmercury (MeHg+) attached to, or in the presence of, dissolved organic matter (DOM). Both Hg(II) and MeHg+ are principally bound to reduced sulfur groups associated with DOM in many freshwater systems. We propose that a direct photolysis mechanism is plausible for reduction of Hg(II) bound to reduced sulfur groups on DOM while an indirect mechanism is supported for photodemethylation of MeHg+ bound to DOM. UV spectra of Hg(II) and MeHg+ bound to thiol containing molecules demonstrate that the Hg(II)–S bond is capable of absorbing UV-light in the solar spectrum to a much greater extent than MeHg+–S bonds. Experiments with chemically distinct DOM isolates suggest that concentration of DOM matters little in the photochemistry if there are enough reduced S sites present to strongly bind MeHg+ and Hg(II); DOM concentration does not play a prominent role in photodemethylation other than to screen light, which was demonstrated in a field experiment in the highly colored St. Louis River where photodemethylation was not observed at depths ≥10 cm. Experiments with thiol ligands yielded slower photodegradation rates for MeHg+ than in experiments with DOM and thiols; rates in the presence of DOM alone were the fastest supporting an intra-DOM mechanism. Hg(II) photoreduction rates, however, were similar in experiments with only DOM, thiols plus DOM, or only thiols suggesting a direct photolysis mechanism. Quenching experiments also support the existence of an intra-DOM photodemethylation mechanism for MeHg+. Utilizing the difference in photodemethylation rates measured for MeHg+ attached to DOM or thiol ligands, the binding constant for MeHg+ attached to thiol groups on DOM was estimated to be 1016.7.

  19. Electronic and optical properties of pure and modified diamondoids studied by many-body perturbation theory and time-dependent density functional theory

    SciTech Connect

    Demján, Tamás; Vörös, Márton; Palummo, Maurizia; Gali, Adam

    2014-08-14

    Diamondoids are small diamond nanoparticles (NPs) that are built up from diamond cages. Unlike usual semiconductor NPs, their atomic structure is exactly known, thus they are ideal test-beds for benchmarking quantum chemical calculations. Their usage in spintronics and bioimaging applications requires a detailed knowledge of their electronic structure and optical properties. In this paper, we apply density functional theory (DFT) based methods to understand the electronic and optical properties of a few selected pure and modified diamondoids for which accurate experimental data exist. In particular, we use many-body perturbation theory methods, in the G{sub 0}W{sub 0} and G{sub 0}W{sub 0}+BSE approximations, and time-dependent DFT in the adiabatic local density approximation. We find large quasiparticle gap corrections that can exceed thrice the DFT gap. The electron-hole binding energy can be as large as 4 eV but it is considerably smaller than the GW corrections and thus G{sub 0}W{sub 0}+BSE optical gaps are about 50% larger than the Kohn-Sham (KS) DFT gaps. We find significant differences between KS time-dependent DFT and GW+BSE optical spectra on the selected diamondoids. The calculated G{sub 0}W{sub 0} quasiparticle levels agree well with the corresponding experimental vertical ionization energies. We show that nuclei dynamics in the ionization process can be significant and its contribution may reach about 0.5 eV in the adiabatic ionization energies.

  20. 100% thiol-functionalized ethylene PMOs prepared by "thiol acid-ene" chemistry.

    PubMed

    Esquivel, Dolores; van den Berg, Otto; Romero-Salguero, Francisco J; Du Prez, Filip; Van der Voort, Pascal

    2013-03-21

    A novel thiol functionalized bis-silane PMO precursor was synthesized by highly efficient thiol acid-ene chemistry between the double bonds of 1,2-(E)-bis(triethoxysilyl)ethene and thioacetic acid. After aminolysis the self-assembly process of the formed SH-precursor with Pluronic P123 under acidic conditions yields the first 100% thiol-PMO material with good structural ordering.

  1. Role of thiols in cellular response to radiation and drugs. Symposium: thiols

    SciTech Connect

    Biaglow, J.E.; Varnes, M.E.; Clark, E.P.; Epp, E.R.

    1983-09-01

    Cellular nonprotein thiols (NPSH) consist of glutathione (GSH) and other low molecular weight species such as cysteine, cysteamine, and coenzyme. A GSH is usually less than the total cellular NPSH, and with thiol reactive agents, such as diethyl maleate (DEM), its rate of depletion is in part dependent upon the cellular capacity for its resynthesis. If resynthesis is blocked by buthionine-S,R-sulfoximine(BSO), the NPSH, including GSH, is depleted more rapidly, Cellular thiol depletion by diamide, N-ethylmaleimide, and BSO may render oxygenated cells more sensitive to radiation. These cells may or may not show a reduction in the oxygen enhancement ratio (OER). Human A549 lung carcinoma cells depleted of their NPSH either by prolonged culture or by BSO treatment do not show a reduced OER but do show increased aerobic responses to radiation. Other nitrocompounds, such as misonidazole, are activated under hypoxic conditions to radical intermediates. When cellular thiols are depleted peroxide is formed. Under hypoxic conditions thiols are depleted because metabolically reduced intermediates react with GSH instead of oxygen. Thiol depletion, under hypoxic conditions, may be the reason that misonidazole and other nitrocompounds show an extra enhancement ratio with hypoxic cells. Thiol depletion by DEM or BSO alters the radiation response of hypoxic cells to misonidazole. In conclusion, we propose an altered thiol model which includes a mechanism for thiol involvement in the aerobic radiation response of cells.

  2. Thiol-induced discharge of acontial nematocytes.

    PubMed

    La Spada, Giuseppina; Sorrenti, Giuseppe; Soffli, Andrea; Montaleone, Bruno; Marino, Angela; Musci, Giovanni

    2002-06-01

    The discharge of nematocytes, the stinging cells of Coelenterata, is a poorly understood phenomenon. In particular, little is known about the chemical stimuli that trigger the discharge. In this paper, we show that thiols are able to initiate the nematocyst discharge in isolated nematocytes. Among the thiols tested, reduced glutathione and cysteine were found to be the most effective. The effect of glutathione was likely two-fold: it formed mixed disulfides with membrane thiols, as shown by the ability of the mercapto-blocking reagent iodoacetamide to abolish its action; and it bound to the membrane through the glutamate moiety, as demonstrated by competitive experiments with free glutamate. Glutathione triggered the discharge at concentrations higher than those sufficient to activate the feeding response of Coelenterates. However, our results demonstrate for the first time that the modification of membrane thiols by selective agents may be a key event in the discharge of nematocytes.

  3. Evolution of thiol protective systems in prokaryotes

    NASA Technical Reports Server (NTRS)

    Fahey, R. C.; Newton, G. L.

    1986-01-01

    Biological thiols are essential elements in most aspects of cell function but undergo rapid oxidation to disulfides in the presence of oxygen. The evolution of systems to protect against such oxygen toxicity was essential to the emergence of aerobic life. The protection system used by eukaryotes is based upon glutathione (GSH) and GSH-dependent enzymes but many bacteria lack GSH and apparently use other mechanisms. The objective of this research is to elaborate the thiol protective mechanisms employed by prokaryotes of widely divergent evolutionary origin and to understand why GSH became the central thiol employed in essentially all higher organisms. Thiol-selective fluorescent labeling and HPLC analysis has been used to determine key monothiol components.

  4. Evolution of thiol protective systems in prokaryotes

    NASA Technical Reports Server (NTRS)

    Fahey, R. C.; Newton, G. L.

    1986-01-01

    Biological thiols are essential elements in most aspects of cell function but undergo rapid oxidation to disulfides in the presence of oxygen. The evolution of systems to protect against such oxygen toxicity was essential to the emergence of aerobic life. The protection system used by eukaryotes is based upon glutathione (GSH) and GSH-dependent enzymes but many bacteria lack GSH and apparently use other mechanisms. The objective of this research is to elaborate the thiol protective mechanisms employed by prokaryotes of widely divergent evolutionary origin and to understand why GSH became the central thiol employed in essentially all higher organisms. Thiol-selective fluorescent labeling and HPLC analysis has been used to determine key monothiol components.

  5. Functionalized 3D Architected Materials via Thiol-Michael Addition and Two-Photon Lithography.

    PubMed

    Yee, Daryl W; Schulz, Michael D; Grubbs, Robert H; Greer, Julia R

    2017-04-01

    Fabrication of functionalized 3D architected materials is achieved by a facile method using functionalized acrylates synthesized via thiol-Michael addition, which are then polymerized using two-photon lithography. A wide variety of functional groups can be attached, from Boc-protected amines to fluoroalkanes. Modification of surface wetting properties and conjugation with fluorescent tags are demonstrated to highlight the potential applications of this technique. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Thiol-based redox switches in prokaryotes.

    PubMed

    Hillion, Melanie; Antelmann, Haike

    2015-05-01

    Bacteria encounter reactive oxygen species (ROS) as a consequence of the aerobic life or as an oxidative burst of activated neutrophils during infections. In addition, bacteria are exposed to other redox-active compounds, including hypochloric acid (HOCl) and reactive electrophilic species (RES) such as quinones and aldehydes. These reactive species often target the thiol groups of cysteines in proteins and lead to thiol-disulfide switches in redox-sensing regulators to activate specific detoxification pathways and to restore the redox balance. Here, we review bacterial thiol-based redox sensors that specifically sense ROS, RES and HOCl via thiol-based mechanisms and regulate gene transcription in Gram-positive model bacteria and in human pathogens, such as Staphylococcus aureus and Mycobacterium tuberculosis. We also pay particular attention to emerging widely conserved HOCl-specific redox regulators that have been recently characterized in Escherichia coli. Different mechanisms are used to sense and respond to ROS, RES and HOCl by 1-Cys-type and 2-Cys-type thiol-based redox sensors that include versatile thiol-disulfide switches (OxyR, OhrR, HypR, YodB, NemR, RclR, Spx, RsrA/RshA) or alternative Cys phosphorylations (SarZ, MgrA, SarA), thiol-S-alkylation (QsrR), His-oxidation (PerR) and methionine oxidation (HypT). In pathogenic bacteria, these redox-sensing regulators are often important virulence regulators and required for adapation to the host immune defense.

  7. Thiol-based redox switches in prokaryotes

    PubMed Central

    Hillion, Melanie; Antelmann, Haike

    2015-01-01

    Summary Bacteria encounter reactive oxygen species (ROS) as consequence of the aerobic life or as oxidative burst of activated neutrophils during infections. In addition, bacteria are exposed to other redox-active compounds including hypochloric acid (HOCl) and reactive electrophilic species (RES), such as quinones and aldehydes. These reactive species often target the thiol groups of cysteines in proteins and lead to thiol-disulfide switches in redox-sensing regulators to activate specific detoxification pathways and to restore the redox balance. Here, we review bacterial thiol-based redox sensors that specifically sense ROS, RES and HOCl via thiol-based mechanisms and regulate gene transcription in Gram-positive model bacteria and in human pathogens, such as Staphylococcus aureus and Mycobacterium tuberculosis. We also pay particular attention to emerging widely conserved HOCl-specific redox regulators that have been recently characterized in Escherichia coli. Different mechanisms are used to sense and respond to ROS, RES and HOCl by 1-Cys-type and 2-Cys-type thiol-based redox sensors that include versatile thiol-disulfide switches (OxyR, OhrR, HypR, YodB, NemR, RclR, Spx, RsrA/RshA) or alternative Cys-phosphorylations (SarZ, MgrA, SarA), thiol-S-alkylation (QsrR), His-oxidation (PerR) and methionine oxidation (HypT). In pathogenic bacteria, these redox-sensing regulators are often important virulence regulators and required for adapation to the host immune defense. PMID:25720121

  8. Diamondoid Characterization in Condensate by Comprehensive Two-Dimensional Gas Chromatography with Time-of-Flight Mass Spectrometry: The Junggar Basin of Northwest China

    PubMed Central

    Li, Shuifu; Hu, Shouzhi; Cao, Jian; Wu, Ming; Zhang, Dongmei

    2012-01-01

    Diamondoids in crude oil are useful for assessing the maturity of oil in high maturation. However, they are very difficult to separate and accurately quantify by conventional geochemical methods due to their low abundance in oil. In this paper, we use comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC×GC-TOFMS) to study the compounds in condensates from the Junggar Basin of northwest China and address their geological and geochemical applications. GC×GC-TOFMS improves the resolution and separation efficiency of the compounds. It not only separates the compounds that coelute in conventional GC-MS (e.g., 4, 8-dimethyl-diamantane and trimethyl-diamantane) but also allows the identification of compounds that were not previously detected (e.g., trimethyl-diamantane (15A)). A reversed-phase column system improves the separation capabilities over the normal phase column system. The diamondoid indexes indicate that a representative condensate from Well DX 10 is highly mature with equivalent Ro being approximately 1.5%. PMID:23109861

  9. Diamondoid characterization in condensate by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry: The Junggar Basin of Northwest China.

    PubMed

    Li, Shuifu; Hu, Shouzhi; Cao, Jian; Wu, Ming; Zhang, Dongmei

    2012-01-01

    Diamondoids in crude oil are useful for assessing the maturity of oil in high maturation. However, they are very difficult to separate and accurately quantify by conventional geochemical methods due to their low abundance in oil. In this paper, we use comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC×GC-TOFMS) to study the compounds in condensates from the Junggar Basin of northwest China and address their geological and geochemical applications. GC×GC-TOFMS improves the resolution and separation efficiency of the compounds. It not only separates the compounds that coelute in conventional GC-MS (e.g., 4, 8-dimethyl-diamantane and trimethyl-diamantane) but also allows the identification of compounds that were not previously detected (e.g., trimethyl-diamantane (15A)). A reversed-phase column system improves the separation capabilities over the normal phase column system. The diamondoid indexes indicate that a representative condensate from Well DX 10 is highly mature with equivalent Ro being approximately 1.5%.

  10. Liquid—liquid interface-mediated Au—ZnO composite membrane using ‘thiol-ene’ click chemistry

    NASA Astrophysics Data System (ADS)

    Ali, Mohammed; Ghosh, Sujit Kumar

    2015-07-01

    A nanoparticle-decorated composite membrane has been devised at the water/CCl4 interface based on the self-assembly of ligand-stabilized gold and zinc oxide nanoparticles, exploiting the ‘thiol-ene’ click chemistry between the thiol groups of 11-mercaptoundecanoic acid-stabilized ZnO nanoparticles and the ene functionality of cinnamic acid attached to gold nanoparticles. The interfacial assembly of ultrasmall particles leads to a multilayer film that exhibits charge-dependent permeability of amino acid molecules across the membrane.

  11. Synthesis of soybean oil-based thiol oligomers.

    PubMed

    Wu, Jennifer F; Fernando, Shashi; Weerasinghe, Dimuthu; Chen, Zhigang; Webster, Dean C

    2011-08-22

    Industrial grade soybean oil (SBO) and thiols were reacted to generate thiol-functionalized oligomers via a thermal, free radical initiated thiol-ene reaction between the SBO double bond moieties and the thiol functional groups. The effect of the reaction conditions, including thiol concentration, catalyst loading level, reaction time, and atmosphere, on the molecular weight and the conversion to the resultant soy-thiols were examined in a combinatorial high-throughput fashion using parallel synthesis, combinatorial FTIR, and rapid gel permeation chromatography (GPC). High thiol functionality and concentration, high thermal free radical catalyst concentration, long reaction time, and the use of a nitrogen reaction atmosphere were found to favor fast consumption of the SBO, and produced high molecular weight products. The thiol conversion during the reaction was inversely affected by a high thiol concentration, but was favored by a long reaction time and an air reaction atmosphere. These experimental observations were explained by the initial low affinity of the SBO and thiol, and the improved affinity between the generated soy-thiol oligomers and unreacted SBO during the reaction. The synthesized soy-thiol oligomers can be used for renewable thiol-ene UV curable materials and high molecular solids and thiourethane thermal cure materials.

  12. Attachment Apparatus

    SciTech Connect

    Morrison, Edward F.

    1998-08-18

    The present invention includes an attachment apparatus comprising a rotation limiting member adapted to be threaded onto a threaded member; and a preload nut adapted to be threaded onto the threaded member. The rotation limiting member comprises a plurality of pins; and the preload nut comprises plurality of slots, preferably wherein the plurality of pins and the plurality of slots are the same in number, which is preferably three. The plurality of pins of the rotation limiting member are filled into a corresponding plurality of slots of the preload nut to form a rotatable unit adapted to be threaded onto the threaded member. In use, the rotatable unit is threaded onto the threaded member. The present invention thus provides a unitized removable device for holes, including holes other than circular in shape, which have an established depth before an end of, or before an enlargement of the hole. The configuration of some exposed part of the device, or the head, is shaped and formed for its intended purpose, such as clamping, anchor points, eye bolts, stud anchor, and the like. The device allows for the installation, preloading and removal of all components of the device, as a unit, without damage to the member for which attachment is required by simple rotations of some exposed part of the device.

  13. Nuclear thiol redox systems in plants.

    PubMed

    Delorme-Hinoux, Valérie; Bangash, Sajid A K; Meyer, Andreas J; Reichheld, Jean-Philippe

    2016-02-01

    Thiol-disulfide redox regulation is essential for many cellular functions in plants. It has major roles in defense mechanisms, maintains the redox status of the cell and plays structural, with regulatory roles for many proteins. Although thiol-based redox regulation has been extensively studied in subcellular organelles such as chloroplasts, it has been much less studied in the nucleus. Thiol-disulfide redox regulation is dependent on the conserved redox proteins, glutathione/glutaredoxin (GRX) and thioredoxin (TRX) systems. We first focus on the functions of glutathione in the nucleus and discuss recent data concerning accumulation of glutathione in the nucleus. We also provide evidence that glutathione reduction is potentially active in the nucleus. Recent data suggests that the nucleus is enriched in specific GRX and TRX isoforms. We discuss the biochemical and molecular characteristics of these isoforms and focus on genetic evidences for their potential nuclear functions. Finally, we make an overview of the different thiol-based redox regulated proteins in the nucleus. These proteins are involved in various pathways including transcriptional regulation, metabolism and signaling. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

  14. Distribution and abundance of organic thiols

    NASA Technical Reports Server (NTRS)

    Fahey, R.

    1985-01-01

    The role of glutathione (GSH) in protecting against the toxicity of oxygen and oxygen by products is well established for all eukaryotes studied except Entamoeba histolytica which lacks mitochrondria, chloroplasts, and microtubules. The GSH is not universal among prokaryotes. Entamoeba histolytica does not produce GSH or key enzymes of GSH metabolism. A general method of thiol analysis based upon fluorescent labeling with monobromobimane and HPLC separation of the resulting thiol derivatives was developed to determine the occurrence of GSH and other low molecular weight thiols in bacteria. Glutathione is the major thiol in cyanobacteria and in most bacteria closely related to the purple photosynthetic bacteria, but GSH was not found in archaebacteria, green bacteria, or GRAM positive bacteria. It suggested that glutathione metabolism was incorporated into eukaryotes at the time that mitochondria and chloroplasts were acquired by endosymbiosis. In Gram positive aerobes, coenzyme A occurs at millimolar levels and CoA disulfide reductases are identified. The CoA, rather than glutathione, may function in the oxygen detoxification processes of these organisms.

  15. A Search for Interstellar Monohydric Thiols

    NASA Astrophysics Data System (ADS)

    Gorai, Prasanta; Das, Ankan; Das, Amaresh; Sivaraman, Bhalamurugan; Etim, Emmanuel E.; Chakrabarti, Sandip K.

    2017-02-01

    It has been pointed out by various astronomers that a very interesting relationship exists between interstellar alcohols and the corresponding thiols (sulfur analog of alcohols) as far as the spectroscopic properties and chemical abundances are concerned. Monohydric alcohols such as methanol and ethanol are widely observed and 1-propanol was recently claimed to have been seen in Orion KL. Among the monohydric thiols, methanethiol (chemical analog of methanol) has been firmly detected in Orion KL and Sgr B2(N2) and ethanethiol (chemical analog of ethanol) has been observed in Sgr B2(N2), though the confirmation of this detection is yet to come. It is very likely that higher order thiols could be observed in these regions. In this paper, we study the formation of monohydric alcohols and their thiol analogs. Based on our quantum chemical calculation and chemical modeling, we find that the Tg conformer of 1-propanethiol is a good candidate of astronomical interest. We present various spectroscopically relevant parameters of this molecule to assist in its future detection in the interstellar medium.

  16. Microfluidic devices using thiol-ene polymers

    NASA Astrophysics Data System (ADS)

    Bou, Simon J. M. C.; Ellis, Amanda V.

    2013-12-01

    Here, a new polymeric microfluidic platform using off-stoichiometric thiol-ene (OSTE) polymers was developed. Thiolene polymers were chosen as they afford rapid UV curing, low volume shrinkage and optical transparency for use in microfluidic devices. Three different off-stoichiometric thiol-ene polymers with 30% excess allyl, 50% excess thiol and a 90% excess thiol (OSTE Allyl-30, OSTE-50 and OSTE-90, respectively) were fabricated. Attenuated reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and solid-state cross polarisation-magic angle spinning (CP-MAS) nuclear magnetic resonance (NMR) spectroscopy confirmed which functional groups (thiol or allyl) were present in excess in the OSTE polymers. The polymers were shown to have a more hydrophilic surface (water contact angle of 65°+/- 3) compared to polydimethylsiloxane (water contact angle of 105° +/- 5). Testing of the mechanical properties showed the glass transition temperatures to be 15.09 °C, 43.15 °C and, 57.48 °C for OSTE-90, OSTE Allyl-30 and, OSTE-50, respectively. The storage modulus was shown to be less than 10 MPa for the OSTE-90 polymer and approximately 1750 MPa for the OSTE Allyl-30 and OSTE-50 polymers. The polymers were then utilised to fabricate microfluidic devices via soft lithography practices and devices sealed using a one-step UV lamination "click" reaction technique. Finally, gold nanoparticles were used to form gold films on the OSTE-90 and OSTE-50 polymers as potential electrodes. Atomic force microscopy and sheet resistances were used to characterise the films.

  17. The versatile low-molecular-weight thiols: Beyond cell protection.

    PubMed

    Wang, Min; Zhao, Qunfei; Liu, Wen

    2015-12-01

    Low-molecular-weight (LMW) thiols are extensively involved in the maintenance of cellular redox potentials and the protection of cells from a variety of reactive chemical and electrophilic species. However, we recently found that the metabolic coupling of two LMW thiols - mycothiol (MSH) and ergothioneine (EGT) - programs the biosynthesis of the anti-infective agent lincomycin A. Remarkably, such a constructive role of the thiols in the biosynthesis of natural products has so far received relatively little attention. We speculate that the unusual thiol EGT might function as a chiral thiolation carrier (for modification) and a novel activator (for glycosylation) of sugar. Additionally, we examine recent evidence for LMW thiols (MSH and others) as sulfur donors of sulfur-containing natural products. Clearly, the LMW thiols have more diverse activities beyond cell protection, and more attention should be paid to the correlation of their functions with thiol-dependent enzymes.

  18. Pathways of peroxynitrite oxidation of thiol groups.

    PubMed

    Quijano, C; Alvarez, B; Gatti, R M; Augusto, O; Radi, R

    1997-02-15

    Peroxynitrite mediates the oxidation of the thiol group of both cysteine and glutathione. This process is associated with oxygen consumption. At acidic pH and a cysteine/peroxynitrite molar ratio of < or = 1.2, there was a single fast phase of oxygen consumption, which increased with increasing concentrations of both cysteine and oxygen. At higher molar ratios the profile of oxygen consumption became biphasic, with a fast phase (phase I) that decreased with increasing cysteine concentration, followed by a slow phase (phase II) whose rate of oxygen consumption increased with increasing cysteine concentration. Oxygen consumption in phase I was inhibited by desferrioxamine and 5,5-dimethyl-1-pyrroline N-oxide, but not by mannitol; superoxide dismutase also inhibited oxygen consumption in phase I, while catalase added during phase II decreased the rate of oxygen consumption. For both cysteine and glutathione, oxygen consumption in phase I was maximal at neutral to acidic pH: in contrast, total thiol oxidation was maximal at alkaline pH. EPR spin-trapping studies using N-tert-butyl-alpha-phenylnitrone indicated that the yield of thiyl radical adducts had a pH profile comparable with that found for oxygen consumption. The apparent second-order rate constants for the reactions of peroxynitrite with cysteine and glutathione were 1290 +/- 30 M-1.S-1 and 281 +/- 6 M-1.S-1 respectively at pH 5.75 and 37 degrees C. These results are consistent with two different pathways participating in the reaction of peroxynitrite with low-molecular-mass thiols: (a) the reaction of the peroxynitrite anion with the protonated thiol group, in a second-order process likely to involve a two-electron oxidation, and (b) the reaction of peroxynitrous acid, or a secondary species derived from it, with the thiolate in a one-electron transfer process that yields thiyl radicals capable of initiating an oxygen-dependent radical chain reaction.

  19. Pathways of peroxynitrite oxidation of thiol groups.

    PubMed Central

    Quijano, C; Alvarez, B; Gatti, R M; Augusto, O; Radi, R

    1997-01-01

    Peroxynitrite mediates the oxidation of the thiol group of both cysteine and glutathione. This process is associated with oxygen consumption. At acidic pH and a cysteine/peroxynitrite molar ratio of < or = 1.2, there was a single fast phase of oxygen consumption, which increased with increasing concentrations of both cysteine and oxygen. At higher molar ratios the profile of oxygen consumption became biphasic, with a fast phase (phase I) that decreased with increasing cysteine concentration, followed by a slow phase (phase II) whose rate of oxygen consumption increased with increasing cysteine concentration. Oxygen consumption in phase I was inhibited by desferrioxamine and 5,5-dimethyl-1-pyrroline N-oxide, but not by mannitol; superoxide dismutase also inhibited oxygen consumption in phase I, while catalase added during phase II decreased the rate of oxygen consumption. For both cysteine and glutathione, oxygen consumption in phase I was maximal at neutral to acidic pH: in contrast, total thiol oxidation was maximal at alkaline pH. EPR spin-trapping studies using N-tert-butyl-alpha-phenylnitrone indicated that the yield of thiyl radical adducts had a pH profile comparable with that found for oxygen consumption. The apparent second-order rate constants for the reactions of peroxynitrite with cysteine and glutathione were 1290 +/- 30 M-1.S-1 and 281 +/- 6 M-1.S-1 respectively at pH 5.75 and 37 degrees C. These results are consistent with two different pathways participating in the reaction of peroxynitrite with low-molecular-mass thiols: (a) the reaction of the peroxynitrite anion with the protonated thiol group, in a second-order process likely to involve a two-electron oxidation, and (b) the reaction of peroxynitrous acid, or a secondary species derived from it, with the thiolate in a one-electron transfer process that yields thiyl radicals capable of initiating an oxygen-dependent radical chain reaction. PMID:9078258

  20. Thiol X Click Foldamers for Polymer Affinity

    DTIC Science & Technology

    2016-06-24

    Research Triangle Park, NC 27709-2211 Thiol-X chemistry , nucleic acids, dynamic thioester polymers REPORT DOCUMENTATION PAGE 11. SPONSOR/MONITOR’S...of Complex, Controlled Polymer Structures from Efficient Chemistries " Invited Lectures Presented at Cornell University, High Polymer Research Group... Chemistry 0.00 1 NAME Total Number: NAME Total Number: Weixian Xi Chen Wang 2 ...... ...... Sub Contractors (DD882) Names of other research staff

  1. Detection of thiol modifications by hydrogen sulfide.

    PubMed

    Williams, E; Pead, S; Whiteman, M; Wood, M E; Wilson, I D; Ladomery, M R; Teklic, T; Lisjak, M; Hancock, J T

    2015-01-01

    Hydrogen sulfide (H2S) is an important gasotransmitter in both animals and plants. Many physiological events, including responses to stress, have been suggested to involve H2S, at least in part. On the other hand, numerous responses have been reported following treatment with H2S, including changes in the levels of antioxidants and the activities of transcription factors. Therefore, it is important to understand and unravel the events that are taking place downstream of H2S in signaling pathways. H2S is known to interact with other reactive signaling molecules such as reactive oxygen species (ROS) and nitric oxide (NO). One of the mechanisms by which ROS and NO have effects in a cell is the modification of thiol groups on proteins, by oxidation or S-nitrosylation, respectively. Recently, it has been reported that H2S can also modify thiols. Here we report a method for the determination of thiol modifications on proteins following the treatment with biological samples with H2S donors. Here, the nematode Caenorhabditis elegans is used as a model system but this method can be used for samples from other animals or plants. © 2015 Elsevier Inc. All rights reserved.

  2. Thiols as myeloperoxidase-oxidase substrates.

    PubMed Central

    Svensson, B E

    1988-01-01

    Nine low-Mr thiols were compared with regard to their ability to function as myeloperoxidase-oxidase substrates under conditions where no auto-oxidation of the thiols could be observed. The methyl and ethyl esters of cysteine were found to be about twice as active as cysteamine at pH 7.0, in terms of increased O2 consumption. Cysteine itself was poorly active, whereas glutathione, N-acetylcysteine and penicillamine were completely inactive as myeloperoxidase-oxidase substrates under these conditions. The structure-activity relationships indicated that both a free thiol and free amino group were required for peroxidase-oxidase activity, and also that a free carboxy group abolished activity. In analogy with cysteamine, the activities of both cysteine esters were inhibited by superoxide dismutase (less than 5 micrograms/ml) and by catalase and not by the hydroxyl-radical scavenger mannitol. In contrast with cysteamine, the activities of both cysteine esters were stimulated more than 2-fold by high concentrations (greater than 5 micrograms/ml) of superoxide dismutase. The activities of both cysteine esters exhibited broad pH optima at pH 7. A mechanism for the myeloperoxidase-oxidase oxidation of the cysteine esters is proposed, which is partly different from that previously proposed for cysteamine. PMID:2845919

  3. Paternal Attachment, Parenting Beliefs and Children's Attachment

    ERIC Educational Resources Information Center

    Howard, Kimberly S.

    2010-01-01

    Relationships between fathers' romantic attachment style, parenting beliefs and father-child attachment security and dependence were examined in a diverse sample of 72 fathers of young children. Paternal romantic attachment style was coded based on fathers' endorsement of a particular style represented in the Hazan and Shaver Three-Category…

  4. Paternal Attachment, Parenting Beliefs and Children's Attachment

    ERIC Educational Resources Information Center

    Howard, Kimberly S.

    2010-01-01

    Relationships between fathers' romantic attachment style, parenting beliefs and father-child attachment security and dependence were examined in a diverse sample of 72 fathers of young children. Paternal romantic attachment style was coded based on fathers' endorsement of a particular style represented in the Hazan and Shaver Three-Category…

  5. Surface modification of cyclomatrix polyphosphazene microsphere by thiol-ene chemistry and lectin recognition

    NASA Astrophysics Data System (ADS)

    Chen, Chen; Zhu, Xue-yan; Gao, Qiao-ling; Fang, Fei; Huang, Xiao-jun

    2016-11-01

    A new synthetic route leading to functional polyphosphazene cyclomatrix microsphere has been developed via thiol-ene click modification. Hexacholorocyclophosphazene (HCCP) was crosslinked with both bisphenol-S and 4,4‧-diallyl bisphenol-S to obtain vinyl polyphosphazene microspheres (VPZM) in order to ensure high crosslinking degree and introduce vinyl moieties. Compared to the microspheres obtained by HCCP and bisphenol-S, the size of VPZM was broadly dispersed from 400 nm to 1.40 μm. Thiol-ene click reactions were carried out to attach functional groups, such as glucosyl, carboxyl, ester and dodecyl groups onto polyphosphazene microspheres, which demonstrated no change in morphology and size after modification. Solid state NMR (SSNMR) and Fourier transform infrared spectoscopy (FT-IR) results showed that the vinyl moieties were introduced in the period of crosslinking and functionalization was also successful via click reactions. Moreover, the microspheres presented a little difference in thermal properties after modification. Concanavalin A (Con-A) fluorescent adsorption was also observed for glucosyl microspheres. Thus, the thiol-ene modified polyphosphazene microspheres displayed chemical flexibility in post-functionalization. These microspheres can be potentially applicated in enzyme immobilization, protein adsorption and chromatographic separation.

  6. Infection free titanium alloys by stabile thiol based nanocoating.

    PubMed

    Cökeliler, Dilek; Göktaş, Hilal; Tosun, Pinar Deniz; Mutlu, Selma

    2010-04-01

    As biomedical materials, titanium and titanium alloys (Ti-6Al-4V) are superior to many materials in terms of mechanical properties and biocompatibility. However, they are still not sufficient for prolonged clinical use because the biocompatibility of these materials must be improved. In this study, the prevention of the attachment of test microorganism on the Ti alloy surfaces by thiol (-SH) and hydroxyl (-OH) functional group containing monomer in plasma based electron beam generator was reported in order to prepare anti-fouling surfaces. The precursor, 11-mercaptoundecanoic acid is used as plasma source to create nano-film with 30-60 nm approximately. The surface chemistry and topology of uncoated and coated samples are characterized by Fourier Transform Infrared Spectroscopy (FTIR) and Atomic Force Microscopy (AFM). Static contact angle measurements are performed to state the change of surface hydrophilicity. All coated samples are tested in-vitro environment with Staphylococcus epidermidis that is chosen as the test bacteria strain in view of its significance for the pathogenesis of medical-device-related infections. This test is repeated after certain period of times and samples are waited in dynamic fluid media in order to investigate the stability of nano-coating. Plasma polymerized 11-mercaptoundecanoic acid film (PP MUA) with 42 +/- 4 nm is found alternative, stabile and simple method to create bacterial anti-fouling surfaces. The static contact angle of the coated surface is 34 +/- 80 whereas the uncoated surface is 57 +/- 50. For the coated surface, the presence of C-OH and C==O groups in infrared spectra defining the PP MUA is achieved by the plasma polymerization. The attachment of the model microorganism on the biomaterial surface prepared by PP MUA is reduced 85.3% if compared to unmodified control surface.

  7. Recent advances in thiol and sulfide reactive probes.

    PubMed

    Wang, Ke; Peng, Hanjing; Wang, Binghe

    2014-06-01

    Because of the biological relevance of thiols and sulfides such as cysteine, homocysteine, glutathione and hydrogen sulfide, their detection has attracted a great deal of research interest. Fluorescent probes are emerging as a new strategy for thiol and hydrogen sulfide analysis due to their high sensitivity, low cost, and ability to detect and image thiols in biological samples. In this short review, we have summarized recent advances in the development of thiol and hydrogen sulfide reactive fluorescent probes. These probes are compared and contrasted with regard to their designing strategies, mechanisms, photophysical properties, and/or reaction kinetics. Biological applications of these probes are also discussed.

  8. [Chemical approaches for trapping protein thiols and their oxidative modification].

    PubMed

    Huang, Chu-Sen; Zhu, Wei-Ping; Xu, Yu-Fang; Qian, Xu-Hong

    2012-03-01

    Redox signal transduction, especially the oxidative modification of proein thiols, correlates with many diseases and becomes an expanding research area. However, there was rare method for quick and specific detection of protein thiols and their oxidative modification in living cells. In this article, we review the current chemical strategies for the detection and quantification of protein thiols and related cysteine oxidation. We also look into the future of the development of fluorescent probes for protein thiols and their potential application in the research of reactive cysteine proteomes and early detection of redox-related diseases.

  9. A Novel Oxidative Stress Mediator in Acute Appendicitis: Thiol/Disulphide Homeostasis

    PubMed Central

    Turan, Umit; Kuvvetli, Adnan; Kilavuz, Huseyin; Karakaya, Burak; Ozaltun, Pınar; Alısık, Murat; Erel, Ozcan

    2016-01-01

    Aim. To investigate the role of a novel oxidative stress marker, thiol/disulphide homeostasis, in patients diagnosed with acute appendicitis (AA). Methods. In this study, seventy-one (43 male and 28 female) patients diagnosed with AA and 71 (30 male and 41 female) healthy volunteers were included. Age, gender, body mass index (BMI), haemoglobin (Hb), white blood cell (WBC), c-reactive protein (CRP), and thiol/disulphide homeostasis parameters (native thiol, total thiol, disulphide, disulphide/native thiol, native thiol/total thiol, and disulphide/total thiol ratios) were compared between the groups. Thiol/disulphide homeostasis was determined by a newly developed method by Erel and Neselioglu. Results. The native thiol, total thiol, and the native thiol/total thiol ratio levels were statistically significantly decreased in the AA compared with the control group (p < 0.001). Disulphide level and the ratios of disulphide/native thiol and disulphide/total thiol were higher in the AA group than in the control group (p < 0.001). There was a negative correlation of CRP with native thiol, total thiol, and native thiol/total thiol ratio while there was a positive correlation of CRP with disulphide/native thiol and disulphide/total thiol in the AA group. In the stepwise regression model, risk factors as disulphide/native thiol (OR = 1.368; p = 0.018) and CRP (OR = 1.635; p = 0.003) were determined as predictors of perforated appendicitis compared to the nonperforated group. Conclusion. This is the first study examining the thiol/disulphide homeostasis as a diagnostic aid in AA and establishing thiol/disulphide homeostatis balance shifted towards the disulphide formation due to thiol oxidation. Further studies are needed to optimize the use of this novel oxidative stress marker in AA. PMID:27642237

  10. Electron-attachment processes

    NASA Astrophysics Data System (ADS)

    Christophorou, L. G.; McCorkle, D. L.; Christodoulides, A. A.

    Topics covered include: modes of production of negative ions, techniques for the study of electron attachment processes, dissociative electron attachment to ground state molecules, dissociative electron attachment to hot molecules (effects of temperature on dissociative electron attachment), molecular parent negative ions, and negative ions formed by ion pair processes and by collisions of molecules with ground state and Rydberg atoms.

  11. Dynamic thiol-disulfide homeostasis in acute ischemic stroke patients.

    PubMed

    Bektas, Hesna; Vural, Gonul; Gumusyayla, Sadiye; Deniz, Orhan; Alisik, Murat; Erel, Ozcan

    2016-12-01

    Dynamic thiol-disulfide homeostasis plays a critical role in the cellular protection provided by antioxidation. The aim of this study was to investigate whether there is a change in thiol-disulfide homeostasis in acute ischemic stroke patients. Patients diagnosed with acute ischemic stroke that had undergone magnetic resonance diffusion-weighted imaging within the first 24 h were prospectively included in this study. The thiol, disulfide, and total thiol levels were measured during the first 24 and 72 h, and the National Institutes of Health Stroke Scale (NIHSS), modified Rankin Scale (mRS), and Barthel Index (BI) of the patients were recorded. Overall, the relationships between the thiol-disulfide levels of the patients and the infarct volumes, NIHSS, mRS, and BI scores were investigated. In this study, 54 patients and 53 healthy controls were included. The mean of the native thiol levels in the stroke group was 356.572 ± 61.659 μmol/L (min/max 228.00/546.40), while it was 415.453 ± 39.436 μmol/L (min/max 323.50/488.70) in the control group (p < 0.001). A negative, significant correlation was observed between the infarct volumes and native thiol levels (ρ = -0.378; p = 0.005), and the disulfide levels were similar between the groups (Z = 0.774; p = 0.439). Significant difference was found between the thiol levels of the mild and moderate-severe NIHSS groups (p = 0.026). The changes in the thiol levels under oxidative stress may be associated with the severity of the stroke. Substitution of thiol deficiency and correction of thiol-disulfide imbalance may be beneficial in ischemic stroke.

  12. Role of endogenous thiols in protection

    NASA Astrophysics Data System (ADS)

    Vos, O.

    Aminothiols represent the most important group of radioprotective compounds. The most effective compounds administered at an optimal dose and time before irradiation are able to provide a protection in mice with a dose reduction factor (DRF) of about 2-2.5. The working mechanism can partly be explained as a scavenging process of radicals induced in water and partly as a chemical repair process of injured DNA. The endogenous aminothiol which has far-out the highest intracellular concentration is glutathione (GSH). The importance of intracellular GSH in determining cellular radiosensitivity has been shown by irradiating cells that had very low GSH levels. Such cells appear to have a high radiosensitivity, especially in hypoxic conditions. On the other hand, it has been demonstrated that induction of a high GSH level (100-200% above the normal level) provides only a small protection. In vitro experiments with DNA indicate that thiols with a high positive charge condense in the vicinity of DNA and are effective protectors, whereas thiols with a negative charge are kep away from it and are poor protectors. In comparison with the most effective exogenous aminothiols like cysteamine and WR1065, GSH is not an effective radioprotector. Putative explanations for this relatively poor protective ability of GSH are presented.

  13. Photoinduced formation of thiols in human hair.

    PubMed

    Fedorkova, M V; Brandt, N N; Chikishev, A Yu; Smolina, N V; Balabushevich, N G; Gusev, S A; Lipatova, V A; Botchey, V M; Dobretsov, G E; Mikhalchik, E V

    2016-11-01

    Raman, scanning electron, and optical microscopy of hair and spectrophotometry of soluble hair proteins are used to study the effect of UV-vis radiation on white hair. The samples of a healthy subject are irradiated using a mercury lamp and compared with non-irradiated (control) hair. The cuticle damage with partial exfoliation is revealed with the aid of SEM and optical microscopy of semifine sections. Gel filtration chromatography shows that the molecular weight of soluble proteins ranges from 5 to 7kDa. Absorption spectroscopy proves an increase in amount of thiols in a heavier fraction of the soluble proteins of irradiated samples under study. Raman data indicate a decrease in the amount of SS and CS bonds in cystines and an increase in the amount of SH bonds due to irradiation. Such changes are more pronounced in peripheral regions of hair. Conformational changes of hair keratins presumably related to the cleavage of disulfide bonds, follow from variations in amide I and low-frequency Raman bands. An increase in the content of thiols in proteins revealed by both photometric data on soluble proteins and Raman microspectroscopy of hair cuts can be used to develop a protocol of the analysis of photoinduced hair modification.

  14. Thiol-ene-methacrylate composites as dental restorative materials

    PubMed Central

    Boulden, Jordan E.; Cramer, Neil B.; Schreck, Kathleen M.; Couch, Charles L.; Bracho-Troconis, Cora; Stansbury, Jeffrey W.; Bowman, Christopher N.

    2010-01-01

    Objectives The objective of this study was to evaluate composite methacrylate-thiol-ene formulations with varying thiol:ene stoichiometry relative to composite dimethacrylate control formulations. It was hypothesized that the methacrylate-thiol-ene systems would exhibit superior properties relative to the dimethacrylate control resins and that excess thiol relative to ene would further enhance shrinkage and conversion associated properties. Methods Polymerization kinetics and functional group conversions were determined by Fourier transform infrared spectroscopy (FTIR). Volume shrinkage was measured with a linometer and shrinkage stress was measured with a tensometer. Flexural modulus and strength, depth of cure, water sorption and solubility tests were all performed according to ISO 4049. Results All of the methacrylate-thiol-ene systems exhibited improvements in methacrylate conversion, flexural strength, shrinkage stress, depth of cure, and water solubility, while maintaining equivalent flexural modulus and water sorption relative to the dimethacrylate control systems. Increasing the thiol to ene stoichiometry resulted in further increased methacrylate functional group conversion and decreased volume shrinkage. Flexural modulus and strength, shrinkage stress, depth of cure, water sorption and solubility did not exhibit statistically significant changes with excess thiol . Significance Due to their improved overall functional group conversion and reduced water sorption, the methacrylate-thiol-ene formulations are expected to exhibit improved biocompatibility relative to the dimethacrylate control systems. Improvements in flexural strength and reduced shrinkage stress may be expected to result in composite restorations with superior longevity and performance. PMID:21122904

  15. Biologically important thiols in various vegetables and fruits.

    PubMed

    Demirkol, Omca; Adams, Craig; Ercal, Nuran

    2004-12-29

    Biological thiols are important antioxidants, and recent studies showed that their contents vary depending on the groups of foodstuffs. Therefore, we investigated the levels of some biological thiols in various vegetables and fruits by using a sensitive high-performance liquid chromatography (HPLC) technique. Biological thiols measured in some vegetables and fruits include glutathione (L-glutamyl-L-cysteinly glycine, GSH), N-acetylcysteine (NAC), captopril [CAP (C9H15NO3S)], homocysteine (HCYS), cysteine (CYS), and gamma-glutamyl cysteine (GGC). Our results show that biological thiol contents are between 3-349 nM/g wet weight in vegetables and 4-136 nM/g wet weight in fruits. CAP is only found in asparagus (28 nM/g wet weight). Furthermore, none of the biological thiols analyzed were found in cabbages, red grapes, blackberries, apples, and peaches. Therefore, various vegetables and fruits differ significantly in their thiol contents. Oxidation of these important thiols may occur and result in the production of toxic byproducts, if they are exposed to radiation and ozone treatment for sterilization purposes. Further studies should be performed to monitor the levels of these biological thiols.

  16. Solvent-switchable continuous-breathing behaviour in a diamondoid metal-organic framework and its influence on CO2 versus CH4 selectivity.

    PubMed

    Carrington, Elliot J; McAnally, Craig A; Fletcher, Ashleigh J; Thompson, Stephen P; Warren, Mark; Brammer, Lee

    2017-09-01

    Understanding the behaviour of flexible metal-organic frameworks (MOFs)-porous crystalline materials that undergo a structural change upon exposure to an external stimulus-underpins their design as responsive materials for specific applications, such as gas separation, molecular sensing, catalysis and drug delivery. Reversible transformations of a MOF between open- and closed-pore forms-a behaviour known as 'breathing'-typically occur through well-defined crystallographic transitions. By contrast, continuous breathing is rare, and detailed characterization has remained very limited. Here we report a continuous-breathing mechanism that was studied by single-crystal diffraction in a MOF with a diamondoid network, (Me2NH2)[In(ABDC)2] (ABDC, 2-aminobenzene-1,4-dicarboxylate). Desolvation of the MOF in two different solvents leads to two polymorphic activated forms with very different pore openings, markedly different gas-adsorption capacities and different CO2 versus CH4 selectivities. Partial desolvation introduces a gating pressure associated with CO2 adsorption, which shows that the framework can also undergo a combination of stepped and continuous breathing.

  17. From isolated diamondoids to a van-der-Waals crystal: A theoretical and experimental analysis of a trishomocubane and a diamantane dimer in the gas and solid phase

    NASA Astrophysics Data System (ADS)

    Tyborski, Christoph; Meinke, Reinhard; Gillen, Roland; Bischoff, Tobias; Knecht, Andre; Richter, Robert; Merli, Andrea; Fokin, Andrey A.; Koso, Tetyana V.; Rodionov, Vladimir N.; Schreiner, Peter R.; Möller, Thomas; Rander, Torbjörn; Thomsen, Christian; Maultzsch, Janina

    2017-07-01

    The electronic properties of sp2/sp3 diamondoids in the crystalline state and in the gas phase are presented. Apparent differences in electronic properties experimentally observed by resonance Raman spectroscopy in the crystalline/gas phase and absorption measurements in the gas phase were investigated by density functional theory computations. Due to a reorganization of the molecular orbitals in the crystalline phase, the HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) energy gaps are lowered significantly by 0.5 eV-1 eV. The π → π* transition is responsible for large absorption in both gas and crystalline phases. It further causes a large increase in the Raman intensity of the C=C stretch vibration when excited resonantly. By resonance Raman spectroscopy we were able to determine the C=C bond length of the trishomocubane dimer to exhibit 1.33 Å in the ground and 1.41 Å in the excited state.

  18. Solvent-switchable continuous-breathing behaviour in a diamondoid metal-organic framework and its influence on CO2 versus CH4 selectivity

    NASA Astrophysics Data System (ADS)

    Carrington, Elliot J.; McAnally, Craig A.; Fletcher, Ashleigh J.; Thompson, Stephen P.; Warren, Mark; Brammer, Lee

    2017-09-01

    Understanding the behaviour of flexible metal-organic frameworks (MOFs)—porous crystalline materials that undergo a structural change upon exposure to an external stimulus—underpins their design as responsive materials for specific applications, such as gas separation, molecular sensing, catalysis and drug delivery. Reversible transformations of a MOF between open- and closed-pore forms—a behaviour known as 'breathing'—typically occur through well-defined crystallographic transitions. By contrast, continuous breathing is rare, and detailed characterization has remained very limited. Here we report a continuous-breathing mechanism that was studied by single-crystal diffraction in a MOF with a diamondoid network, (Me2NH2)[In(ABDC)2] (ABDC, 2-aminobenzene-1,4-dicarboxylate). Desolvation of the MOF in two different solvents leads to two polymorphic activated forms with very different pore openings, markedly different gas-adsorption capacities and different CO2 versus CH4 selectivities. Partial desolvation introduces a gating pressure associated with CO2 adsorption, which shows that the framework can also undergo a combination of stepped and continuous breathing.

  19. Transition-metal-catalyzed synthesis of phenols and aryl thiols

    PubMed Central

    Liu, Shasha

    2017-01-01

    Phenols and aryl thiols are fundamental building blocks in organic synthesis and final products with interesting biological activities. Over the past decades, substantial progress has been made in transition-metal-catalyzed coupling reactions, which resulted in the emergence of new methods for the synthesis of phenols and aryl thiols. Aryl halides have been extensively studied as substrates for the synthesis of phenols and aryl thiols. In very recent years, C–H activation represents a powerful strategy for the construction of functionalized phenols directly from various arenes. However, the synthesis of aryl thiols through C–H activation has not been reported. In this review, a brief overview is given of the recent advances in synthetic strategies for both phenols and aryl thiols. PMID:28405239

  20. Selective purification of the thiol peptides of myosin

    PubMed Central

    Weeds, A. G.; Hartley, B. S.

    1968-01-01

    1. A method for selective purification of thiol peptides is described. Thiol groups in a protein are treated with radioactive cystine by disulphide–thiol interchange. The labelled cystine peptides in a digest can then be fractionated for peptide `maps'. Performic acid oxidation of paper strips containing the radioactive peptides followed by further ionophoresis yields the purified cysteic acid peptides. 2. The thiol peptides in a peptic digest of cystine-exchanged myosin were purified in this way, and their amino acid sequences were determined. 3. The conclusion that myosin contains at least 16, and probably between 20 and 22, unique thiol sequences indicates that the molecule consists of two chemically equivalent components. PMID:5660634

  1. Submicrodeterminations of thiols, disulphides and thiol esters in serum by using o-hydroxymercuribenzoic acid and dithiofluorescein

    PubMed Central

    Wroński, Mieczysław

    1967-01-01

    1. Methods are described for selective estimation of thiols, disulphides and thiol esters in standard solutions and in serum. The methods are based on the reaction with the excess of o-hydroxymercuribenzoic acid (HMB) in alkaline solution with subsequent addition of dithiofluorescein in excess and determination of the extinction at 588mμ. The sensitivity of the methods amounts to 1·5×10−9g.equiv. in 5ml. of final solution. Of results obtained on standard solutions 80% have the errors within the range ±4%. 2. It has been found that serum contains an unidentified substance (substance X) producing green complexes with dithiofluorescein which undergo decomposition on addition of formaldehyde. The correction for substance X must be estimated in a separate sample and taken into account. The concentration of substance X can be calculated from extinctions measured at 588mμ and 635mμ in the presence of dithiofluorescein in excess. 3. The selective determination of thiols and disulphides is based on different reaction rates with formaldehyde. The complexes between HMB and cysteine can be selectively decomposed by formaldehyde, and free glutathione can be selectively removed by formaldehyde in the presence of protein thiols. 4. Thiols are determined in the presence of triethylamine, thiols plus disulphides in the presence of triethylamine and sulphite, and thiols plus thiol esters in the presence of dimethylamine, with subsequent addition of ammonium sulphate. PMID:6049936

  2. Thiol specific oxidative stress response in Mycobacteria.

    PubMed

    Dosanjh, Nirpjit S; Rawat, Mamta; Chung, Ji-Hae; Av-Gay, Yossef

    2005-08-01

    The cellular response of mycobacteria to thiol specific oxidative stress was studied in Mycobacterium bovis BCG cultures. Two-dimensional gel electrophoresis revealed that upon diamide treatment at least 60 proteins were upregulated. Fourteen of these proteins were identified by MALDI-MS; four proteins, AhpC, Tpx, GroEL2, and GroEL1 are functionally related to oxidative stress response; eight proteins, LeuC, LeuD, Rv0224c, Rv3029c, AsnB, Rv2971, PheA and HisH are classified as part of the bacterial intermediary metabolism and respiration pathways; protein EchA14 belong to lipid metabolism, and NrdE, belongs to the mycobacterial information pathway category. Reverse transcription followed by quantitative real time PCR in response to diamide stress demonstrated that protein expression is directly proportional to the corresponding gene transcription.

  3. From thiol to sulfonic acid: modeling the oxidation pathway of protein thiols by hydrogen peroxide.

    PubMed

    van Bergen, Laura A H; Roos, Goedele; De Proft, Frank

    2014-08-07

    Hydrogen peroxide is a natural oxidant that can oxidize protein thiols (RSH) via sulfenic acid (RSOH) and sulfinic acid (RSO2H) to sulfonic acid (RSO3H). In this paper, we study the complete anionic and neutral oxidation pathway from thiol to sulfonic acid. Reaction barriers and reaction free energies for all three oxidation steps are computed, both for the isolated substrates and for the substrates in the presence of different model ligands (CH4, H2O, NH3) mimicking the enzymatic environment. We found for all three barriers that the anionic thiolate is more reactive than the neutral thiol. However, the assistance of the environment in the neutral pathway in a solvent-assisted proton-exchange (SAPE) mechanism can lower the reaction barrier noticeably. Polar ligands can decrease the reaction barriers, whereas apolar ligands do not influence the barrier heights. The same holds for the reaction energies: they decrease (become more negative) in the presence of polar ligands whereas apolar ligands do not have an influence. The consistently negative consecutive reaction energies for the oxidation in the anionic pathway when going from thiolate over sulfenic and sulfinic acid to sulfonic acid are in agreement with biological reversibility.

  4. Photopolymerized Thiol-Ene Systems as Shape Memory Polymers.

    PubMed

    Nair, Devatha P; Cramer, Neil B; Scott, Timothy F; Bowman, Christopher N; Shandas, Robin

    2010-09-03

    In this study we introduce the use of thiol-ene photopolymers as shape memory polymer systems. The thiol-ene polymer networks are compared to a commonly utilized acrylic shape memory polymer and shown to have significantly improved properties for two different thiol-ene based polymer formulations. Using thermomechanical and mechanical analysis, we demonstrate that thiol-ene based shape memory polymer systems have comparable thermomechanical properties while also exhibiting a number of advantageous properties due to the thiol-ene polymerization mechanism which results in the formation of a homogenous polymer network with low shrinkage stress and negligible oxygen inhibition. The resulting thiol-ene shape memory polymer systems are tough and flexible as compared to the acrylic counterparts. The polymers evaluated in this study were engineered to have a glass transition temperature between 30 and 40 °C, exhibited free strain recovery of greater than 96% and constrained stress recovery of 100%. The thiol-ene polymers exhibited excellent shape fixity and a rapid and distinct shape memory actuation response.

  5. Belt attachment and system

    DOEpatents

    Schneider, Abraham D.; Davidson, Erick M.

    2016-02-02

    Disclosed herein is a belt assembly including a flexible belt with an improved belt attachment. The belt attachment includes two crossbars spaced along the length of the belt. The crossbars retain bearings that allow predetermined movement in six degrees of freedom. The crossbars are connected by a rigid body that attaches to the bearings. Implements that are attached to the rigid body are simply supported but restrained in pitching rotation.

  6. Attachment Without Fear.

    PubMed

    Bell, David C

    2009-12-01

    John Bowlby hypothesized an attachment system that interacts with caregiving, exploration, and fear systems in the brain, with a particular emphasis on fear. Neurobiological research confirms many of his hypotheses and also raises some new questions. A psychological model based on this neurobiological research is presented here. The model extends conventional attachment theory by describing additional attachment processes independent of fear. In this model, the attachment elements of trust, openness, and dependence interact with the caregiving elements of caring, empathy, and responsibility.

  7. Special Attachments. Module 19.

    ERIC Educational Resources Information Center

    South Carolina State Dept. of Education, Columbia. Office of Vocational Education.

    This module on special attachments, one in a series dealing with industrial sewing machines, their attachments, and operation, covers four topics: gauges; cording attachment; zipper foot; and hemming, shirring, and binding. For each topic these components are provided: an introduction, directions, an objective, learning activities, student…

  8. Attachment over Time.

    ERIC Educational Resources Information Center

    Lewis, Michael; Feiring, Candice; Rosenthal, Saul

    2000-01-01

    Examined continuity in attachment classification from infancy through adolescence and related it to autobiographical memories of childhood, divorce, and maladjustment in white middle-class children. Found no continuity in attachment classification from 1 to 18 years and no relation between infant attachment status and adolescent adjustment.…

  9. The roles of thiol oxidoreductases in yeast replicative aging.

    PubMed

    Hacioglu, Elise; Esmer, Isil; Fomenko, Dmitri E; Gladyshev, Vadim N; Koc, Ahmet

    2010-01-01

    Thiol-based redox reactions are involved in the regulation of a variety of biological functions, such as protection against oxidative stress, signal transduction and protein folding. Some proteins involved in redox regulation have been shown to modulate life span in organisms from yeast to mammals. To assess the role of thiol oxidoreductases in aging on a genome-wide scale, we analyzed the replicative life span of yeast cells lacking known and candidate thiol oxidoreductases. The data suggest the role of several pathways in controlling yeast replicative life span, including thioredoxin reduction, protein folding and degradation, peroxide reduction, PIP3 signaling, and ATP synthesis.

  10. Neurobiology of Infant Attachment

    PubMed Central

    Moriceau, Stephanie

    2007-01-01

    A strong attachment to the caregiver is critical for survival in altricial species, including humans. While some behavioral aspects of attachment have been characterized, its neurobiology has only recently received attention. Using a mammalian imprinting model, we are assessing the neural circuitry that enables infant rats to attach quickly to a caregiver, thus enhancing survival in the nest. Specifically, the hyper-functioning noradrenergic locus coeruleus (LC) enables pups to learn rapid, robust preference for the caregiver. Conversely, a hypo-functional amygdala appears to prevent the infant from learning aversions to the caregiver. Adult LC and amygdala functional emergence correlates with sensitive period termination. This study suggests the neonatal brain is not an immature version of the adult brain but is uniquely designed to optimize attachment to the caregiver. Although human attachment may not rely on identical circuitry, the work reviewed here suggests a new conceptual framework in which to explore human attachments, particularly attachments to abusive caregivers. PMID:16252291

  11. Hierarchically Flower-like N-Doped Porous Carbon Materials Derived from an Explosive 3-Fold Interpenetrating Diamondoid Copper Metal-Organic Framework for a Supercapacitor.

    PubMed

    Li, Zuo-Xi; Zou, Kang-Yu; Zhang, Xue; Han, Tong; Yang, Ying

    2016-07-05

    A peculiar copper metal-organic framework (Cu-MOF) was synthesized by a self-assembly method, which presents a 3-fold interpenetrating diamondoid net based on the square-planar Cu(II) node. Although it exhibits a high degree of interpenetration, the Cu-MOF still exhibits a one-dimensional channel, which provides a template for constructing porous materials through the "precursor" strategy. Furthermore, the explosive ClO4(-) ion, which resided in the channel, could induce the quick decomposition of organic ingredients and release a huge amount of gas, which is beneficial for the porosity of postsynthetic materials. Significantly, we first utilize this explosive MOF to prepare a series of Cu@C composites through the calcination-thermolysis method at different temperatures, which contain copper particles exhibiting various shapes and combinations with the carbon substrate. Considering the hole-forming effect of copper particles, Cu@C composites were etched by HCl to afford a sequence of hierarchically flower-like N-doped porous carbon materials (NPCs), which retain the original morphology of the Cu-MOF. Interestingly, NPC-900, originating from the calcination of the Cu-MOF at 900 °C, exhibits a more regular flower-like morphology, the largest specific surface area, abundant porosities, and multiple nitrogen functionalities. The remarkable specific capacitances are 138 F g(-1) at 5 mV s(-1) and 149 F g(-1) at 0.5 A g(-1) for the NPC-900 electrode in a 6 M potassium hydroxide aqueous solution. Moreover, the retention of capacitance remains 86.8% (125 F g(-1)) at 1 A g(-1) over 2000 cycles, which displays good chemical stability. These findings suggest that NPC-900 can be applied as a suitable electrode for a supercapacitor.

  12. Thiol Dioxygenases: Unique Families of Cupin Proteins

    PubMed Central

    Simmons, C. R.; Karplus, P. A.; Dominy, J. E.

    2011-01-01

    Proteins in the cupin superfamily have a wide range of biological functions in archaea, bacteria and eukaryotes. Although proteins in the cupin superfamily show very low overall sequence similarity, they all contain two short but partially conserved cupin sequence motifs separated by a less conserved intermotif region that varies both in length and amino acid sequence. Furthermore, these proteins all share a common architecture described as a 6-stranded β-barrel core, and this canonical cupin or “jelly roll” β-barrel is formed with cupin motif 1, the intermotif region, and cupin motif 2 each forming two of the core six β-strands in the folded protein structure. The recently obtained crystal structures of cysteine dioxygenase (CDO), with contains conserved cupin motifs, show that it has the predicted canonical cupin β-barrel fold. Although there had been no reports of CDO activity in prokaryotes, we identified a number of bacterial cupin proteins of unknown function that share low similarity with mammalian CDO and that conserve many residues in the active site pocket of CDO. Putative bacterial CDOs predicted to have CDO activity were shown to have similar substrate specificity and kinetic parameters as eukaryotic CDOs. Information gleaned from crystal structures of mammalian CDO along with sequence information for homologs shown to have CDO activity facilitated the identification of a CDO family fingerprint motif. One key feature of the CDO fingerprint motif is that the canonical metal-binding glutamate residue in cupin motif 1 is replaced by a cysteine (in mammalian CDOs) or by a glycine (bacterial CDOs). The recent report that some putative bacterial CDO homologs are actually 3-mercaptopropionate dioxygenases suggests that the CDO family may include proteins with specificities for other thiol substrates. A paralog of CDO in mammals was also identified and shown to be the other mammalian thiol dioxygenase, cysteamine dioxygenase (ADO). A tentative

  13. Low Ubiquinone Content in Escherichia coli Causes Thiol Hypersensitivity

    PubMed Central

    Zeng, H.; Snavely, I.; Zamorano, P.; Javor, G. T.

    1998-01-01

    Thiol hypersensitivity in a mutant of Escherichia coli (IS16) was reversed by complementation with a plasmid that carried the ubiX gene. The mutant had low ubiquinone content. Complementation elevated the ubiquinone level and eliminated thiol hypersensitivity. Analysis of chromosomal ubiX genes indicated that both parent and mutant strains were ubiX mutants. The low ubiquinone content of IS16 was possibly caused by a ubiD ubiX genotype. A ubiA mutant also exhibited thiol hypersensitivity. Neither IS16 nor the ubiA mutant strain could produce alkaline phosphatase (in contrast to their parent strains) after 2 h of induction, thus showing Dsb− phenotypes. The phenomena of thiol hypersensitivity and low ubiquinone content may be linked by their connections to the periplasmic disulfide bond redox machinery. PMID:9658014

  14. Association of thiol disulfide homeostasis with slow coronary flow.

    PubMed

    Kundi, Harun; Gok, Murat; Cetin, Mustafa; Kiziltunç, Emrullah; Topcuoglu, Canan; Neşelioğlu, Salim; Erel, Ozcan; Ulusoy, Feridun Vasfi

    2016-08-01

    Objective The aim of this study was to investigate the role of thiol disulfide homeostasis in the presence of slow coronary flow. Material and methods In this cross-sectional study, a total of 110 patients who admitted to our hospital between March 2014 and December 2015 were included in the study. There were 65 patients in the slow coronary flow, and 45 patients in the normal flow groups. Results We found significant differences between slow coronary flow and the normal flow groups for thiol disulfide homeostasis, and the results of our study indicated that hsCRP, and thiol disulfide ratio were independently associated with slow coronary flow. Conclusion Our study showed that thiol disulfide homeostasis was significantly and independently related to the presence of slow coronary flow.

  15. Reversible inactivation of CO dehydrogenase with thiol compounds

    SciTech Connect

    Kreß, Oliver; Gnida, Manuel; Pelzmann, Astrid M.; Marx, Christian; Meyer-Klaucke, Wolfram; Meyer, Ortwin

    2014-05-09

    Highlights: • Rather large thiols (e.g. coenzyme A) can reach the active site of CO dehydrogenase. • CO- and H{sub 2}-oxidizing activity of CO dehydrogenase is inhibited by thiols. • Inhibition by thiols was reversed by CO or upon lowering the thiol concentration. • Thiols coordinate the Cu ion in the [CuSMo(=O)OH] active site as a third ligand. - Abstract: Carbon monoxide dehydrogenase (CO dehydrogenase) from Oligotropha carboxidovorans is a structurally characterized member of the molybdenum hydroxylase enzyme family. It catalyzes the oxidation of CO (CO + H{sub 2}O → CO{sub 2} + 2e{sup −} + 2H{sup +}) which proceeds at a unique [CuSMo(=O)OH] metal cluster. Because of changing activities of CO dehydrogenase, particularly in subcellular fractions, we speculated whether the enzyme would be subject to regulation by thiols (RSH). Here we establish inhibition of CO dehydrogenase by thiols and report the corresponding K{sub i}-values (mM): L-cysteine (5.2), D-cysteine (9.7), N-acetyl-L-cysteine (8.2), D,L-homocysteine (25.8), L-cysteine–glycine (2.0), dithiothreitol (4.1), coenzyme A (8.3), and 2-mercaptoethanol (9.3). Inhibition of the enzyme was reversed by CO or upon lowering the thiol concentration. Electron paramagnetic resonance spectroscopy (EPR) and X-ray absorption spectroscopy (XAS) of thiol-inhibited CO dehydrogenase revealed a bimetallic site in which the RSH coordinates to the Cu-ion as a third ligand ([Mo{sup VI}(=O)OH{sub (2)}SCu{sup I}(SR)S-Cys]) leaving the redox state of the Cu(I) and the Mo(VI) unchanged. Collectively, our findings establish a regulation of CO dehydrogenase activity by thiols in vitro. They also corroborate the hypothesis that CO interacts with the Cu-ion first. The result that thiol compounds much larger than CO can freely travel through the substrate channel leading to the bimetallic cluster challenges previous concepts involving chaperone function and is of importance for an understanding how the sulfuration step in

  16. Thiol oxidation by nitrosative stress: Cellular localization in human spermatozoa.

    PubMed

    Cabrillana, María E; Uribe, Pamela; Villegas, Juana V; Álvarez, Juan; Sánchez, Raúl; Fornés, Miguel W

    2016-10-01

    Peroxynitrite is a highly reactive nitrogen species and when it is generated at high levels it causes nitrosative stress, an important cause of impaired sperm function. High levels of peroxynitrite have been shown to correlate with decreased semen quality in infertile men. Thiol groups in sperm are mainly found in enzymes, antioxidant molecules, and structural proteins in the axoneme. Peroxynitrite primarily reacts with thiol groups of cysteine-containing proteins. Although it is well known that peroxynitrite oxidizes sulfhydryl groups in sperm, the subcellular localization of this oxidation remains unknown. The main objective of this study was to establish the subcellular localization of peroxynitrite-induced nitrosative stress in thiol groups and its relation to sperm motility in human spermatozoa. For this purpose, spermatozoa from healthy donors were exposed in vitro to 3-morpholinosydnonimine (SIN-1), a compound which generates peroxynitrite. In order to detect peroxynitrite and reduced thiol groups, the fluorescent probes, dihydrorhodamine 123 and monobromobimane (mBBr), were used respectively. Sperm viability was analyzed by propidium iodide staining. Peroxynitrite generation and thiol redox state were monitored by confocal microscopy whereas sperm viability was evaluated by flow cytometry. Sperm motility was analyzed by CASA using the ISAS(®) system. The results showed that exposure of human spermatozoa to peroxynitrite results in increased thiol oxidation which is mainly localized in the sperm head and principal piece regions. Thiol oxidation was associated with motility loss. The high susceptibility of thiol groups to peroxynitrite-induced oxidation could explain, at least in part, the negative effect of reactive nitrogen species on sperm motility. DHR: dihydrorhodamine 123; mBBr: monobromobimane ONOO(-): peroxynitrite RNS: reactive nitrogen species RFI: relative fluorescence intensity SIN-1: 3-morpholinosydnonimine CASA: Computer-Aided Sperm Analysis

  17. Quantifying Reversible Oxidation of Protein Thiols in Photosynthetic Organisms

    NASA Astrophysics Data System (ADS)

    Slade, William O.; Werth, Emily G.; McConnell, Evan W.; Alvarez, Sophie; Hicks, Leslie M.

    2015-04-01

    Photosynthetic organisms use dynamic post-translational modifications to survive and adapt, which include reversible oxidative modifications of protein thiols that regulate protein structure, function, and activity. Efforts to quantify thiol modifications on a global scale have relied upon peptide derivatization, typically using isobaric tags such as TMT, ICAT, or iTRAQ that are more expensive, less accurate, and provide less proteome coverage than label-free approaches—suggesting the need for improved experimental designs for studies requiring maximal coverage and precision. Herein, we present the coverage and precision of resin-assisted thiol enrichment coupled to label-free quantitation for the characterization of reversible oxidative modifications on protein thiols. Using C. reinhardtii and Arabidopsis as model systems for algae and plants, we quantified 3662 and 1641 unique cysteinyl peptides, respectively, with median coefficient of variation (CV) of 13% and 16%. Further, our method is extendable for the detection of protein abundance changes and stoichiometries of cysteine oxidation. Finally, we demonstrate proof-of-principle for our method, and reveal that exogenous hydrogen peroxide treatment regulates the C. reinhardtii redox proteome by increasing or decreasing the level of oxidation of 501 or 67 peptides, respectively. As protein activity and function is controlled by oxidative modifications on protein thiols, resin-assisted thiol enrichment coupled to label-free quantitation can reveal how intracellular and environmental stimuli affect plant survival and fitness through oxidative stress.

  18. Quantifying reversible oxidation of protein thiols in photosynthetic organisms.

    PubMed

    Slade, William O; Werth, Emily G; McConnell, Evan W; Alvarez, Sophie; Hicks, Leslie M

    2015-04-01

    Photosynthetic organisms use dynamic post-translational modifications to survive and adapt, which include reversible oxidative modifications of protein thiols that regulate protein structure, function, and activity. Efforts to quantify thiol modifications on a global scale have relied upon peptide derivatization, typically using isobaric tags such as TMT, ICAT, or iTRAQ that are more expensive, less accurate, and provide less proteome coverage than label-free approaches--suggesting the need for improved experimental designs for studies requiring maximal coverage and precision. Herein, we present the coverage and precision of resin-assisted thiol enrichment coupled to label-free quantitation for the characterization of reversible oxidative modifications on protein thiols. Using C. reinhardtii and Arabidopsis as model systems for algae and plants, we quantified 3662 and 1641 unique cysteinyl peptides, respectively, with median coefficient of variation (CV) of 13% and 16%. Further, our method is extendable for the detection of protein abundance changes and stoichiometries of cysteine oxidation. Finally, we demonstrate proof-of-principle for our method, and reveal that exogenous hydrogen peroxide treatment regulates the C. reinhardtii redox proteome by increasing or decreasing the level of oxidation of 501 or 67 peptides, respectively. As protein activity and function is controlled by oxidative modifications on protein thiols, resin-assisted thiol enrichment coupled to label-free quantitation can reveal how intracellular and environmental stimuli affect plant survival and fitness through oxidative stress.

  19. Short communication: characterization of soluble thiols in bovine milk.

    PubMed

    Niero, G; De Marchi, M; Masi, A; Penasa, M; Cassandro, M

    2015-09-01

    Antioxidants are molecules essential for the maintenance of cell homeostasis and their intake through the diet has positive effects on human health. Among antioxidants, low-molecular-weight (LMW) thiols represent an important class of compounds. The aim of this study was to identify LMW thiols in bovine milk. A total of 96 individual milk samples from Brown Swiss, Holstein-Friesian, Alpine Grey, and Simmental cattle breeds were collected in 8 herds. The LMW thiols were extracted from the soluble fraction of milk and, following a derivatization protocol, they were separated by reverse phase HPLC and detected fluorimetrically. Six thiol species were detected and 2, glutathione (GSH) and cysteine-glycine (Cys-Gly), were identified and quantified. Regardless of the breed, the average concentration of Cys-Gly in milk was greater than that of GSH. Overall, milk from dual-purpose breeds (Simmental and Alpine Grey) was richer in LMW thiols than milk from dairy cows (Holstein-Friesian and Brown Swiss). Glutathione and Cys-Gly, closely linked metabolically, were strongly correlated. Pearson correlations of Cys-Gly with protein and casein contents were moderately low, and no relationship was found between GSH and milk chemical composition. Future research should focus on the identification of all detected LMW thiol species.

  20. The Expanding Landscape of the Thiol Redox Proteome*

    PubMed Central

    Yang, Jing; Carroll, Kate S.; Liebler, Daniel C.

    2016-01-01

    Cysteine occupies a unique place in protein chemistry. The nucleophilic thiol group allows cysteine to undergo a broad range of redox modifications beyond classical thiol-disulfide redox equilibria, including S-sulfenylation (-SOH), S-sulfinylation (-SO2H), S-sulfonylation (-SO3H), S-nitrosylation (-SNO), S-sulfhydration (-SSH), S-glutathionylation (-SSG), and others. Emerging evidence suggests that these post-translational modifications (PTM) are important in cellular redox regulation and protection against oxidative damage. Identification of protein targets of thiol redox modifications is crucial to understanding their roles in biology and disease. However, analysis of these highly labile and dynamic modifications poses challenges. Recent advances in the design of probes for thiol redox forms, together with innovative mass spectrometry based chemoproteomics methods make it possible to perform global, site-specific, and quantitative analyses of thiol redox modifications in complex proteomes. Here, we review chemical proteomic strategies used to expand the landscape of thiol redox modifications. PMID:26518762

  1. Evaluation of thiol-disulphide homeostasis in radiation workers.

    PubMed

    Koc, Ural; Tan, Sinan; Ertem, Ahmet Goktug; Gumus, Mehmet; Ozbek, Betul; Erel, Ozcan

    2017-07-01

    To evaluate thiol-disulphide homeostasis - a novel, easily calculated, readily available, and relatively cheap oxidative stress marker - in radiation workers and compare the results with healthy controls. A total of 108 participants were enrolled in the study including 63 hospital workers occupationally exposed to ionizing radiation in the units of interventional radiology, interventional cardiology and nuclear medicine. A control group consisted of 45 individuals staff in the same hospital. Serum thiol-disulphide homeostasis measurement was investigated via the spectrophotometric method newly described by Erel and Neşelioğlu. The mean serum native thiol levels of radiation workers (528.96 ± 86.42 μmol/l) was significantly lower than control subjects (561.05 ± 104.83 μmol/l) (p = .045). The mean serum total thiol levels of radiation workers (547.70 ± 91.50 μmol/l) was lower than control subjects (580.36 ± 112.24 μmol/l). Nevertheless, there was no significant difference between total thiol of exposed workers and controls. The results show that long-term low dose ionizing radiation may lead to oxidative stress and have side-effects in antioxidant thiol groups. We may suggest supporting radiation workers by safe antioxidant nutritional formulations and following up via both physical dosimetry and biodosimetric methods.

  2. Metallophilic interactions in polymeric group 11 thiols

    NASA Astrophysics Data System (ADS)

    Kolari, Kalle; Sahamies, Joona; Kalenius, Elina; Novikov, Alexander S.; Kukushkin, Vadim Yu.; Haukka, Matti

    2016-10-01

    Three polymeric group 11 transition metal polymers featuring metallophilic interactions were obtained directly via self-assembly of metal ions and 4-pyridinethiol ligands. In the cationic [Cu2(S-pyH)4]n2+ with [ZnCl4]n2- counterion (1) and in the neutral [Ag(S-py) (S-pyH)]n (2) 4-pyridinethiol (S-pyH) and its deprotonated form (S-py) are coordinated through the sulfur atom. Both ligands are acting as bridging ligands linking the metal centers together. In the solid state, the gold(I) polymer [Au(S-pyH)2]Cl (3) consists of the repeating cationic [Au(S-pyH)2]+ units held together by aurophilic interactions. Compound 1 is a zig-zag chain, whereas the metal chains in the structures of 2 and 3 are linear. The protonation level of the thiol ligand had an impact on the crystallization of polymers. Both nature of the metal center and reaction conditions affected the polymerization. QTAIM analysis confirmed direct metal-metal contacts only in polymers 1 and 3. In polymer 2, no theoretical evidence of argentophilic contacts was obtained even though the AgṡṡṡAg distance was found to be less than sum of the Bondi's van der Waals radius of silver.

  3. Masked thiol sugars: chemical behavior and synthetic applications of S-glycopyranosyl-N-monoalkyl dithiocarbamates.

    PubMed

    Megia-Fernandez, Alicia; de la Torre-Gonzalez, Diego; Parada-Aliste, Jose; Lopez-Jaramillo, Francisco Javier; Hernandez-Mateo, Fernando; Santoyo-Gonzalez, Francisco

    2014-02-01

    The chemical behavior of S-glycopyranosyl-N-monoalkyl dithiocarbamates (DTCs) as masked 1-glycosyl thiols, easily prepared by the nucleophilic displacement of 1-halo sugars with dithiocarbamate salts of primary amines, has been studied and synthetically exploited. This behavior relies on the abstraction of the proton of the carbamate functionality that allows controlled access to thiolate sugar intermediates. The basic character of the DTC salts used as reagents leads to thiolates that evolve in situ to symmetrical diglycosyldisulfides (DGDSs) when long reaction times are allowed. Alternatively, controlled unmasking of the thiolate function can be efficiently attained by treatment with an external base of isolated anomeric glycosyl DTCs, the formation of which is prevalent when using short reaction times. In this manner, a second methodology for the preparation of symmetrical DGDSs and a chemical protocol for the S-glycosylation of any electrophilic substrate are established. The applications of this last strategy for the preparation of thioglycosyl vinyl sulfones, thiodisaccharides, and S-linked homo- and heterodivalent neoglycoconjugates are described as a proof-of-concept of the great potential of the sugar DTCs in any chemical scenario in which the covalent attachment of a thiol sugar is required. The evaluation of the biological functionality of some divalent sulfurated sugar systems is also described.

  4. Investigation of thiol-disulphide balance in patients with acute urticaria and chronic spontaneous urticaria.

    PubMed

    Akbas, Ayse; Kilinc, Fadime; Sener, Sertac; Aktaş, Akın; Baran, Pervin; Ergin, Merve

    2017-09-01

    Thiol-disulphide balance plays a major role in health and diseases. This balance may be disrupted by various diseases. We aimed to determine status of the effect of thiol-disulphide balance in urticaria. We aimed to investigate the thiol-disulphide balance in patients with acute urticaria (AUP) and chronic spontaneous urticaria (CSU). Study included 53 AUP and 47 healthy controls plus 57 patients with chronic spontaneous urticaria (CSUP) and 57 healthy controls. Levels of native thiols, disulphides and total thiols were evaluated in plasma using a new and automated spectrophotometric method. Ratios of disulphides/total thiols, disulphides/native thiols and native thiols/total thiols were calculated. For AU, there was no statistical difference compared to control group in levels of native thiols, disulphides and total thiols. For CSU, however, there was an increase in levels of native thiols, disulphides and total thiols and the ratio of thiol/disulphide in favour of disulphide. Thiol-disulphide balance was not affected by AU but shifted towards to disulphide in CSU indicating the presence of oxidative stress (OS).

  5. Temperament and attachment disorders.

    PubMed

    Zeanah, Charles H; Fox, Nathan A

    2004-03-01

    Reviewed in this article is research on children with reactive attachment disorder (RAD) who exhibit specific patterns of socially aberrant behavior resulting from being maltreated or having limited opportunities to form selective attachments. There are no data explaining why 2 different patterns of the disorder, an emotionally withdrawn-inhibited pattern and an indiscriminate-disinhibited pattern, arise from similarly aberrant environments. In this article, we consider whether temperamental differences might contribute to the different manifestations of reactive attachment disorder (RAD) in the context of adverse environments. Although the association between attachment and temperament has been studied extensively and has been the subject of spirited debate within the field of child development, there are no extant data on the influence of temperament on the development of attachment disorders. We consider possible directions for research efforts designed to explore the biological underpinnings of the complex phenomenon of attachment disorders.

  6. Blade attachment assembly

    SciTech Connect

    Garcia-Crespo, Andres Jose; Delvaux, John McConnell; Miller, Diane Patricia

    2016-05-03

    An assembly and method for affixing a turbomachine rotor blade to a rotor wheel are disclosed. In an embodiment, an adaptor member is provided disposed between the blade and the rotor wheel, the adaptor member including an adaptor attachment slot that is complementary to the blade attachment member, and an adaptor attachment member that is complementary to the rotor wheel attachment slot. A coverplate is provided, having a coverplate attachment member that is complementary to the rotor wheel attachment slot, and a hook for engaging the adaptor member. When assembled, the coverplate member matingly engages with the adaptor member, and retains the blade in the adaptor member, and the assembly in the rotor wheel.

  7. Attachment Without Fear

    PubMed Central

    Bell, David C.

    2012-01-01

    John Bowlby hypothesized an attachment system that interacts with caregiving, exploration, and fear systems in the brain, with a particular emphasis on fear. Neurobiological research confirms many of his hypotheses and also raises some new questions. A psychological model based on this neurobiological research is presented here. The model extends conventional attachment theory by describing additional attachment processes independent of fear. In this model, the attachment elements of trust, openness, and dependence interact with the caregiving elements of caring, empathy, and responsibility. PMID:22879835

  8. Manipulation of thiol contents in plants.

    PubMed

    Höfgen, R; Kreft, O; Willmitzer, L; Hesse, H

    2001-01-01

    As sulfur constitutes one of the macronutrients necessary for the plant life cycle, sulfur uptake and assimilation in higher plants is one of the crucial factors determining plant growth and vigour, crop yield and even resistance to pests and stresses. Inorganic sulfate is mostly taken up as sulfate from the soil through the root system or to a lesser extent as volatile sulfur compounds from the air. In a cascade of enzymatic steps inorganic sulfur is converted to the nutritionally important sulfur-containing amino acids cysteine and methionine (Hell, 1997; Hell and Rennenberg, 1998; Saito, 1999). Sulfate uptake and allocation between plant organs or within the cell is mediated by specific transporters localised in plant membranes. Several functionally different sulfate transporters have to be postulated and have been already cloned from a number of plant species (Clarkson et al., 1993; Hawkesford and Smith, 1997; Takahashi et al., 1997; Yamaguchi, 1997). Following import into the plant and transport to the final site of reduction, the plastid, the chemically relatively inert sulfate molecule is activated through binding to ATP forming adenosine-5'-phosphosulfate (APS). This enzymatic step is controlled through the enzyme ATP-sulfurylase (ATP-S). APS can be further phosphorylated to form 3'-phosphoadenosine-5'-phosphosulfate (PAPS) which serves as sulfate donor for the formation of sulfate esters such as the biosynthesis of sulfolipids (Schmidt and Jäger, 1992). However, most of the APS is reduced to sulfide through the enzymes APS-reductase (APR) and sulfite reductase (SIR). The carbon backbone of cysteine is provided through serine, thus directly coupling photosynthetic processes and nitrogen metabolism to sulfur assimilation. L-serine is activated by serine acetyltransferase (SAT) through the transfer to an acetyl-group from acetyl coenzyme A to form O-acetyl-L-serine (OAS) which is then sulhydrylated using sulfide through the enzyme O-acetyl-L-serine thiol

  9. Benzofurazan Sulfides for Thiol Imaging and Quantification in Live Cells through Fluorescence Microscopy

    PubMed Central

    Li, Yinghong; Yang, Yang; Guan, Xiangming

    2012-01-01

    Thiol groups play a significant role in various cellular functions. Cellular thiol concentrations can be affected by various physiological or pathological factors. A fluorescence imaging agent that can effectively and specifically image thiols in live cells through fluorescence microscopy is desirable for live cell thiol monitoring. Benzofurazan sulfides 1a–e were synthesized and found to be thiol specific fluorogenic agents except 1d. They are not fluorescent but form strong fluorescent thiol adducts after reacting with thiols through a sulfide-thiol exchange reaction. On the other hand, they exhibit no reaction with other biologically relevant nucleophilic functional groups such as -NH2, -OH, or -COOH revealing the specificity for the detection of thiols. Sulfide 1a was selected to confirm its ability to image cellular thiols through fluorescence microscopy. The compound was demonstrated to effectively image and quantify thiol changes in live cells through fluorescence microscopy using 430 nm and 520 nm as the excitation and emission wavelengths respectively. The quantification results of total thiol in live cells obtained from fluorescence microscopy were validated by an HPLC/UV total thiol assay method. The reagents and method will be of a great value to thiol redox-related research. PMID:22794193

  10. Reactive Attachment Disorder.

    ERIC Educational Resources Information Center

    Chapman, Sue

    2002-01-01

    Written by a British parent, this case study tells the story of an adopted child who experienced many difficulties adjusting to life at home and school. It describes attachment disorder, possible causes of attachment difficulties, the bonding cycle, therapeutic parenting, and how schools can support the re-nurturing process. (Contains references.)…

  11. Temperament and Attachment Disorders

    ERIC Educational Resources Information Center

    Zeanah, Charles H.; Fox, Nathan A.

    2004-01-01

    Reviewed in this article is research on children with reactive attachment disorder (RAD) who exhibit specific patterns of socially aberrant behavior resulting from being maltreated or having limited opportunities to form selective attachments. There are no data explaining why 2 different patterns of the disorder, an emotionally withdrawn-inhibited…

  12. Infant Feeding and Attachment.

    ERIC Educational Resources Information Center

    Ainsworth, Mary D. Salter; Tracy, Russel L.

    This paper has two major purposes: first, to consider how infant feeding behavior may fit into attachment theory; and second, to cite some evidence to show how an infant's early interaction with his mother in the feeding situation is related to subsequent development. It was found that sucking and rooting are precursor attachment behaviors that…

  13. Separation and Attachment

    ERIC Educational Resources Information Center

    Honig, Alice Sterling

    2005-01-01

    Developing secure attachments with babies gives them a very special gift--the foundation for good infant mental health! In this article, the author discusses how to develop secure attachments with babies. Babies who are in the care of others during the day often suffer from separations from their special adults. Thirteen "tips" to ensure that…

  14. Attachment Theory and Mindfulness

    ERIC Educational Resources Information Center

    Snyder, Rose; Shapiro, Shauna; Treleaven, David

    2012-01-01

    We initiate a dialog between two central areas in the field of psychology today: attachment theory/research and mindfulness studies. The impact of the early mother-infant relationship on child development has been well established in the literature, with attachment theorists having focused on the correlation between a mother's capacity for…

  15. Attachment Line Blockage Models

    NASA Technical Reports Server (NTRS)

    1995-01-01

    Photographs shows the attachment-line experiment model with fairing and fence for supersonic attachment-line experiments. The fairing is intended to eliminate the wing/fuselage juncture shock and align the flow for the streamlined fence. The streamlined fence traps the turbulent fuselage boundary layer to prevent turbulent contamination of the leading edge flow.

  16. Attachment Theory and Mindfulness

    ERIC Educational Resources Information Center

    Snyder, Rose; Shapiro, Shauna; Treleaven, David

    2012-01-01

    We initiate a dialog between two central areas in the field of psychology today: attachment theory/research and mindfulness studies. The impact of the early mother-infant relationship on child development has been well established in the literature, with attachment theorists having focused on the correlation between a mother's capacity for…

  17. [Mentalization and attachment transmission].

    PubMed

    Böhmann, Johann; Fritsch, Sophia; Lück, Monika; Stumpe, Anna; Taubner, Svenja; Vesterling, Christina

    2014-01-01

    The present study was investigating the predictive role of maternal mentalizing and general as well as depressive symptom burden for attachment security at the end of the first year on a sample of 44 mother-child-dyads from a low-risk community study. Maternal mentalizing was assessed in a multidimensional way as Reflective Functioning (off-line) and Mind-Mindedness (on-line). The design was longitudinal measuring maternal Mind-Mindedness from a videotaped mother-child-play-interaction at the age of three months. General and depressive symptom burden was assessed using the SCL-90-R when the children were nine months old. Maternal attachment and Reflective-Functioning, using the Adult-Attachment-Interview, as well as children's attachment behavior, using the Strange-Situation-Test, were investigated at the age of twelve months. Secure maternal attachment was associated with higher Reflective Functioning, higher frequency of Mind-Mindedness and lower general and depressive symptom burden. A moderation-analysis showed a statistical trend (p = .08) that the interaction of the frequency of mind-related comments, general symptom severity and maternal attachment has a predictive value for infantile attachment security. Results can be tentatively interpreted that mothers with insecure attachment who had a lower general symptom burden and who related to their three-months old babies with a high frequency of mind-related-comments were more likely to have securely attached children. Thus, results may serve as a groundwork for projects aiming to prevent the transmission of insecure attachment by strengthening maternal Mind-Mindedness and working on the reduction of maternal general symptom burden.

  18. Late-life attachment.

    PubMed

    Freitas, Mélanie; Rahioui, Hassan

    2017-03-01

    Old age is likely to cause a crisis in one's life because of the vulnerabilities it brings up, acting as stressful elements disrupting the elder's feeling of security. It leads to the activation of what is called his attachment system, consisting in attachment styles and interpersonal emotional regulation strategies. To recover a higher sense of safety, the elder would refer to his attachment figures, that is to say closed people paying attention to him, showing towards him availability and consideration. However older adults particularly see their tolerance threshold lowered, regarding an accumulation of losses (true or symbolic) and stressful events within their lifetime. In a psychological and organic exhaustion phenomenon, the risk is to wear out the interpersonal emotional regulation strategies. These are as much vulnerabilities that may increase psychiatric decompensation, including depression. To resolve the tension of this period and to found a necessary secure feeling, the elder will have to redesign the attachment links previously settled and proceed to adjustments to this new context. The need of relational closeness comes back in the elders' attachment behaviour, counting on attachment figures not only to help their loneliness or dependency, but essentially to support them in a narcissist and affective way. That is why attachment theory enlightens the late life period, such as the new challenges older adults have to face. Many studies recognize its value in understanding the transition to old age, but without proposing conceptualization. We aim first to focus on attachment conception to say how much it is relevant with elderly, and then to describe specific terms of attachment within this population in order to better understand those patients. To finish, we must think about new therapeutic proposals taking into consideration the attachment perspective for a better understanding of old age transition.

  19. Designed Chemical Intervention with Thiols for Prophylactic Contraception

    PubMed Central

    Jain, Ashish; Verma, Vikas; Sharma, Vikas; Kushwaha, Bhavana; Lal, Nand; Kumar, Lalit; Rawat, Tara; Dwivedi, Anil K.; Maikhuri, Jagdamba P.; Sharma, Vishnu L.; Gupta, Gopal

    2013-01-01

    Unlike somatic cells, sperm have several-fold more available-thiols that are susceptible to redox-active agents. The present study explains the mechanism behind the instant sperm-immobilizing and trichomonacidal activities of pyrrolidinium pyrrolidine-1-carbodithioate (PPC), a novel thiol agent rationally created for prophylactic contraception by minor chemical modifications of some known thiol drugs. PPC, and its three derivatives (with potential active-site blocked by alkylation), were synthesized and evaluated against live human sperm and metronidazole-susceptible and resistant Trichomonas vaginalis, in vitro. Sperm hexokinase activity was evaluated by coupled enzyme assay. PPC irreversibly immobilized 100% human sperm in ∼30 seconds and totally eliminated Trichomonas vaginalis more efficiently than nonoxynol-9 and metronidazole. It significantly inhibited (P<0.001) thiol-sensitive sperm hexokinase. However, the molecule completely lost all its biological activities once its thiol group was blocked by alkylation. PPC was subsequently formulated into a mucoadhesive vaginal film using GRaS excipients and evaluated for spermicidal and microbicidal activities (in vitro), and contraceptive efficacy in rabbits. PPC remained fully active in quick-dissolving, mucoadhesive vaginal-film formulation, and these PPC-films significantly reduced pregnancy and fertility rates in rabbits. The films released ∼90% of PPC in simulated vaginal fluid (pH 4.2) at 37°C in 5 minutes, in vitro. We have thus discovered a common target (reactive thiols) on chiefly-anaerobic, redox-sensitive cells like sperm and Trichomonas, which is susceptible to designed chemical interference for prophylactic contraception. The active thiol in PPC inactivates sperm and Trichomonas via interference with crucial sulfhydryl-disulfide based reactions, e.g. hexokinase activation in human sperm. In comparison to non-specific surfactant action of OTC spermicide nonoxynol-9, the action of thiol-active PPC

  20. Introduction of thiol moieties, including their thiol-ene reactions and air oxidation, onto polyelectrolyte multilayer substrates.

    PubMed

    Madaan, Nitesh; Romriell, Naomi; Tuscano, Joshua; Schlaad, Helmut; Linford, Matthew R

    2015-12-01

    We describe the derivatization of uncross-linked and cross-linked layer-by-layer (LbL) assemblies of polyelectrolytes (polyallylamine hydrochloride and polyacrylic acid) with sulfydryl groups via Traut's reagent (2-iminothiolane). This thiolation was optimized with regards to temperature, concentration, and pH. The stability of the resulting -SH groups in the air was determined by X-ray photoelectron spectroscopy (XPS). This air oxidation has obvious implications for the use of thiol-ene reactions in materials chemistry, and there appears to be little on this topic in the literature. Three main S 2s signals were observed by XPS: at 231.5 eV (oxidized sulfur), 227.6 eV (thiol groups), and 225.4 eV (thiolate groups). Due to their rapid oxidation, we recommend that thiolated surfaces be used immediately after they are prepared. As driven by 254 nm UV light, thiol groups on polyelectrolyte multilayers react with 1,2-polybutadiene (PBd), and residual carbon-carbon double bonds on adsorbed PBd similarly react with another thiol. In the case of a fluorinated thiol, surfaces with high water contact angles (ca. 120°) are obtained. Modest exposures to light result in derivatization, while longer exposures damage the assemblies. Polyelectrolyte-thiol-PBd-thiol assemblies delaminate from their substrates when immersed for long periods of time in water. Surface silanization with an amino silane prevents this delamination and leads to stable assemblies. These assemblies withstand various stability tests. Techniques used to analyze the materials in this study include X-ray photoelectron spectroscopy (XPS), spectroscopic ellipsometry (SE), atomic force microscopy (AFM), and contact angle goniometry. Copyright © 2015 Elsevier Inc. All rights reserved.

  1. Thiol/disulfide redox states in signaling and sensing

    PubMed Central

    Go, Young-Mi; Jones, Dean P.

    2015-01-01

    Rapid advances in redox systems biology are creating new opportunities to understand complexities of human disease and contributions of environmental exposures. New understanding of thiol-disulfide systems have occurred during the past decade as a consequence of the discoveries that thiol and disulfide systems are maintained in kinetically controlled steady-states displaced from thermodynamic equilibrium, that a widely distributed family of NADPH oxidases produces oxidants that function in cell signaling, and that a family of peroxiredoxins utilize thioredoxin as a reductant to complement the well-studied glutathione antioxidant system for peroxide elimination and redox regulation. This review focuses on thiol/disulfide redox state in biologic systems and the knowledge base available to support development of integrated redox systems biology models to better understand the function and dysfunction of thiol-disulfide redox systems. In particular, central principles have emerged concerning redox compartmentalization and utility of thiol/disulfide redox measures as indicators of physiologic function. Advances in redox proteomics show that, in addition to functioning in protein active sites and cell signaling, cysteine residues also serve as redox sensors to integrate biologic functions. These advances provide a framework for translation of redox systems biology concepts to practical use in understanding and treating human disease. Biological responses to cadmium, a widespread environmental agent, are used to illustrate the utility of these advances to the understanding of complex pleiotropic toxicities. PMID:23356510

  2. The control of hyperhomocysteinemia through thiol exchange mechanisms by mesna.

    PubMed

    Di Giuseppe, Danila; Priora, Raffaella; Coppo, Lucia; Ulivelli, Monica; Bartalini, Sabina; Summa, Domenico; Margaritis, Antonios; Frosali, Simona; Di Simplicio, Paolo

    2014-02-01

    In hyperhomocysteinemic patients, after reaction with homocysteine-albumin mixed disulfides (HSS-ALB), mesna (MSH) forms the mixed disulfide with Hcy (HSSM) which can be removed by renal clearance, thus reducing the plasma concentration of total homocysteine (tHcy). In order to assess the HSS-ALB dethiolation via thiol exchange reactions, the distribution of redox species of cysteine, cysteinylglycine, homocysteine and glutathione was investigated in the plasma of healthy subjects: (i) in vitro, after addition of 35 μM reduced homocysteine (HSH) to plasma for 72 h, followed by MSH addition (at the concentration range 10-600 μM) for 25 min; (ii) in vivo, after oral treatment with methionine (methionine, 200 mg/kg body weight, observation time 2-6 h). In both experiments the distribution of redox species, but not the total amount of each thiol, was modified by thiol exchange reactions of albumin and cystine, with changes thermodynamically related to the pKa values of thiols in the corresponding mixed disulfides. MSH provoked a dose-response reversal of the redox state of aged plasma, and the thiol action was confirmed by in vivo experiments. Since it was observed that the dimesna production could be detrimental for the in vivo optimization of HSSM formation, we assume that the best plasma tHcy lowering can be obtained at MSH doses producing the minimum dimesna concentration in each individual.

  3. The impact of thiol peroxidases on redox regulation.

    PubMed

    Flohé, Leopold

    2016-01-01

    The biology of glutathione peroxidases and peroxiredoxins is reviewed with emphasis on their role in metabolic regulation. Apart from their obvious function in balancing oxidative challenge, these thiol peroxidases are not only implicated in orchestrating the adaptive response to oxidative stress, but also in regulating signaling triggered by hormones, growth factors and cytokines. The mechanisms presently discussed comprise dampening of redox-sensitive regulatory processes by elimination of hydroperoxides, suppression of lipoxygenase activity, committing suicide to save H2O2 for signaling, direct binding to receptors or regulatory proteins in a peroxidase activity-independent manner, or acting as sensors for hydroperoxides and as transducers of oxidant signals. The various mechanistic proposals are discussed in the light of kinetic data, which unfortunately are scarce. Taking into account pivotal criteria of a meaningful regulatory circuit, kinetic plausibility and specificity, the mechanistic concepts implying a direct sensor/transducer function of the thiol peroxidases appear most appealing. With rate constants for the reaction with hydroperoxide of 10(5)-10(8) M(-1) s(-1), thiol peroxidases are qualified as kinetically preferred hydroperoxide sensors, and the ability of the oxidized enzymes to react with defined protein thiols lends specificity to the transduction process. The versatility of thiol peroxidases, however, allows multiple ways of interaction with regulatory pathways.

  4. Thiol Chemistry in Peroxidase Catalysis and Redox Signaling

    PubMed Central

    Fukuto, Jon M.; Forman, Henry Jay

    2008-01-01

    Abstract The oxidation chemistry of thiols and disulfides of biologic relevance is described. The review focuses on the interaction and kinetics of hydrogen peroxide with low-molecular-weight thiols and protein thiols and, in particular, on sulfenic acid groups, which are recognized as key intermediates in several thiol oxidation processes. In particular, sulfenic and selenenic acids are formed during the catalytic cycle of peroxiredoxins and glutathione peroxidases, respectively. In turn, these enzymes are in close redox communication with the thioredoxin and glutathione systems, which are the major controllers of the thiol redox state. Oxidants formed in the cell originate from several different sources, but the major producers are NADPH oxidases and mitochondria. However, a different role of the oxygen species produced by these sources is apparent as oxidants derived from NADPH oxidase are involved mainly in signaling processes, whereas those produced by mitochondria induce cell death in pathways including also the thioredoxin system, presently considered an important target for cancer chemotherapy. Antioxid. Redox Signal. 10, 1549–1564. PMID:18479206

  5. Chemoselective Attachment of Biologically Active Proteins to Surfaces by Native Chemical Ligation

    SciTech Connect

    Cheung, C L; de Yoreo, J J; Coleman, M; Camarero, J A

    2003-11-22

    The present work describes our ongoing efforts towards the creation of micro and nanoscaled ordered arrays of protein covalently attached to site-specific chemical linkers patterned by different microlithographic techniques. We present a new and efficient solid-phase approach for the synthesis of chemically modified long alkyl-thiols. These compounds can be used to introduce chemoselective reacting groups onto silicon-based surfaces. We show that these modified thiols can be used for creating nano- and micrometric chemical patterns by using different lithographic techniques. We show that these patterns can react chemoselectively with proteins which have been recombinantly modified to contain complementary chemical groups at specific positions thus resulting in the oriented attachment of the protein to the surface.

  6. Alkylthiol self-assembled monolayers on Au(111) with tailored tail groups for attaching gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Kutsenko, V. Y.; Lopatina, Y. Y.; Bossard-Giannesini, L.; Marchenko, O. A.; Pluchery, O.; Snegir, S. V.

    2017-06-01

    Self-assembled monolayers (SAMs) on Au(111) are able to control the functionality of a gold surface. We use scanning tunnelling microscopy (STM) in air and contact angle measurements to compare the morphology and the chemistry of three alkylthiol SAMs differing by their tail groups: 1,9-nonanedithiol (NDT), 1,4-butanedithiol (BDT) and 11-mercaptoundecanol (MUOH). STM reveals very different morphologies: a hexagonal lattice for MUOH and parallel rows for NDT and BDT. In the case of NDT, we find that the thiol tail groups may form disulfide bridges with long immersion times. The availability of the -SH group for chemical reactions is demonstrated by attaching gold nanoparticles (AuNPs). When the thiol tail group is available, AuNPs readily attach as shown with atomic force microscopy (AFM). When disulfide bridges are formed, the gold surface is not able to bind nanoparticles.

  7. Modification of regenerated cellulose membrane based on thiol dendrimer.

    PubMed

    Vázquez, M Isabel; Algarra, Manuel; Benavente, Juana

    2015-10-20

    This work describes the modification of a highly swollen commercial regenerated cellulose (RC) membrane with a dendritic molecule (thiol DAB dendrimer of generation 3) by the dip coating method, and its possible use in electrochemical systems with saline solutions fluxes. Moreover, cellulosic membrane modification with dendrimer covered-CdSe quantum dot was also performed, since it allows dendrimer assortment by fluorescence. Changes in electrical, mechanical and diffusive membrane parameters were determined by impedance spectroscopy, elasticity curves and diffusional permeability measurements. The results indicate a reduction in the free volume of the RC chains in the original membrane associated with the thiol dendrimer inclusion, which reduces diffusive permeability. This demonstrates the possibility of using the thiol dendrimer-modified membrane in low/medium concentration level (0.001M/0.01M) devices with NaCl and PbCl2 solutions.

  8. Occurrence of low molecular weight thiols in biological systems

    NASA Technical Reports Server (NTRS)

    Fahey, Robert C.; Newton, Gerald L.

    1983-01-01

    Bromobimane labeling and high performance chromatography analysis were applied to various species of bacteria, plant tissues, and animal tissues. The reaction between thiols and monobromobimane is studied. Chromatograms revealing peaks produced by nonthiols and thiols are analyzed and compared. It is observed that all the bacteria species contain hydrogen sulfide, and glutathione is contained in facultative and aerobic gram-negative bacteria. For the plant tissues, the data reveal that mung bean sprouts contain homoglutathione and no glutathione; alfalfa sprouts contain homoglutathione and glutathione; the pea seed, nonlegumes, and fungi contain glutathione and no homoglutathione. It is detected that the main thiol in the animal tissues is glutathione. Based on the data, it is suggested that glutathione has an essential function in higher organisms.

  9. Cysteine-functional polymers via thiol-ene conjugation.

    PubMed

    Kuhlmann, Matthias; Reimann, Oliver; Hackenberger, Christian P R; Groll, Jürgen

    2015-03-01

    A thiofunctional thiazolidine is introduced as a new low-molar-mass building block for the introduction of cysteine residues via a thiol-ene reaction. Allyl-functional polyglycidol (PG) is used as a model polymer to demonstrate polymer-analogue functionalization through reaction with the unsaturated side-chains. A modified trinitrobenzenesulfonic acid (TNBSA) assay is used for the redox-insensitive quantification and a precise final cysteine content can be predetermined at the polymerization stage. Native chemical ligation at cysteine-functional PG is performed as a model reaction for a chemoselective peptide modification of this polymer. The three-step synthesis of the thiofunctional thiazolidine reactant, together with the standard thiol-ene coupling and the robust quantification assay, broadens the toolbox for thiol-ene chemistry and offers a generic and straightforward approach to cysteine-functional materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Occurrence of low molecular weight thiols in biological systems

    NASA Technical Reports Server (NTRS)

    Fahey, Robert C.; Newton, Gerald L.

    1983-01-01

    Bromobimane labeling and high performance chromatography analysis were applied to various species of bacteria, plant tissues, and animal tissues. The reaction between thiols and monobromobimane is studied. Chromatograms revealing peaks produced by nonthiols and thiols are analyzed and compared. It is observed that all the bacteria species contain hydrogen sulfide, and glutathione is contained in facultative and aerobic gram-negative bacteria. For the plant tissues, the data reveal that mung bean sprouts contain homoglutathione and no glutathione; alfalfa sprouts contain homoglutathione and glutathione; the pea seed, nonlegumes, and fungi contain glutathione and no homoglutathione. It is detected that the main thiol in the animal tissues is glutathione. Based on the data, it is suggested that glutathione has an essential function in higher organisms.

  11. The neurobiology of attachment.

    PubMed

    Insel, T R; Young, L J

    2001-02-01

    It is difficult to think of any behavioural process that is more intrinsically important to us than attachment. Feeding, sleeping and locomotion are all necessary for survival, but humans are, as Baruch Spinoza famously noted, "a social animal" and it is our social attachments that we live for. Over the past decade, studies in a range of vertebrates, including humans, have begun to address the neural basis of attachment at a molecular, cellular and systems level. This review describes some of the important insights from this work.

  12. Thinking about children's attachments.

    PubMed

    Rees, C A

    2005-10-01

    Disordered parental attachment can commit children to lives characterised by relationship difficulties, behaviour problems, educational failure, and poor self-esteem. It is a major root of trans-generational neglect and abuse and frequently underlies mental health problems, drug and alcohol addiction, homelessness, and crime. Early childhood setting of hypothalamus-pituitary-adrenal axis function appears to contribute to these costly difficulties. More broadly, the concept of attachment can contribute to defining and managing the psychosocial dimension of routine paediatric care. The current under-representation of attachment in paediatric education, practice, and research needs to be rectified.

  13. Photon Induced Electron Attachment.

    DTIC Science & Technology

    1984-12-01

    initial measure- ments was that high switch currents and long pulse durations appear to lead to substantially enhanced attachment rates in C3F8 ...similar conditions, but with 1.9 x 1015 C3F8 molecules/cm 3 added to the switch gas mixture. The initial current rise is comparable in both plots, but the...enhanced attachment during the switch opening time period. B. C0O Laser Excitation The photon enhanced attachment of the three gases NF3, C3F8 I and

  14. The effectiveness of a lipid peroxide in oxidizing protein and non-protein thiols

    PubMed Central

    Little, C.; O'Brien, P. J.

    1968-01-01

    1. Thiol oxidation by a lipid peroxide or hydrogen peroxide was as efficient in denatured non-haem proteins as in small thiols. Both peroxides were relatively ineffective in oxidizing haemoprotein thiols, especially at low pH. Increased amounts of haematin decreased greatly the efficiency of GSH oxidation by peroxides especially at low pH. 2. Other than the haematin ring, the thiol group was found to be probably the group in proteins most sensitive to modification by peroxides. 3. At low concentrations, the fatty acid moiety of a lipid peroxide appeared to impede thiol oxidation in proteins, probably by hydrophobic bonding to the protein, rather than to stimulate thiol oxidation by denaturing the protein and thereby increasing the exposure and reactivity of the thiol group. 4. The relative rates of thiol oxidation by peroxides in the different thiols were: haemoprotein thiols>small thiols>other protein thiols. In all cases, thiol oxidation was much more rapid by the lipid peroxide than by hydrogen peroxide. PMID:5637351

  15. Distribution, adaptation and physiological meaning of thiols from vertebrate hemoglobins.

    PubMed

    Reischl, Evaldo; Dafre, Alcir Luiz; Franco, Jeferson Luis; Wilhelm Filho, Danilo

    2007-01-01

    In the present review, the sequences of hemoglobins (Hb) of 267 adult vertebrate species belonging to eight major vertebrate taxa are examined for the presence and location of cysteinyl residues in an attempt at correlation with their ecophysiology. Essentially, all vertebrates have surface cysteinyl residues in Hb molecules whereby their thiol groups may become highly reactive. Thiol-rich Hbs may display eight or more thiols per tetramer. In vertebrates so far examined, the cysteinyl residues occur in 44 different sequence positions in alpha chains and 41 positions in beta chains. Most of them are conservatively located and occur in only a few positions in Teleostei, Aves and Mammalia, whereas they are dispersed in Amphibia. The internal cysteinyl residue alpha104 is ubiquitous in vertebrates. Residue beta93 is highly conserved in reptiles, birds and mammals. The number of cysteine residues per tetramer with solvent access varies in vertebrates, mammalians and bony fish having the lowest number of external residues, whereas nearly all external cysteine residues in Aves and Lepidosauria are of the surface crevice type. In cartilaginous fish, amphibians, Crocodylidae and fresh water turtles, a substantial portion of the solvent accessible thiols are of the totally external type. Recent evidence shows that some Hb thiol groups are highly reactive and undergo extensive and reversible S-thiolation, and that they may be implicated in interorgan redox equilibrium processes. Participation of thiol groups in nitric oxide ((*)NO) metabolism has also been proved. The evidence argues for a new physiologically relevant role for Hb via involvement in free radical and antioxidant metabolism.

  16. Enhancement of bismuth antibacterial activity with lipophilic thiol chelators.

    PubMed Central

    Domenico, P; Salo, R J; Novick, S G; Schoch, P E; Van Horn, K; Cunha, B A

    1997-01-01

    The antibacterial properties of bismuth are greatly enhanced when bismuth is combined with certain lipophilic thiol compounds. Antibacterial activity was enhanced from 25- to 300-fold by the following seven different thiols, in order of decreasing synergy: 1,3-propanedithiol, dimercaprol (BAL), dithiothreitol, 3-mercapto-2-butanol, beta-mercaptoethanol, 1-monothioglycerol, and mercaptoethylamine. The dithiols produced the greatest synergy with bismuth at optimum bismuth-thiol molar ratios of from 3:1 to 1:1. The monothiols were generally not as synergistic and required molar ratios of from 1:1 to 1:4 for optimum antibacterial activity. The most-active mono- or dithiols were also the most soluble in butanol. The intensity of the yellow formed by bismuth-thiol complexes reflected the degree of chelation and correlated with antibacterial potency at high molar ratios. The bismuth-BAL compound (BisBAL) was active against most bacteria, as assessed by broth dilution, agar diffusion, and agar dilution analyses. Staphylococci (MIC, 5 to 7 microM Bi3+) and Helicobacter pylori (MIC, 2.2 microM) were among the most sensitive bacteria. Gram-negative bacteria were sensitive (MIC, < 17 microM). Enterococci were relatively resistant (MIC, 63 microM Bi3+). The MIC range for anaerobes was 15 to 100 microM Bi3+, except for Clostridium difficile (MIC, 7.5 microM). Bactericidal activity averaged 29% above the MIC. Bactericidal activity increased with increasing pH and/or increasing temperature. Bismuth-thiol solubility, stability, and antibacterial activity depended on pH and the bismuth-thiol molar ratio. BisBAL was stable but ineffective against Escherichia coli at pH 4. Activity and instability (reactivity) increased with increasing alkalinity. BisBAL was acid soluble at a molar ratio of greater than 3:2 and alkaline soluble at a molar ratio of less than 2:3. In conclusion, certain lipophilic thiol compounds enhanced bismuth antibacterial activity against a broad spectrum of

  17. Efficient curing of vinyl carbonates by thiol-ene polymerization.

    PubMed

    Mautner, Andreas; Qin, Xiaohua; Kapeller, Barbara; Russmueller, Guenter; Koch, Thomas; Stampfl, Juergen; Liska, Robert

    2012-12-13

    Vinyl carbonates have recently been identified as a suitable alternative to (meth)acrylates, especially due to the low irritancy and cytotoxicity of these monomers. The drawback of some vinyl carbonates containing abstractable hydrogens arises through their moderate reactivity compared with acrylates. Within this paper, we use the thiol-ene concept to enhance the photoreactivity of vinyl carbonates to a large extent to reach the level of those of similar acrylates. Mechanical properties of the final thiol-ene polymers were determined by nanoindentation. Furthermore, low toxicity of all components was confirmed by osteoblast cell culture experiments.

  18. General and practical formation of thiocyanates from thiols.

    PubMed

    Frei, Reto; Courant, Thibaut; Wodrich, Matthew D; Waser, Jerome

    2015-02-02

    A new method for the cyanation of thiols and disulfides using cyanobenziodoxol(on)e hypervalent iodine reagents is described. Both aliphatic and aromatic thiocyanates can be accessed in good yields in a few minutes at room temperature starting from a broad range of thiols with high chemioselectivity. The complete conversion of disulfides to thiocyanates was also possible. Preliminary computational studies indicated a low energy concerted transition state for the cyanation of the thiolate anion or radical. The developed thiocyanate synthesis has broad potential for various applications in synthetic chemistry, chemical biology and materials science.

  19. Radicals Are Required for Thiol Etching of Gold Particles.

    PubMed

    Dreier, Timothy A; Ackerson, Christopher J

    2015-08-03

    Etching of gold with an excess of thiol ligand is used in both synthesis and analysis of gold particles. Mechanistically, the process of etching gold with excess thiol is unclear. Previous studies have obliquely considered the role of oxygen in thiolate etching of gold. Herein, we show that oxygen or a radical initiator is a necessary component for efficient etching of gold by thiolates. Attenuation of the etching process by radical scavengers in the presence of oxygen, and the restoration of activity by radical initiators under inert atmosphere, strongly implicate the oxygen radical. These data led us to propose an atomistic mechanism in which the oxygen radical initiates the etching process.

  20. Multiscale Surface-Attached Hydrogel Thin Films with Tailored Architecture.

    PubMed

    Chollet, Benjamin; Li, Mengxing; Martwong, Ekkachai; Bresson, Bruno; Fretigny, Christian; Tabeling, Patrick; Tran, Yvette

    2016-05-11

    A facile route for the fabrication of surface-attached hydrogel thin films with well-controlled chemistry and tailored architecture on wide range of thickness from nanometers to micrometers is reported. The synthesis, which consists in cross-linking and grafting the preformed and ene-reactive polymer chains through thiol-ene click chemistry, has the main advantage of being well-controlled without the addition of initiators. As thiol-ene click reaction can be selectively activated by UV-irradiation (in addition to thermal heating), micropatterned hydrogel films are easily synthesized. The versatility of our approach is illustrated by the possibility to fabricate various chemical polymer networks, like stimuli-responsive hydrogels, on various solid substrates, such as silicon wafers, glass, and gold surfaces. Another attractive feature is the development of new complex hydrogel films with targeted architecture. The fabrication of various architectures for polymer films is demonstrated: multilayer hydrogel films in which single-networks are stacked one onto the other, interpenetrating networks films with mixture of two networks in the same layer, and nanocomposite hydrogel films where nanoparticles are stably trapped inside the mesh of the network. Thanks to its simplicity and its versatility this novel approach to surface-attached hydrogel films should have a strong impact in the area of polymer coatings.

  1. Mirror Attachment For Borescope

    NASA Technical Reports Server (NTRS)

    Gearhart, John F.; Peloquin, James E.

    1994-01-01

    Attachment for articulated borescope provides views into small, normally inaccessible spaces. Simple small round mirror on extension arm welded to borescope head. Tilted at angle to axis of borescope head, mirror provides views sideways to borescope head. Disassembly of turbopump blades not necessary to enable fluorescent-penetrant-dye inspection. Attachment used to inspect difficult-to-reach internal parts of other assemblies. Also used for inspection with ordinary white light.

  2. Mirror Attachment For Borescope

    NASA Technical Reports Server (NTRS)

    Gearhart, John F.; Peloquin, James E.

    1994-01-01

    Attachment for articulated borescope provides views into small, normally inaccessible spaces. Simple small round mirror on extension arm welded to borescope head. Tilted at angle to axis of borescope head, mirror provides views sideways to borescope head. Disassembly of turbopump blades not necessary to enable fluorescent-penetrant-dye inspection. Attachment used to inspect difficult-to-reach internal parts of other assemblies. Also used for inspection with ordinary white light.

  3. Micromechanical die attachment surcharge

    DOEpatents

    Filter, William F.; Hohimer, John P.

    2002-01-01

    An attachment structure is disclosed for attaching a die to a supporting substrate without the use of adhesives or solder. The attachment structure, which can be formed by micromachining, functions purely mechanically in utilizing a plurality of shaped pillars (e.g. round, square or polygonal and solid, hollow or slotted) that are formed on one of the die or supporting substrate and which can be urged into contact with various types of mating structures including other pillars, a deformable layer or a plurality of receptacles that are formed on the other of the die or supporting substrate, thereby forming a friction bond that holds the die to the supporting substrate. The attachment structure can further include an alignment structure for precise positioning of the die and supporting substrate to facilitate mounting the die to the supporting substrate. The attachment structure has applications for mounting semiconductor die containing a microelectromechanical (MEM) device, a microsensor or an integrated circuit (IC), and can be used to form a multichip module. The attachment structure is particularly useful for mounting die containing released MEM devices since these devices are fragile and can otherwise be damaged or degraded by adhesive or solder mounting.

  4. Selective anodic desorption for assembly of different thiol monolayers on the individual electrodes of an array.

    PubMed

    Collman, James P; Hosseini, Ali; Eberspacher, Todd A; Chidsey, Christopher E D

    2009-06-02

    The close proximity of two individually addressable electrodes in an interdigitated array provides a unique platform for electrochemical study of multicatalytic processes. Here, we report a "plug-and-play" approach to control the underlying self-assembled monolayer and the electroactive species on each individually addressable electrode of an interdigitated array. The method presented here uses selective anodic desorption of a monolayer from one of the individually addressable electrodes and rapid formation of a different self-assembled monolayer on the freshly cleaned electrode. We illustrate this strategy by introducing variations in the length of the linker to the electroactive species in the self-assembled monolayer, which determines the rate of electron transfer. In order to separate the assembly of the monolayer from the choice of the electroactive species, we use CuI-catalyzed triazole formation ("click" chemistry) to covalently attach an acetylene-terminated electroactive species to an azide-terminated thiol monolayer selectively on each electrode. The resulting variations in the electron-transfer rate to surface-attached ferrocene and in the rate of catalytic oxidation of ascorbate by the ferrocenium/ferrocene couple demonstrate an application of this approach.

  5. Tunable degradation of maleimide-thiol adducts in reducing environments

    PubMed Central

    Baldwin, Aaron D.; Kiick, Kristi L.

    2011-01-01

    Addition chemistries are widely used in preparing biological conjugates, and in particular, maleimide-thiol adducts have been widely employed. Here we show that the resulting succinimide thioether formed by a Michael type addition of a thiol to N-ethylmaleimide (NEM), generally accepted as stable, can in fact undergo retro and exchange reactions in the presence of other thiol compounds at physiological pH and temperature, offering a novel strategy for controlled release. Model studies (1H NMR, HPLC) of NEM conjugated to 4-mercaptophenylacetic acid (MPA), N-acetylcysteine, or 3-mercaptopropionic acid (MP) incubated with glutathione showed half lives of conversion from 20–80 hrs, with extents of conversion from 20–90% for MPA and N-acetylcysteine conjugates. Ring-opened the resultant succinimide thioether as well as any MP adduct did not show retro and exchange reactions. The kinetics of the retro reactions can be modulated by the Michael donor’s reactivity; therefore the degradation of maleimide-thiol adducts could be tuned for controlled release of drugs or degradation of materials at timescales different than those currently possible via disulfide-mediated release. Such approaches may find a new niche for controlled release in reducing environments relevant in chemotherapy and sub-cellular trafficking. PMID:21863904

  6. Rapid Access to Phospholipid Analogs Using Thiol-yne Chemistry

    DTIC Science & Technology

    2015-05-19

    dioleyldithioether PC, concentrating encapsulated nanoparticles . We imagine that these readily accessible lipids could find a number of applications...dithioether PC, concentrating encapsulated nanoparticles . We imagine that these readily accessible lipids could find a number of applications as...alkyne and thiol precursors allows access to numerous lipid analogs. The resulting dithioether phosphati- dylcholines (PCs) offer a biocompatible

  7. Hybrid Organic/Inorganic Thiol-ene-Based Photopolymerized Networks

    PubMed Central

    Schreck, Kathleen M.; Leung, Diana; Bowman, Christopher N.

    2011-01-01

    The thiol-ene reaction serves as a more oxygen tolerant alternative to traditional (meth)acrylate chemistry for forming photopolymerized networks with numerous desirable attributes including energy absorption, optical clarity, and reduced shrinkage stress. However, when utilizing commercially available monomers, many thiol-ene networks also exhibit decreases in properties such as glass transition temperature (Tg) and crosslink density. In this study, hybrid organic/inorganic thiol-ene resins incorporating silsesquioxane (SSQ) species into the photopolymerized networks were investigated as a route to improve these properties. Thiol- and ene-functionalized SSQs (SH-SSQ and allyl-SSQ, respectively) were synthesized via alkoxysilane hydrolysis/condensation chemistry, using a photopolymerizable monomer [either pentaerythriol tetrakis(3-mercaptopropionate) (PETMP) or 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TATATO)] as the reaction solvent. The resulting SSQ-containing solutions (SSQ-PETMP and SSQ-TATATO) were characterized, and their incorporation into photopolymerized networks was evaluated. PMID:21984847

  8. Synthesis of a photo-caged aminooxy alkane thiol.

    PubMed

    Mancini, Rock J; Li, Ronald C; Tolstyka, Zachary P; Maynard, Heather D

    2009-12-07

    A photo-caged aminooxy alkane thiol synthesized in 7 steps and 15% overall yield was used to form a self-assembled monolayer (SAM). Photo-deprotection on the surface was confirmed by FT-IR spectroscopy and contact angle goniometry. Conjugation of a small molecule ketone, ethyl levulinate, further confirmed the presence of aminooxy groups on the surface.

  9. From sulfur to homoglutathione: Thiol metabolism in soybean

    USDA-ARS?s Scientific Manuscript database

    Sulfur is an essential plant nutrient and is metabolized into the sulfur-containing amino acids (cysteine and methionine) and into molecules that protect plants against oxidative and environmental stresses. Although studies of thiol metabolism in the model plant Arabidopsis thaliana (thale cress) h...

  10. Are free radicals involved in thiol-based redox signaling?

    PubMed

    Winterbourn, Christine C

    2015-03-01

    Cells respond to many stimuli by transmitting signals through redox-regulated pathways. It is generally accepted that in many instances signal transduction is via reversible oxidation of thiol proteins, although there is uncertainty about the specific redox transformations involved. The prevailing view is that thiol oxidation occurs by a two electron mechanism, most commonly involving hydrogen peroxide. Free radicals, on the other hand, are considered as damaging species and not generally regarded as important in cell signaling. This paper examines whether it is justified to dismiss radicals or whether they could have a signaling role. Although there is no direct evidence that radicals are involved in transmitting thiol-based redox signals, evidence is presented that they are generated in cells when these signaling pathways are activated. Radicals produce the same thiol oxidation products as two electron oxidants, although by a different mechanism, and at this point radical-mediated pathways should not be dismissed. There are unresolved issues about how radical mechanisms could achieve sufficient selectivity, but this could be possible through colocalization of radical-generating and signal-transducing proteins. Colocalization is also likely to be important for nonradical signaling mechanisms and identification of such associations should be a priority for advancing the field.

  11. Autism and Attachment: The Attachment Q-Sort

    ERIC Educational Resources Information Center

    Rutgers, Anna H.; Van Ijzendoorn, Marinus H.; Bakermans-Kranenburg, Marian J.; Swinkels, Sophie H. N.

    2007-01-01

    Children with autism are able to show secure attachment behaviours to their parents/caregivers. Most studies on attachment in children with autism used a (modified) Strange Situation Procedure (SSP) to examine attachment security. An advantage of the Attachment Q-Sort (AQS) over the SSP is that it can be attuned to the secure-base behaviour of…

  12. Properties of methacrylate-thiol-ene formulations as dental restorative materials

    PubMed Central

    Cramer, Neil B.; Couch, Charles L.; Schreck, Kathleen M.; Boulden, Jordan E.; Wydra, Robert; Stansbury, Jeffrey W.; Bowman, Christopher N.

    2010-01-01

    Objectives The objective of this study was to evaluate ternary methacrylate-thiol-ene systems, with varying thiol-ene content and thiol:ene stoichiometry, as dental restorative resin materials. It was hypothesized that an off-stoichiometric thiol-ene component would enhance interactions between the methacrylate and thiol-ene processes to reduce shrinkage stress while maintaining equivalent mechanical properties. Methods Polymerization kinetics and functional group conversions were determined by Fourier transform infrared spectroscopy (FTIR). Cured resin mechanical properties were evaluated using a three-point flexural test, carried out with a hydraulic universal test system. Polymerization shrinkage stress was measured with a tensometer coupled with simultaneous real-time conversion monitoring. Results The incorporation of thiol-ene mixtures as reactive diluents into conventional dimethacrylate resins previously was shown to combine synergistically advantageous methacrylate mechanical properties with the improved polymerization kinetics and reduced shrinkage stress of thiol-ene systems. In these systems, due to thiol consumption resultant from both the thiol-ene reaction and chain transfer involving the methacrylate polymerization, the optimum thiol:ene stoichiometry deviates from the traditional 1:1 ratio. Increasing the thiol:ene stoichiometry up to 3:1 results in systems with equivalent flexural modulus, 6 – 20 % reduced flexural strength, and 5 – 33 % reduced shrinkage stress relative to 1:1 stoichiometric thiol:ene systems. Significance Due to their improved overall functional group conversion, and shrinkage stress reduction while maintaining equivalent flexural modulus, methacrylate-thiol-ene resins, particularly those with excess thiol, beyond the conventional 1:1 thiol:ene molar ratio, yield superior dental restorative materials compared with purely dimethacrylate resins. PMID:20553973

  13. Ceramic blade attachment system

    DOEpatents

    Boyd, G.L.

    1994-12-13

    A turbine blade having a preestablished rate of thermal expansion is attached to a turbine wheel having a preestablished rate of thermal expansion being greater than the preestablished rate of thermal expansion of the turbine blade. The turbine blade has a root portion having a pair of recessed portions thereon. The turbine wheel includes a plurality of openings in which the turbine blade is positioned. Each of the openings have a pair of grooves therein in which are positioned a pair of pins having a generally rectangular cross-section and a reaction surface thereon. A pair of cylindrical rollers interposed respective ones of the pair of reaction surfaces and the pair of recessed portions. The attachment system or turbine assembly provides an economical, reliable and effective attachment of a component having a preestablished rate of thermal expansion to a component having a greater preestablished rate of thermal expansion. 3 figures.

  14. Reactive attachment disorder.

    PubMed

    Hornor, Gail

    2008-01-01

    Child abuse and neglect affects the lives of many American children and can result in physical injury and disability as well as psychological trauma. Reactive attachment disorder (RAD) is one possible psychological consequence of child abuse and neglect for very young children, younger than 5 years of age. RAD is described as markedly disturbed and developmentally inappropriate social relatedness usually beginning before age 5 years. These behavioral manifestations are the direct result of and come after pathogenic care. To better understand RAD, it is first necessary to understand attachment; therefore, attachment theory is examined. Risk factors for the development of RAD are presented. Implications for pediatric nurse practitioner practice are explored. The pediatric nurse practitioner can play a vital role in recognizing RAD and ensuring that children with this disorder receive prompt mental health assessment and therapy.

  15. Ceramic blade attachment system

    DOEpatents

    Boyd, Gary L.

    1994-01-01

    A turbine blade having a preestablished rate of thermal expansion is attached to a turbine wheel having a preestablished rate of thermal expansion being greater than the preestablished rate of thermal expansion of the turbine blade. The turbine blade has a root portion having a pair of recessed portions thereon. The turbine wheel includes a plurality of openings in which the turbine blade is positioned. Each of the openings have a pair of grooves therein in which are positioned a pair of pins having a generally rectangular cross-section and a reaction surface thereon. A pair of cylindrical rollers interposed respective ones of the pair of reaction surfaces and the pair of recessed portions. The attachment system or turbine assembly provides an economical, reliable and effective attachment of a component having a preestablished rate of thermal expansion to a component having a greater preestablished rate of thermal expansion.

  16. Ladder attachment platform

    DOEpatents

    Swygert,; Richard, W [Springfield, SC

    2012-08-28

    A ladder attachment platform is provided that includes a base for attachment to a ladder that has first and second side rails and a plurality of rungs that extend between in a lateral direction. Also included is a user platform for having a user stand thereon that is carried by the base. The user platform may be positioned with respect to the ladder so that it is not located between a first plane that extends through the first side rail and is perpendicular to the lateral direction and a second plane that extends through the second side rail and is perpendicular to the lateral direction.

  17. Internal pipe attachment mechanism

    DOEpatents

    Bast, R.M.; Chesnut, D.A.; Henning, C.D.; Lennon, J.P.; Pastrnak, J.W.; Smith, J.A.

    1994-12-13

    An attachment mechanism is described for repairing or extending fluid carrying pipes, casings, conduits, etc. utilizing one-way motion of spring tempered fingers to provide a mechanical connection between the attachment mechanism and the pipe. The spring tempered fingers flex to permit insertion into a pipe to a desired insertion depth. The mechanical connection is accomplished by reversing the insertion motion and the mechanical leverage in the fingers forces them outwardly against the inner wall of the pipe. A seal is generated by crushing a sealing assembly by the action of setting the mechanical connection. 6 figures.

  18. Internal pipe attachment mechanism

    DOEpatents

    Bast, Richard M.; Chesnut, Dwayne A.; Henning, Carl D.; Lennon, Joseph P.; Pastrnak, John W.; Smith, Joseph A.

    1994-01-01

    An attachment mechanism for repairing or extending fluid carrying pipes, casings, conduits, etc. utilizing one-way motion of spring tempered fingers to provide a mechanical connection between the attachment mechanism and the pipe. The spring tempered fingers flex to permit insertion into a pipe to a desired insertion depth. The mechanical connection is accomplished by reversing the insertion motion and the mechanical leverage in the fingers forces them outwardly against the inner wall of the pipe. A seal is generated by crushing a sealing assembly by the action of setting the mechanical connection.

  19. Magnetically attached sputter targets

    DOEpatents

    Makowiecki, D.M.; McKernan, M.A.

    1994-02-15

    An improved method and assembly for attaching sputtering targets to cathode assemblies of sputtering systems which includes a magnetically permeable material is described. The magnetically permeable material is imbedded in a target base that is brazed, welded, or soldered to the sputter target, or is mechanically retained in the target material. Target attachment to the cathode is achieved by virtue of the permanent magnets and/or the pole pieces in the cathode assembly that create magnetic flux lines adjacent to the backing plate, which strongly attract the magnetically permeable material in the target assembly. 11 figures.

  20. Magnetically attached sputter targets

    DOEpatents

    Makowiecki, Daniel M.; McKernan, Mark A.

    1994-01-01

    An improved method and assembly for attaching sputtering targets to cathode assemblies of sputtering systems which includes a magnetically permeable material. The magnetically permeable material is imbedded in a target base that is brazed, welded, or soldered to the sputter target, or is mechanically retained in the target material. Target attachment to the cathode is achieved by virtue of the permanent magnets and/or the pole pieces in the cathode assembly that create magnetic flux lines adjacent to the backing plate, which strongly attract the magnetically permeable material in the target assembly.

  1. Thiol adsorption on metal oxides: an approach for selective deposition on zinc oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Soares, Jason W.; Steeves, Diane M.; Singh, Jagdeep; Im, Jisun; Whitten, James E.

    2011-02-01

    We have previously discovered a novel, facile approach to encapsulate ZnO nanorods within thiol complexes. This approach results in a thiol uptake of 30-40% and a 400-500 nm thick thiol-Zn-thiol complex encapsulation layer surrounding ZnO nanorods. By controlling experimental parameters, it is possible to control the thiol deposition, enabling less uptake, which results in a surface monolayer instead of encapsulation. Through this approach, thiol modification of other metal oxide materials, namely TiO2, Al2O3, and MgO, has been attempted. FTIR analysis indicates that thiol adsorption occurs only on ZnO; chemisorption of thiols on other nanoparticles is not evident. Ultrahigh vacuum single crystal adsorption studies demonstrate that ZnO(0001) is also more susceptible to thiol monolayer formation, as evidenced by lack of methanethiol adsorption on TiO2(110) and MgO(0001). These results indicate that the facile thiol modification approach opens a new avenue for surface modification of multi-component metal oxide materials by enabling selective thiol modification of ZnO. This work has potential applicability for creating multiple ligand-functionalized materials, which could be useful for the design of novel multiplexing sensors and photovoltaics.

  2. Attachment and Personality Disorders

    ERIC Educational Resources Information Center

    Sinha, Preeti; Sharan, Pratap

    2007-01-01

    Personality disorders (PDs) arise from core psychopathology of interpersonal relationships and understanding of self and others. The distorted representations of self and others, as well as unhealthy relationships that characterize persons with various PDs, indicate the possibility that persons with PDs have insecure attachment. Insecure…

  3. Day Care and Attachment

    ERIC Educational Resources Information Center

    Portnoy, Fern C.; Simmons, Carolyn H.

    1978-01-01

    The attachment behavior of 35 white, middle-class 3 1/2- to 4-year-olds who had experienced different rearing histories was observed through a series of standardized episodes involving separations and reunions with the mother and a stranger. (Author/JMB)

  4. Induction Curing of Thiol-acrylate and Thiolene Composite Systems

    PubMed Central

    Ye, Sheng; Cramer, Neil B.; Stevens, Blake E.; Sani, Robert L.; Bowman, Christopher N.

    2011-01-01

    Induction curing is demonstrated as a novel type of in situ radiation curing that maintains most of the advantages of photocuring while eliminating the restriction of light accessibility. Induction curing is utilized to polymerize opaque composites comprised of thiol-acrylate and thiol-ene resins, nanoscale magnetic particles, and carbon nanotubes. Nanoscale magnetic particles are dispersed in the resin and upon exposure to the magnetic field, these particles lead to induction heating that rapidly initiates the polymerization. Heat transfer profiles and reaction kinetics of the samples are modeled during the reactions with varying induction heater power, species concentration, species type and sample thickness, and the model is compared with the experimental results. Thiol-ene polymerizations achieved full conversion between 1.5 minutes and 1 hour, depending on the field intensity and the composition, with the maximum reaction temperature decreasing from 146 – 87 °C when the induction heater power was decreased from 8 – 3 kW. The polymerization reactions of the thiol-acrylate system were demonstrated to achieve full conversion between 0.6 and 30 minutes with maximum temperatures from 139 to 86 °C. The experimental behavior was characterized and the temperature profile modeled for the thiol-acrylate composite comprised of sub100nm nickel particles and induction heater power in the range of 32 to 20 kW. A 9°C average deviation was observed between the modeling and experimental results for the maximum temperature rise. The model also was utilized to predict reaction temperatures and kinetics for systems with varying thermal initiator concentration, initiator half-life, monomer molecular weight and temperature gradients in samples with varying thickness, thereby demonstrating that induction curing represents a designable and tunable polymerization method. Finally, induction curing was utilized to cure thiol-acrylate systems containing carbon nanotubes where 1 wt

  5. Thiol/disulfide homeostasis as a novel indicator of oxidative stress in children with simple febrile seizures.

    PubMed

    Elmas, Bahri; Erel, Özcan; Ersavaş, Dilek; Yürümez, Yusuf

    2017-08-14

    Simple febrile seizures are generally benign, but during the seizure, elevated levels of glutamate and high levels of oxygen use due to the high metabolic brain activity result in oxidative stress. However, the relationship between febrile seizures and oxidative stress remains unclear. In this study, we investigated thiol/disulfide homeostasis as a new oxidative stress parameter in patients with simple febrile seizures. This study was performed between February 2016 and May 2016 at the Pediatric Emergency Unit. The study population consisted of 40 patients with a diagnosis of simple febrile seizure and 30 control participants aged 8-59 months. Total thiol, native thiol and disulfide levels, disulfide/native thiol, disulfide/total thiol, and native thiol/total thiol ratios were used as thiol/disulfide homeostasis parameters and were quantified in patient and control groups. Furthermore, correlations with seizure duration were investigated. In the patient group, native and total thiol levels and native thiol/total thiol ratios were low, and disulfide levels, disulfide/native thiol, and disulfide/total thiol ratios were significantly higher than in the control group. Negative correlations were observed between seizure duration, total and native thiol levels, and native thiol/total thiol ratio, whereas positive correlations were observed between seizure duration and disulfide/native thiol and disulfide/total thiol ratio. The sensitivities of both disulfide/native thiol and disulfide/total thiol ratios were high for simple febrile seizures. Simple febrile seizures may cause impairment in favor of disulfide bonds in thiol/disulfide homeostasis. Overall, these changes may contribute to neuronal cell damage after simple febrile seizures.

  6. God attachment, mother attachment, and father attachment in early and middle adolescence.

    PubMed

    Sim, Tick Ngee; Yow, Amanda Shixian

    2011-06-01

    The present study examined the interplay of attachment to God, attachment to mother, and attachment to father with respect to adjustment (hope, self-esteem, depression) for 130 early and 106 middle adolescents in Singapore. Results showed that the parental attachments were generally linked (in expected directions) to adjustment. God attachment, however, had unique results. At the bivariate level, God attachment was only linked to early adolescents' self-esteem. When considered together with parental attachments (including interactions), God attachment did not emerge as the key moderator in attachment interactions and yielded some unexpected results (e.g., being positively linked to depression). These results are discussed viz-a-viz the secure base and safe haven functions that God and parental attachments may play during adolescence.

  7. Cadmium-Responsive Thiols in the Ectomycorrhizal Fungus Paxillus involutus

    PubMed Central

    Courbot, Mikael; Diez, Laurent; Ruotolo, Roberta; Chalot, Michel; Leroy, Pierre

    2004-01-01

    Molecular and cellular mechanisms underlying the sustained metal tolerance of ectomycorrhizal fungi are largely unknown. Some of the main mechanisms involved in metal detoxification appear to involve the chelation of metal ions in the cytosol with thiol-containing compounds, such as glutathione, phytochelatins, or metallothioneins. We used an improved high-performance liquid chromatography method for the simultaneous measurement of thiol-containing compounds from cysteine and its derivatives (γ-glutamylcysteine, glutathione) to higher-molecular-mass compounds (phytochelatins). We found that glutathione and γ-glutamylcysteine contents increased when the ectomycorrhizal fungus Paxillus involutus was exposed to cadmium. An additional compound with a 3-kDa molecular mass, most probably related to a metallothionein, increased drastically in mycelia exposed to cadmium. The relative lack of phytochelatins and the presence of a putative metallothionein suggest that ectomycorrhizal fungi may use a different means to tolerate heavy metals, such as Cd, than do their plant hosts. PMID:15574943

  8. Thiol-ene clickable hyaluronans: from macro-to nanogels.

    PubMed

    Hachet, Emilie; Sereni, Nicolas; Pignot-Paintrand, Isabelle; Ravaine, Valérie; Szarpak-Jankowska, Anna; Auzély-Velty, Rachel

    2014-04-01

    The fabrication of hyaluronic acid (HA) nanogels using a thiol-ene reaction has been demonstrated. HA was modified with pentenoate groups and then cross-linked with poly(ethylene glycol)-bis(thiol) by exposure to UV light. The cross-linking density and thereby the rigidity of the obtained gels were precisely controlled by the degree of substitution of pentenoate-modified HA. Their swelling properties also depended on cross-linking density. To produce hydrogels at the nanoscale, hyaluronic acid precursors were solely confined inside liposomes before cross-linking and purified after cross-linking. The size of the resulting nanogels followed their swelling properties and was also affected by their cross-linking density. Such bionanogels with tunable mechanical and swelling properties have potential in drug delivery.

  9. Investigation of thiol derivatized gold nanoparticle sensors for gas analysis

    NASA Astrophysics Data System (ADS)

    Stephens, Jared S.

    Analysis of volatile organic compounds (VOCs) in air and exhaled breath by sensor array is a very useful testing technique. It can provide non-invasive, fast, inexpensive testing for many diseases. Breath analysis has been very successful in identifying cancer and other diseases by using a chemiresistor sensor or array with gold nanoparticles to detect biomarkers. Acetone is a biomarker for diabetes and having a portable testing device could help to monitor diabetic and therapeutic progress. An advantage to this testing method is it is conducted at room temperature instead of 200 degrees Celsius. 3. The objective of this research is to determine the effect of thiol derivatized gold nanoparticles based on sensor(s) detection of VOCs. The VOCs to be tested are acetone, ethanol, and a mixture of acetone and ethanol. Each chip is tested under all three VOCs and three concentration levels (0.1, 1, and 5.0 ppm). VOC samples are used to test the sensors' ability to detect and differentiate VOCs. Sensors (also referred to as a chip) are prepared using several types of thiol derivatized gold nanoparticles. The factors are: thiol compound and molar volume loading of the thiol in synthesis. The average resistance results are used to determine the VOC selectivity of the sensors tested. The results show a trend of increasing resistance as VOC concentration is increased relative to dry air; which is used as baseline for VOCs. Several sensors show a high selectivity to one or more VOCs. Overall the 57 micromoles of 4-methoxy-toluenethiol sensor shows the strongest selectivity for VOCs tested. 3. Gerfen, Kurt. 2012. Detection of Acetone in Air Using Silver Ion Exchanged ZSM-5 and Zinc Oxide Sensing Films. Master of Science thesis, University of Louisville.

  10. HNO Is Produced by the Reaction of NO with Thiols.

    PubMed

    Suarez, Sebastian A; Muñoz, Martina; Alvarez, Lucia; Venâncio, Mateus F; Rocha, Willian R; Bikiel, Damian E; Marti, Marcelo A; Doctorovich, Fabio

    2017-10-04

    Azanone (nitroxyl, HNO) is a highly reactive compound whose biological role is still a matter of debate. One possible route for its formation is NO reduction by biological reductants. These reactions have been historically discarded due to the negative redox potential for the NO,H+/HNO couple. However, the NO to HNO conversion mediated by vitamins C, E, and aromatic alcohols has been recently shown to be feasible from a chemical standpoint. Based on these precedents, we decided to study the reaction of NO with thiols as potential sources of HNO. Using two complementary approaches, trapping by a Mn porphyrin and an HNO electrochemical sensor, we found that under anaerobic conditions aliphatic and aromatic thiols (as well as selenols) are able to convert NO to HNO, albeit at different rates. Further mechanistic analysis using ab initio methods shows that the reaction between NO and the thiol produces a free radical adduct RSNOH(•), which reacts with a second NO molecule to produce HNO and a nitrosothiol. The nitrosothiol intermediate reacts further with RSH to produce a second molecule of HNO and RSSR, as previously reported.

  11. Organized thiol functional groups in mesoporous core shell colloids

    SciTech Connect

    Marchena, Martin H.; Granada, Mara; Bordoni, Andrea V.; Joselevich, Maria; Troiani, Horacio; Williams, Federico J.; Wolosiuk, Alejandro

    2012-03-15

    The co-condensation in situ of tetraethoxysilane (TEOS) and mercaptopropyltrimethoxysilane (MPTMS) using cetyltrimethylammonium bromide (CTAB) as a template results in the synthesis of multilayered mesoporous structured SiO{sub 2} colloids with 'onion-like' chemical environments. Thiol groups were anchored to an inner selected SiO{sub 2} porous layer in a bilayered core shell particle producing different chemical regions inside the colloidal layered structure. X-Ray Photoelectron Spectroscopy (XPS) shows a preferential anchoring of the -SH groups in the double layer shell system, while porosimetry and simple chemical modifications confirm that pores are accessible. We can envision the synthesis of interesting colloidal objects with defined chemical environments with highly controlled properties. - Graphical abstract: Mesoporous core shell SiO{sub 2} colloids with organized thiol groups. Highlights: Black-Right-Pointing-Pointer Double shell mesoporous silica colloids templated with CTAB. Black-Right-Pointing-Pointer Sequential deposition of mesoporous SiO{sub 2} layers with different chemistries. Black-Right-Pointing-Pointer XPS shows the selective functionalization of mesoporous layers with thiol groups.

  12. Thiol-ene Clickable Poly(glycidol) Hydrogels for Biofabrication.

    PubMed

    Stichler, Simone; Jungst, Tomasz; Schamel, Martha; Zilkowski, Ilona; Kuhlmann, Matthias; Böck, Thomas; Blunk, Torsten; Teßmar, Jörg; Groll, Jürgen

    2017-01-01

    In this study we introduce linear poly(glycidol) (PG), a structural analog of poly(ethylene glycol) bearing side chains at each repeating unit, as polymer basis for bioink development. We prepare allyl- and thiol-functional linear PG that can rapidly be polymerized to a three-dimensionally cross-linked hydrogel network via UV mediated thiol-ene click reaction. Influence of polymer concentration and UV irradiation on mechanical properties and swelling behavior was examined. Thiol-functional PG was synthesized in two structural variations, one containing ester groups that are susceptible to hydrolytic cleavage, and the other one ester-free and stable against hydrolysis. This allowed the preparation of degradable and non-degradable hydrogels. Cytocompatibility of the hydrogel was demonstrated by encapsulation of human bone marrow-derived mesenchymal stem cells (hBMSCs). Rheological properties of the hydrogels were adjusted for dispense plotting by addition of high molecular weight hyaluronic acid. The optimized formulation enabled highly reproducible plotting of constructs composed of 20 layers with an overall height of 3.90 mm.

  13. Differential stress induced by thiol adsorption on facetted nanocrystals.

    PubMed

    Watari, Moyu; McKendry, Rachel A; Vögtli, Manuel; Aeppli, Gabriel; Soh, Yeong-Ah; Shi, Xiaowen; Xiong, Gang; Huang, Xiaojing; Harder, Ross; Robinson, Ian K

    2011-09-25

    Polycrystalline gold films coated with thiol-based self-assembled monolayers (SAM) form the basis of a wide range of nanomechanical sensor platforms. The detection of adsorbates with such devices relies on the transmission of mechanical forces, which is mediated by chemically derived stress at the organic-inorganic interface. Here, we show that the structure of a single 300-nm-diameter facetted gold nanocrystal, measured with coherent X-ray diffraction, changes profoundly after the adsorption of one of the simplest SAM-forming organic molecules. On self-assembly of propane thiol, the crystal's flat facets contract radially inwards relative to its spherical regions. Finite-element modelling indicates that this geometry change requires large stresses that are comparable to those observed in cantilever measurements. The large magnitude and slow kinetics of the contraction can be explained by an intermixed gold-sulphur layer that has recently been identified crystallographically. Our results illustrate the importance of crystal edges and grain boundaries in interface chemistry and have broad implications for the application of thiol-based SAMs, ranging from nanomechanical sensors to coating technologies.

  14. Identification of the thiol ester lipids in apolipoprotein B

    SciTech Connect

    Huang, G.; Lee, D.M.; Singh, S.

    1988-03-08

    Human plasma low-density lipoproteins of 1.032-1.043 g/mL density were totally delipidized. The reduced and carboxymethylated apolipoprotein B was incubated with 50 mM (/sup 14/C) methylamine at pH 8.5 at 30 /sup 0/C. Covalent incorporation of (/sup 14/C) methylamine was observed with concomitant generation of new sulfhydryl groups, which could be blocked with (/sup 3/H)- or (/sup 14/C)iodoacetic acid. One type of the (/sup 14/C) methylamine-modified products was separated from the protein and was found to be lipid in nature. Its R/sub f/ on thin-layer chromatography (TLC) was similar to that of the synthetic N-methyl fatty acyl amides. After purification with TLC and transesterification in 3 N methanolic HCl, methyl esters of C/sub 16/ and C/sub 18/ fatty acids at 1:1 ratio were identified by gas-liquid chromatography. The transesterification method was verified with the known N-methyl fatty acyl amides. These results suggest the presence of labile thiol ester linked palmitate and stearate in apolipoprotein B. Under mild alkaline conditions, the thiol ester bonds are broken by methylamine and form N-methyl fatty acyl amides and release new -SH groups. Intramolecular thiol ester bonds linked between cysteine side chains and acidic amino acid residues were also found present, which will be reported separately.

  15. Identification of the thiol ester linked lipids in apolipoprotein B

    SciTech Connect

    Huang, G.; Lee, D.M.; Singh, S.

    1988-03-08

    Human plasma low-density lipoproteins of 1.032-1.043 g/mL density were totally delipidized. The reduced and carboxymethylated apolipoprotein B was incubated with 50 mM (/sup 14/C)methylamine at pH 8.5 at 30 degrees C. Covalent incorporation of (/sup 14/C)methylamine was observed with concomitant generation of new sulfhydryl groups, which could be blocked with (/sup 3/H)- or (/sup 14/C)iodoacetic acid. One type of the (/sup 14/C)methylamine-modified products was separated from the protein and was found to be lipid in nature. Its Rf on thin-layer chromatography (TLC) was similar to that of the synthetic N-methyl fatty acyl amides. After purification with TLC and transesterification in 3 N methanolic HCl, methyl esters of C16 and C18 fatty acids at 1:1 ratio were identified by gas-liquid chromatography. The transesterification method was verified with the known N-methyl fatty acyl amides. These results suggest the presence of labile thiol ester linked palmitate and stearate in apolipoprotein B. Under mild alkaline conditions, the thiol ester bonds are broken by methylamine and form N-methyl fatty acyl amides and release new-SH groups. Intramolecular thiol ester bonds linked between cysteine side chains and acidic amino acid residues were also found present, which will be reported separately.

  16. Analytical detection of biological thiols in a microchip capillary channel.

    PubMed

    Chand, Rohit; Jha, Sandeep Kumar; Islam, Kamrul; Han, Dawoon; Shin, Ik-Soo; Kim, Yong-Sang

    2013-02-15

    Sulfur-containing amino acids, such as cysteine and homocysteine play crucial roles in biological systems for the diagnosis of medical states. In this regard, this paper deals with separation, aliquot and detection of amino thiols on a microchip capillary electrophoresis with electrochemical detection in an inverted double Y-shaped microchannel. Unlike the conventional capillary electrophoresis, the modified microchannel design helps in storing the separated thiols in different reservoirs for further analysis, if required; and also eliminates the need of electrodes regeneration. The device was fabricated using conventional photolithographic technique which consisted of gold microelectrodes on a soda lime glass wafer and microchannels in PDMS mold. Multiple detections were performed using in-house fabricated dual potentiostat. Based on amperometric detection, cysteine and homocysteine were analyzed in 105 s and 120 s, respectively after diverting in branched channels. Repeated experiments proved the good reproducibility of the device. The device produced a linear response for both cysteine and homocysteine in electrochemical analysis. To prove the practicality of device, we also analyzed cysteine and homocysteine in real blood samples without any pre-treatment. Upon calculation, the device showed a very low limit of detection of 0.05 μM. The modified microchip design shall find a broad range of analytical applications involving assays of thiols and other biological compounds.

  17. Turbine nozzle attachment system

    DOEpatents

    Norton, P.F.; Shaffer, J.E.

    1995-10-24

    A nozzle guide vane assembly having a preestablished rate of thermal expansion is positioned in a gas turbine engine and is attached to conventional metallic components. The nozzle guide vane assembly includes a pair of legs extending radially outwardly from an outer shroud and a pair of mounting legs extending radially inwardly from an inner shroud. Each of the pair of legs and mounting legs have a pair of holes therein. A plurality of members attached to the gas turbine engine have a plurality of bores therein which axially align with corresponding ones of the pair of holes in the legs. A plurality of pins are positioned within the corresponding holes and bores radially positioning the nozzle guide vane assembly about a central axis of the gas turbine engine. 3 figs.

  18. Turbine nozzle attachment system

    DOEpatents

    Norton, Paul F.; Shaffer, James E.

    1995-01-01

    A nozzle guide vane assembly having a preestablished rate of thermal expansion is positioned in a gas turbine engine and being attached to conventional metallic components. The nozzle guide vane assembly includes a pair of legs extending radially outwardly from an outer shroud and a pair of mounting legs extending radially inwardly from an inner shroud. Each of the pair of legs and mounting legs have a pair of holes therein. A plurality of members attached to the gas turbine engine have a plurality of bores therein which axially align with corresponding ones of the pair of holes in the legs. A plurality of pins are positioned within the corresponding holes and bores radially positioning the nozzle guide vane assembly about a central axis of the gas turbine engine.

  19. Fluorescence lifetime attachment LIFA

    NASA Astrophysics Data System (ADS)

    van der Oord, Cornelius J. R.; Stoop, Karel W. J.; van Geest, Lambertus K.

    2001-05-01

    We present the Lambert Instruments Fluorescence Lifetime Attachment LIFA. LIFA enables easy to use and affordable microscopy and macroscopic FLIM. The system implements the homodyne detection scheme for measuring the fluorescence lifetime in each pixel of the image. The microscopy system features an ultra bright LED illuminator, the LI-(mu) Cam intensified CCD camera a high frequency signal generator. The illuminator replaces the excitation light source of a standard fluorescence microscopy, while the LI-(mu) CAM intensified CCD camera is attached to the photo-port. Both the illuminator and the intensifier are modulated at a frequency up to 100 MHz at a series of phase differences. The lifetime image is calculated from the series of images on a personal computer.

  20. Thermal and Mechanical Properties of Sequential and Simultaneous Thiol-Ene-Isocyanate Networks

    NASA Astrophysics Data System (ADS)

    McNair, Olivia; Brent, Davis; Savin, Daniel

    2011-03-01

    Ternary networks containing having stoichiometrically balanced thiol /(ene+isocyanate) ranging from 0 to 20 mol% isocyanate were synthesized via sequential or simultaneous thiol/ene and thiol/isocyanate click reactions. The effects of cross-link density were studied using three thiols, GDMP (difunctional), 3T (trifunctional) and 4T (tetrafunctional) respectively. TEA catalyzes the isocyanate-thiol coupling and chain extension, while the photoinitiator DMPA initiates a radical thiol-ene crosslinking process. Real-time FTIR was used to study kinetics of both light and dark reactions utilizing thiol, ene and isocyanate peaks which appear independently. It was found that difunctional thiols and isocyanates reacted initially, forming chain extended prepolymers end-capped with thiol functionalities. Upon UV irradiation, thiol functionalized prepolymers reacted with TTT, a trifunctional ene, forming networks containing incorporated thiourethane linkages. Initial DSC results indicated higher Tgs for higher cross-linked networks; however, isocyanate content has significant effects on each system. Films were also be thermally characterized via DMA and mechanical properties measured using MTS.

  1. Fast and selective modification of thiol proteins/peptides by N-(phenylseleno)phthalimide.

    PubMed

    Wang, Zhengfang; Zhang, Yun; Zhang, Hao; Harrington, Peter B; Chen, Hao

    2012-03-01

    We previously reported that selenamide reagents such as ebselen and N-(phenylseleno)phthalimide (NPSP) can be used to selectively derivatize thiols for mass spectrometric analysis, and the introduced selenium tags are useful as they could survive or removed with collision-induced dissociation (CID). Described herein is the further study of the reactivity of various protein/peptide thiols toward NPSP and its application to derivatize thiol peptides in protein digests. With a modified protocol (i.e., dissolving NPSP in acetonitrile instead of aqueous solvent), we found that quantitative conversion of thiols can be obtained in seconds, using NPSP in a slight excess amount (NPSP:thiol of 1.1-2:1). Further investigation shows that the thiol reactivity toward NPSP reflects its chemical environment and accessibility in proteins/peptides. For instance, adjacent basic amino acid residues increase the thiol reactivity, probably because they could stabilize the thiolate form to facilitate the nucleophilic attack of thiol on NPSP. In the case of creatine phosphokinase, the native protein predominately has one thiol reacted with NPSP while all of four thiol groups of the denatured protein can be derivatized, in accordance with the corresponding protein conformation. In addition, thiol peptides in protein/peptide enzymatic digests can be quickly and effectively tagged by NPSP following tri-n-butylphosphine (TBP) reduction. Notably, all three thiols of the peptide QCCASVCSL in the insulin peptic digest can be modified simultaneously by NPSP. These results suggest a novel and selective method for protecting thiols in the bottom-up approach for protein structure analysis.

  2. Fast and Selective Modification of Thiol Proteins/Peptides by N-(Phenylseleno)phthalimide

    NASA Astrophysics Data System (ADS)

    Wang, Zhengfang; Zhang, Yun; Zhang, Hao; Harrington, Peter B.; Chen, Hao

    2012-03-01

    We previously reported that selenamide reagents such as ebselen and N-(phenylseleno)phthalimide (NPSP) can be used to selectively derivatize thiols for mass spectrometric analysis, and the introduced selenium tags are useful as they could survive or removed with collision-induced dissociation (CID). Described herein is the further study of the reactivity of various protein/peptide thiols toward NPSP and its application to derivatize thiol peptides in protein digests. With a modified protocol (i.e., dissolving NPSP in acetonitrile instead of aqueous solvent), we found that quantitative conversion of thiols can be obtained in seconds, using NPSP in a slight excess amount (NPSP:thiol of 1.1-2:1). Further investigation shows that the thiol reactivity toward NPSP reflects its chemical environment and accessibility in proteins/peptides. For instance, adjacent basic amino acid residues increase the thiol reactivity, probably because they could stabilize the thiolate form to facilitate the nucleophilic attack of thiol on NPSP. In the case of creatine phosphokinase, the native protein predominately has one thiol reacted with NPSP while all of four thiol groups of the denatured protein can be derivatized, in accordance with the corresponding protein conformation. In addition, thiol peptides in protein/peptide enzymatic digests can be quickly and effectively tagged by NPSP following tri- n-butylphosphine (TBP) reduction. Notably, all three thiols of the peptide QCCASVCSL in the insulin peptic digest can be modified simultaneously by NPSP. These results suggest a novel and selective method for protecting thiols in the bottom-up approach for protein structure analysis.

  3. Adsorption of Dissolved Metals in the Berkeley Pit using Thiol-Functionalized Self-Assembled Monolayers on Mesoporous Supports (Thiol-SAMMS)

    SciTech Connect

    Betancourt, Amaury P.; Mattigod, Shas V.; Wellman, Dawn M.

    2010-03-07

    The Berkeley Pit in Butte, Montana, is heavily contaminated with dissolved metals. Adsorption and extraction of these metals can be accomplished through the use of a selective adsorbent. For this research, the adsorbent used was thiol-functionalized Self-Assembled Monolayers on Mesoporous Supports (thiol-SAMMS), which was developed at Pacific Northwest National Laboratory (PNNL). Thiol-SAMMS selectively binds to numerous types of dissolved metals. The objective of this research was to evaluate the loading and kinetics of aluminum, beryllium, copper, and zinc on thiol-SAMMS. For the loading tests, a series of Berkeley Pit water to thiol-SAMMS ratios (mL:g) were tested. These ratios were 1000:1, 500:1, 100:1, and 50:1. Berkeley Pit water is acidic (pH {approx} 2.5). This can affect the performance of SAMMS materials. Therefore, the effect of pH was evaluated by conducting parallel series of loading tests wherein the Berkeley Pit water was neutralized before or after addition of thiol-SAMMS, and a series of kinetics tests wherein the Berkeley Pit water was neutralized before addition of thiol-SAMMS for the first test and was not neutralized for the second test. For the kinetics tests, one Berkeley Pit water to thiol-SAMMS ratio was tested, which was 2000:1. The results of the loading and kinetics tests suggest that a significant decrease in dissolved metal concentration at Berkeley Pit could be realized through neutralization of Berkeley Pit water. Thiol-SAMMS technology has a limited application under the highly acidic conditions posed by the Berkeley Pit. However, thiol-SAMMS could provide a secondary remedial technique which would complete the remedial system and remove dissolved metals from the Berkeley Pit to below drinking water standards.

  4. Inhibition of the Vacuolar-like ATPase from Halobacterium saccharovorum by Thiol Reagents: Evidence for Different Functional Thiols

    NASA Technical Reports Server (NTRS)

    Hochstein, L. I.; Stanlotter, H.; Emrich, E.; Morrison, David (Technical Monitor)

    1994-01-01

    N-Ethylmaleimide (NEM) inhibited the vacuolar-like ATPase from Halobacterium saccharovorum (K(sub i) approximately 1 mM) by modifying one or more of the thiols located on the largest of the subunit. ATP protected against inhibition and coincidentally prevented NEM binding which suggested that NEM acts at or near the catalytic site. p-Chloromercuriphenylsulfonate (PCMS) also inhibited this ATPase (K(sub i) approximately 90 microM). ATP did not protect against PCMS inhibition. Dithiothreitol (DTT) partially reversed PCMS inhibition and restored approximately half of the initial activity of 90% inhibited enzyme. DTT did not restore activity of the NEM-inhibited enzyme or the PCMS-inhibited enzyme when it was subsequently incubated with NEM. The failure of ATP to protect against PCMS inhibition and the inability of DTT to restore activity of enzyme incubated in the presence of PCMS and NEM suggests these reagents react with different thiols and that the PCMS-sensitive thiol may have a structural role.

  5. Inhibition of the Vacuolar-like ATPase from Halobacterium saccharovorum by Thiol Reagents: Evidence for Different Functional Thiols

    NASA Technical Reports Server (NTRS)

    Hochstein, L. I.; Stanlotter, H.; Emrich, E.; Morrison, David (Technical Monitor)

    1994-01-01

    N-Ethylmaleimide (NEM) inhibited the vacuolar-like ATPase from Halobacterium saccharovorum (K(sub i) approximately 1 mM) by modifying one or more of the thiols located on the largest of the subunit. ATP protected against inhibition and coincidentally prevented NEM binding which suggested that NEM acts at or near the catalytic site. p-Chloromercuriphenylsulfonate (PCMS) also inhibited this ATPase (K(sub i) approximately 90 microM). ATP did not protect against PCMS inhibition. Dithiothreitol (DTT) partially reversed PCMS inhibition and restored approximately half of the initial activity of 90% inhibited enzyme. DTT did not restore activity of the NEM-inhibited enzyme or the PCMS-inhibited enzyme when it was subsequently incubated with NEM. The failure of ATP to protect against PCMS inhibition and the inability of DTT to restore activity of enzyme incubated in the presence of PCMS and NEM suggests these reagents react with different thiols and that the PCMS-sensitive thiol may have a structural role.

  6. Attachment: Theoretical Development and Critique

    ERIC Educational Resources Information Center

    Slater, Ruth

    2007-01-01

    Zeanah argues that ethological attachment theory, as outlined by John Bowlby, has provided one of the most important frameworks for understanding crucial risk and protective factors in social and emotional development. However, although attachment theory and the notion of attachment disorders have influenced such initiatives, many psychologists,…

  7. Attachment Theory: Retrospect and Prospect.

    ERIC Educational Resources Information Center

    Bretherton, Inge

    1985-01-01

    Provides overview of attachment theory as parented by John Bowlby in "Attachment and Loss". Uses two major concepts from this work to interpret refinements and elaborations of attachment theory attibuted to Mary Ainsworth. Considers how recent insights into development of socioemotional understanding and development of event…

  8. Attachment and Relationships: Beyond Parenting.

    ERIC Educational Resources Information Center

    Honig, Alice Sterling

    Using a question-answer format, this paper examines the concept of attachment and its importance for parents and caregivers of young children. Twenty topics are addressed through an examination of relevant theory, research findings, and clinical evidence: (1) a "who's who" list of researchers on attachment; (2) definition of attachment;…

  9. Attachment Theory: Retrospect and Prospect.

    ERIC Educational Resources Information Center

    Bretherton, Inge

    1985-01-01

    Provides overview of attachment theory as parented by John Bowlby in "Attachment and Loss". Uses two major concepts from this work to interpret refinements and elaborations of attachment theory attibuted to Mary Ainsworth. Considers how recent insights into development of socioemotional understanding and development of event…

  10. Adopting Children with Attachment Problems.

    ERIC Educational Resources Information Center

    Hughes, Daniel A.

    1999-01-01

    Notes that attachment behavior in infants is a facet of normal child development, and that children with attachment problems require special attention during and after the adoption process. Presents actions needed to increase the probability that such children can be successfully adopted, detailed attachment patterns, and parenting strategies and…

  11. Attachment: Theoretical Development and Critique

    ERIC Educational Resources Information Center

    Slater, Ruth

    2007-01-01

    Zeanah argues that ethological attachment theory, as outlined by John Bowlby, has provided one of the most important frameworks for understanding crucial risk and protective factors in social and emotional development. However, although attachment theory and the notion of attachment disorders have influenced such initiatives, many psychologists,…

  12. Attachment as Regulation: A Commentary.

    ERIC Educational Resources Information Center

    Pipp, Sandra; Harmon, Robert J.

    1987-01-01

    Discusses ways in which Myron Hofer's work (1987), which draws on studies of rodents and primates, alters the traditional perspective on human attachment. Emphasizes the importance of the component of attachment that does not develop in explaining attachment in the first six months of life. (PCB)

  13. Total, free, and protein-bound thiols in plasma of peritoneal dialysis and predialysis patients.

    PubMed

    Przemysław, Włodek; Piotr, Książek; Grażyna, Chwatko; Danuta, Kowalczyk-Pachel; Małgorzata, Iciek; Bernadeta, Marcykiewicz; Małgorzata, Suliga; Witold, Smoleński

    2011-12-01

    Thiol compounds such as glutathione, homocysteine, and cysteinyl-glycine are the natural reservoir of reductive capacity of the cells. Chronic renal failure is accompanied by disturbances in redox status of plasma thiols. The aim of the present study was to compare the changes in concentrations of different forms of thiols in plasma of terminal renal failure patients, nondialyzed and on peritoneal dialysis. Total concentrations of different redox forms of thiols were determined by high performance liquid chromatography. We observed that total concentration of glutathione in terminal renal failure patients decreased and total concentration of the remaining thiols in these patients significantly increased. Continuous ambulatory peritoneal dialysis had the following features in comparison with nondialyzed patients: (1) glutathione and cysteine concentration was restored and (2) free fraction of thiols rose, while protein-bound fraction dropped (except for homocysteine). Continuous ambulatory peritoneal dialysis corrects total concentration of glutathione and cysteine, in comparison with nondialyzed patients.

  14. Controlling surface functionality through generation of thiol groups in a self-assembled monolayer.

    SciTech Connect

    Lud, S. Q.; Neppl, S.; Richter, G.; Bruno, P.; Gruen, D. M.; Jordan, R.; Feulner, P.; Stutzmann, M.; Garrido, J. A.; Materials Science Division; Technische Univ. Munchen

    2010-01-01

    A lithographic method to generate reactive thiol groups on functionalized synthetic diamond for biosensor and molecular electronic applications is developed. We demonstrate that ultrananocrystalline diamond (UNCD) thin films covalently functionalized with surface-generated thiol groups allow controlled thiol-disulfide exchange surface hybridization processes. The generation of the thiol functional head groups was obtained by irradiating phenylsulfonic acid (PSA) monolayers on UNCD surfaces. The conversion of the functional headgroup of the self-assembled monolayer was verified by using X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS), and fluorescence microscopy. Our findings indicate the selective generation of reactive thiol surface groups. Furthermore, we demonstrate the grafting of yeast cytochrome c to the thiol-modified diamond surface and the electron transfer between protein and electrode.

  15. Thiol switches in redox regulation of chloroplasts: balancing redox state, metabolism and oxidative stress.

    PubMed

    Dietz, Karl-Josef; Hell, Rüdiger

    2015-05-01

    In photosynthesizing chloroplasts, rapidly changing energy input, intermediate generation of strong reductants as well as oxidants and multiple participating physicochemical processes and pathways, call for efficient regulation. Coupling redox information to protein function via thiol modifications offers a powerful mechanism to activate, down-regulate and coordinate interdependent processes. Efficient thiol switching of target proteins involves the thiol-disulfide redox regulatory network, which is highly elaborated in chloroplasts. This review addresses the features of this network. Its conditional function depends on specificity of reduction and oxidation reactions and pathways, thiol redox buffering, but also formation of heterogeneous milieus by microdomains, metabolite gradients and macromolecular assemblies. One major player is glutathione. Its synthesis and function is under feedback redox control. The number of thiol-controlled processes and involved thiol switched proteins is steadily increasing, e.g., in tetrapyrrole biosynthesis, plastid transcription and plastid translation. Thus chloroplasts utilize an intricate and versatile redox regulatory network for intraorganellar and retrograde communication.

  16. Site-dependent atomic and molecular affinities of hydrocarbons, amines and thiols on diamond nanoparticles

    NASA Astrophysics Data System (ADS)

    Lai, Lin; Barnard, Amanda S.

    2016-04-01

    Like many of the useful nanomaterials being produced on the industrial scale, the surface of diamond nanoparticles includes a complicated mixture of various atomic and molecular adsorbates, attaching to the facets following synthesis. Some of these adsorbates may be functional, and adsorption is encouraged to promote applications in biotechnology and nanomedicine, but others are purely adventurous and must be removed prior to use. In order to devise more effective treatments it is advantageous to know the relative strength of the interactions of the adsorbates with the surface, and ideally how abundant they are likely to be under different conditions. In this paper we use a series of explicit electronic structure simulations to map the distribution of small hydrocarbons, amines and thiols on a 2.9 nm diamond nanoparticle, with atomic level resolution, in 3-D. We find a clear relationship between surface reconstructions, facet orientation, and the distribution of the different adsorbates; with a greater concentration expected on the (100) and (110) facets, particularly when the supersaturation in the reservoir is high. Adsorption on the (111) facets is highly unlikely, suggesting that controlled graphitization may be a useful stage in the cleaning and treatment of nanodiamonds, prior to the deliberate coating with functional adsorbates needed for drug delivery applications.

  17. Report of the APSAC task force on attachment therapy, reactive attachment disorder, and attachment problems.

    PubMed

    Chaffin, Mark; Hanson, Rochelle; Saunders, Benjamin E; Nichols, Todd; Barnett, Douglas; Zeanah, Charles; Berliner, Lucy; Egeland, Byron; Newman, Elana; Lyon, Tom; LeTourneau, Elizabeth; Miller-Perrin, Cindy

    2006-02-01

    Although the term attachment disorder is ambiguous, attachment therapies are increasingly used with children who are maltreated, particularly those in foster care or adoptive homes. Some children described as having attachment disorders show extreme disturbances. The needs of these children and their caretakers are real. How to meet their needs is less clear. A number of attachment-based treatment and parenting approaches purport to help children described as attachment disordered. Attachment therapy is a young and diverse field, and the benefits and risks of many treatments remain scientifically undetermined. Controversies have arisen about potentially harmful attachment therapy techniques used by a subset of attachment therapists. In this report, the Task Force reviews the controversy and makes recommendations for assessment, treatment, and practices. The report reflects American Professional Society on the Abuse of Children's (APSAC) position and also was endorsed by the American Psychological Association's Division 37 and the Division 37 Section on Child Maltreatment.

  18. Functional Microcapsules via Thiol-Ene Photopolymerization in Droplet-Based Microfluidics.

    PubMed

    Amato, Douglas V; Lee, Hyomin; Werner, Jörg G; Weitz, David A; Patton, Derek L

    2017-02-01

    Thiol-ene chemistry was exploited in droplet-based microfluidics to fabricate advanced microcapsules with tunable encapsulation, degradation, and thermal properties. In addition, by utilizing the thiol-ene photopolymerization with tunable cross-link density, we demonstrate the importance of monomer conversion on the retention of omniphilic cargo in double emulsion templated microcapsules. Furthermore, we highlight the rapid cure kinetics afforded by thiol-ene chemistry in a continuous flow photopatterning device for hemispherical microparticle production.

  19. Space Station attached payloads

    NASA Technical Reports Server (NTRS)

    Clark, Lenwood G.

    1990-01-01

    The Space Station Freedom is being designed and developed with user requirements being used to shape the configuration. Plans include accommodation provisions for a wide variety of attached payloads including the Earth sciences research activities which are the focus of this conference. The station program is even beginning some preliminary payload manifesting which involves planning for accommodation of payload during the station's assembly flights. Potential payload organizations should be aware of the station's plans for payload accommodations so as to guide their own payload activities for future space station use.

  20. The thiol pool in human plasma: The central contribution of albumin to redox processes

    PubMed Central

    Turell, Lucía; Radi, Rafael; Alvarez, Beatriz

    2013-01-01

    The plasma compartment has particular features regarding the nature and concentration of low and high molecular weight thiols and oxidized derivatives. Plasma is relatively poor in thiol-based antioxidants; thiols are in lower concentrations than in cells and mostly oxidized. The different thiol-disulfide pairs are not in equilibrium and the steady-state concentrations of total thiols as well as reduced versus oxidized ratios are maintained by kinetic barriers, including the rates of reactions and transport processes. The single thiol of human serum albumin (HSA-SH) is the most abundant plasma thiol. It is an important target for oxidants and electrophiles due to its reactivity with a wide variety of species and its relatively high concentration. A relatively stable sulfenic (HSA-SO3H) acid can be formed in albumin exposed to oxidants. Plasma increases in mixed disulfides (HSA-SSR) or in sulfinic (HSA-SO2H) and sulfonic (HSA-SO3H) acids are associated with different pathologies and may constitute biomarkers of the antioxidant role of the albumin thiol. In this work we provide a critical review of the plasma thiol pool with a focus on human serum albumin. PMID:23747983

  1. Hydrogen sulfide deactivates common nitrobenzofurazan-based fluorescent thiol labeling reagents.

    PubMed

    Montoya, Leticia A; Pluth, Michael D

    2014-06-17

    Sulfhydryl-containing compounds, including thiols and hydrogen sulfide (H2S), play important but differential roles in biological structure and function. One major challenge in separating the biological roles of thiols and H2S is developing tools to effectively separate the reactivity of these sulfhydryl-containing compounds. To address this challenge, we report the differential responses of common electrophilic fluorescent thiol labeling reagents, including nitrobenzofurazan-based scaffolds, maleimides, alkylating agents, and electrophilic aldehydes, toward cysteine and H2S. Although H2S reacted with all of the investigated scaffolds, the photophysical response to each scaffold was significantly different. Maleimide-based, alkylating, and aldehydic thiol labeling reagents provided a diminished fluorescence response when treated with H2S. By contrast, nitrobenzofurazan-based labeling reagents were deactivated by H2S addition. Furthermore, the addition of H2S to thiol-activated nitrobenzofurazan-based reagents reduced the fluorescence signal, thus establishing the incompatibility of nitrobenzofurazan-based thiol labeling reagents in the presence of H2S. Taken together, these studies highlight the differential reactivity of thiols and H2S toward common thiol-labeling reagents and suggest that sufficient care must be taken when labeling or measuring thiols in cellular environments that produce H2S due to the potential for both false-positive and eroded responses.

  2. Low-molecular-weight thiols in plants: functional and analytical implications.

    PubMed

    Pivato, Micaela; Fabrega-Prats, Marta; Masi, Antonio

    2014-10-15

    Low-molecular-weight (LMW) thiols are a class of highly reactive compounds massively involved in the maintenance of cellular redox homeostasis. They are implicated in plant responses to almost all stress factors, as well as in the regulation of cellular metabolism. The most studied LMW thiols are glutathione and its biosynthetically related compounds (cysteine, γ-glutamylcysteine, cysteinylglycine, and phytochelatins). Other LMW thiols are described in the literature, such as thiocysteine, cysteamine, homocysteine, lipoic acid, and many species-specific volatile thiols. Here, we review the known LMW thiols in plants, briefly describing their physico-chemical properties, their relevance in post-translational protein modification, and recently-developed thiol detection methods. Current research points to a huge thiol biodiversity in plants and many species-specific and organ-specific thiols remain to be identified. Recent advances in technology should help researchers in this very challenging task, helping us to decipher the roles of thiols in plant metabolism. Copyright © 2014. Published by Elsevier Inc.

  3. Oxidation of dissolved elemental mercury by thiol compounds under anoxic conditions.

    PubMed

    Zheng, Wang; Lin, Hui; Mann, Benjamin F; Liang, Liyuan; Gu, Baohua

    2013-11-19

    Mercuric ion, Hg(2+), forms strong complexes with thiolate compounds that commonly dominate Hg(II) speciation in natural freshwater. However, reactions between dissolved aqueous elemental mercury (Hg(0)aq) and organic ligands in general, and thiol compounds in particular, are not well studied although these reactions likely affect Hg speciation and cycling in the environment. In this study, we compared the reaction rates between Hg(0)aq and a number of selected organic ligands with varying molecular structures and sulfur (S) oxidation states in dark, anoxic conditions to assess the role of these ligands in Hg(0)aq oxidation. Significant Hg(0)aq oxidation was observed with all thiols but not with ligands containing no S. Compounds with oxidized S (e.g., disulfide) exhibited little or no reactivity toward Hg(0)aq either at pH 7. The rate and extent of Hg(0)aq oxidation varied greatly depending on the chemical and structural properties of thiols, thiol/Hg ratios, and the presence or absence of electron acceptors. Smaller aliphatic thiols and higher thiol/Hg ratios resulted in higher Hg(0)aq oxidation rates than larger aromatic thiols at lower thiol/Hg ratios. The addition of electron acceptors (e.g., humic acid) also led to substantially increased Hg(0)aq oxidation. Our results suggest that thiol-induced oxidation of Hg(0)aq is important under anoxic conditions and can affect Hg redox transformation and bioavailability for microbial methylation.

  4. Solvent-Free Synthesis and Fluorescence of a Thiol-Reactive Sensor for Undergraduate Organic Laboratories.

    PubMed

    Patterson, Anastasia L; May, Mary D; Visser, Bryan J; Kislukhin, Alexander A; Vosburg, David A

    2013-12-10

    A green organic laboratory experiment was developed in which students synthesize a sensor for thiols using a microscale, solventless Diels-Alder reaction at room temperature or 37 °C. The molecular probe is easily purified by column chromatography in a Pasteur pipet and characterized by thin-layer chromatography and NMR spectroscopy. The thiol-reactive sensor becomes intensely fluorescent upon exposure to thiols from N-acetylcysteine, bovine serum albumin, or human hair (pretreated with a reducing agent to reveal cysteine thiols in α-keratin). This fluorescence is observable even with micrograms of probe.

  5. Solvent-Free Synthesis and Fluorescence of a Thiol-Reactive Sensor for Undergraduate Organic Laboratories

    PubMed Central

    Patterson, Anastasia L.; May, Mary D.; Visser, Bryan J.; Kislukhin, Alexander A.; Vosburg, David A.

    2013-01-01

    A green organic laboratory experiment was developed in which students synthesize a sensor for thiols using a microscale, solventless Diels–Alder reaction at room temperature or 37 °C. The molecular probe is easily purified by column chromatography in a Pasteur pipet and characterized by thin-layer chromatography and NMR spectroscopy. The thiol-reactive sensor becomes intensely fluorescent upon exposure to thiols from N-acetylcysteine, bovine serum albumin, or human hair (pretreated with a reducing agent to reveal cysteine thiols in α-keratin). This fluorescence is observable even with micrograms of probe. PMID:24415795

  6. Abilities of peroxidases to catalyse peroxidase-oxidase oxidation of thiols.

    PubMed Central

    Svensson, B E

    1988-01-01

    The abilities of various peroxidases to catalyse the peroxidase-oxidase oxidation of seven aminothiols were studied. Cysteamine and cysteine esters were found to be peroxidase-oxidase substrates for eosinophil peroxidase and myeloperoxidase, whereas other thiols tested were inactive or poorly active with these peroxidases. With lactoperoxidase and horseradish peroxidase, all the tested thiols were inactive or poorly active as peroxidase-oxidase substrates. These studies suggest that a main reason for thiols being poor peroxidase-oxidase substrates is because these thiols are poor peroxidatic substrates. PMID:2852004

  7. Hydrogen Sulfide Deactivates Common Nitrobenzofurazan-Based Fluorescent Thiol Labeling Reagents

    PubMed Central

    2015-01-01

    Sulfhydryl-containing compounds, including thiols and hydrogen sulfide (H2S), play important but differential roles in biological structure and function. One major challenge in separating the biological roles of thiols and H2S is developing tools to effectively separate the reactivity of these sulfhydryl-containing compounds. To address this challenge, we report the differential responses of common electrophilic fluorescent thiol labeling reagents, including nitrobenzofurazan-based scaffolds, maleimides, alkylating agents, and electrophilic aldehydes, toward cysteine and H2S. Although H2S reacted with all of the investigated scaffolds, the photophysical response to each scaffold was significantly different. Maleimide-based, alkylating, and aldehydic thiol labeling reagents provided a diminished fluorescence response when treated with H2S. By contrast, nitrobenzofurazan-based labeling reagents were deactivated by H2S addition. Furthermore, the addition of H2S to thiol-activated nitrobenzofurazan-based reagents reduced the fluorescence signal, thus establishing the incompatibility of nitrobenzofurazan-based thiol labeling reagents in the presence of H2S. Taken together, these studies highlight the differential reactivity of thiols and H2S toward common thiol-labeling reagents and suggest that sufficient care must be taken when labeling or measuring thiols in cellular environments that produce H2S due to the potential for both false-positive and eroded responses. PMID:24852143

  8. Branching Reaction in Melanogenesis: The Effect of Intramolecular Cyclization on Thiol Binding

    NASA Astrophysics Data System (ADS)

    Kishida, Ryo; Kasai, Hideaki; Aspera, Susan Meñez; Arevalo, Ryan Lacdao; Nakanishi, Hiroshi

    2017-01-01

    With the aid of density functional theory-based first principles calculations, we investigated energetics and electronic structure changes in reactions involving dopaquinone to give insights into the branching behaviors in melanogenesis. The reactions we investigated are the intramolecular cyclization and thiol binding, which are competing with each other. It was found that, in order to accomplish thiol binding, charge transfer of around one electron from thiol to dopaquinone occurs. Furthermore, intramolecular cyclization of dopaquinone increases the lowest unnoccupied molecular orbital level substantially. This result clearly shows prevention of the binding of thiol by intramolecular cyclization.

  9. A Two-Photon Fluorescent Probe for Lysosomal Thiols in Live Cells and Tissues

    PubMed Central

    Fan, Jiangli; Han, Zhichao; Kang, Yao; Peng, Xiaojun

    2016-01-01

    Lysosome-specific fluorescent probes are exclusive to elucidate the functions of lysosomal thiols. Moreover, two-photon microscopy offers advantages of less phototoxicity, better three dimensional spatial localization, deeper penetration depth and lower self-absorption. However, such fluorescent probes for thiols are still rare. In this work, an efficient two-photon fluorophore 1,8-naphthalimide-based probe conjugating a 2,4-dinitrobenzenesulfonyl chloride and morpholine was designed and synthesized, which exhibited high selectivity and sensitivity towards lysosomal thiols by turn-on fluorescence method quantitatively and was successfully applied to the imaging of thiols in live cells and tissues by two-photon microscopy. PMID:26794434

  10. Recent progress in luminescent and colorimetric chemosensors for detection of thiols.

    PubMed

    Jung, Hyo Sung; Chen, Xiaoqiang; Kim, Jong Seung; Yoon, Juyoung

    2013-07-21

    In the past few decades, the development of optical probes for thiols has attracted great attention because of the biological importance of the thiol-containing molecules such as cysteine (Cys), homocysteine (Hcy), and glutathione (GSH). This tutorial review focuses on various thiol detection methods based on luminescent or colorimetric spectrophotometry published during the period 2010-2012. The discussion covers a diversity of sensing mechanisms such as Michael addition, cyclization with aldehydes, conjugate addition-cyclization, cleavage of sulfonamide and sulfonate esters, thiol-halogen nucleophilic substitution, disulfide exchange, native chemical ligation (NCL), metal complex-displace coordination, and nanomaterial-related and DNA-based chemosensors.

  11. Thiol/disulphide homeostasis as a novel indicator of oxidative stress in sudden sensorineural hearing loss.

    PubMed

    Dinc, M E; Ulusoy, S; Is, A; Ayan, N N; Avincsal, M O; Bicer, C; Erel, O

    2016-05-01

    To investigate a novel oxidative stress marker, thiol/disulphide literature homeostasis, in patients with idiopathic sudden sensorineural hearing loss, and to compare the results with healthy controls for the first time. Thirty-two patients with idiopathic sudden sensorineural hearing loss and 30 healthy individuals were included in the study. Serum native thiol, total thiol and disulphide levels were measured, and disulphide/native thiol and disulphide/total thiol ratios were determined in all subjects. Serum native thiol and total thiol levels were significantly lower in patients with sudden sensorineural hearing loss compared with controls (p < 0.05). Of the 32 patients, 25 had lower native thiol levels than controls (333.2 ± 73.9 vs 381.8 ± 35.6 μmol/l, p = 0.002) and 24 had lower total thiol levels (375.1 ± 74.3 vs 426.1 ± 39.3 μmol/l, p = 0.002). The changes in oxidative markers evident in a significant number of patients may be associated with oxidative stress, which may, in turn, have caused sudden sensorineural hearing loss in those patients.

  12. Thiol-chromene click chemistry: a coumarin-based derivative and its use as regenerable thiol probe and in bioimaging applications.

    PubMed

    Yang, Yutao; Huo, Fangjun; Yin, Caixia; Zheng, Anmin; Chao, Jianbin; Li, Yingqi; Nie, Zongxiu; Martínez-Máñez, Ramón; Liu, Diansheng

    2013-09-15

    The synthesis and characterization of a coumarin-chromene (8, 9-dihydro-2H-cyclopenta[b]pyrano[2,3-f]chromene-2,10(7aH)-dione) (1) derivative and its use for thiol chemosensing in water was reported. Experimental details showed 1 acts as a probe for the detection of thiols including cysteine (Cys), homocysteine (Hcy) and glutathione (GSH), whereas amino acids which do not contain thiols induced no changes in UV-vis spectra and fluorescence emission properties of 1. A possible detection mechanism is a nucleophilic attack of thiols to the α,β-unsaturated ketone in 1 that resulted in a fluorescent coumarin derivative. Further studies showed that 1-thiol derivatives can be applied to the design of regenerative chemodosimeters for Cu(2+), Hg(2+) and Cd(2+) in water based on M(n+)-promoted desulfurization and recovery of 1. Furthermore, the optical properties of the probe and its Cys-addition product were theoretically studied. The ability of probe 1 to detect thiols in living cells (HepG2 cells) via an enhancement of the fluorescence was proved. Moreover, the applicability of 1 for the direct determination of biorelevant thiols in a complex matrix such as human plasma was also demonstrated. Copyright © 2013 Elsevier B.V. All rights reserved.

  13. Neighborhood Quality and Attachment

    PubMed Central

    Poortinga, Wouter; Calve, Tatiana; Jones, Nikki; Lannon, Simon; Rees, Tabitha; Rodgers, Sarah E.; Lyons, Ronan A.; Johnson, Rhodri

    2016-01-01

    Various studies have shown that neighborhood quality is linked to neighborhood attachment and satisfaction. However, most have relied upon residents’ own perceptions rather than independent observations of the neighborhood environment. This study examines the reliability and validity of the revised Residential Environment Assessment Tool (REAT 2.0), an audit instrument covering both public and private spaces of the neighborhood environment. The research shows that REAT 2.0 is a reliable, easy-to-use instrument and that most underlying constructs can be validated against residents’ own neighborhood perceptions. The convergent validity of the instrument, which was tested against digital map data, can be improved for a number of miscellaneous urban form items. The research further found that neighborhood attachment was significantly associated with the overall REAT 2.0 score. This association can mainly be attributed to the property-level neighborhood quality and natural elements components. The research demonstrates the importance of private spaces in the outlook of the neighborhood environment. PMID:28260806

  14. Ceramic blade attachment system

    DOEpatents

    Frey, G.A.; Jimenez, O.D.

    1996-12-03

    A turbine blade having a preestablished rate of thermal expansion is attached to a turbine flange having a preestablished rate of thermal expansion being greater than the preestablished rate of thermal expansion of the turbine blade. The turbine flange includes a first upstanding flange and a second upstanding flange having a groove formed between them. The turbine flange further includes a recess. Each of the first and second upstanding flanges have a plurality of bores therein. A turbine blade has a first member and a second member positioned in one of the groove and the recess. Each of the first member and the second member have a plurality of bores therein. A pin is positioned in respective ones of the plurality of bores in the first and second upstanding members and the first and second members and attach the blade to the turbine flange. The pin has a preestablished rate of thermal expansion being substantially equal to the rate of thermal expansion of the blade. 4 figs.

  15. Ceramic blade attachment system

    DOEpatents

    Frey, deceased, Gary A.; Jimenez, Oscar D.

    1996-01-01

    A turbine blade having a preestablished rate of thermal expansion is attached to a turbine flange having a preestablished rate of thermal expansion being greater than the preestablished rate of thermal expansion of the turbine blade. The turbine flange includes a first upstanding flange and a second upstanding flange having a groove formed therebetween. The turbine flange further includes a recess. Each of the first and second upstanding flanges have a plurality of bores therein. A turbine blade has a first member and a second member positioned in one of the groove and the recess. Each of the first member and the second member have a plurality of bores therein. And, a pin is positioned in respective ones of the plurality of bores in the first and second upstanding members and the first and second members and attach the blade to the turbine flange. The pin has a preestablished rate of thermal expansion being substantially equal to the rate of thermal expansion of the blade.

  16. Evaluation of benzofuroxan as a chromophoric oxidizing agent for thiol groups by using its reactions with papain, ficin, bromelain and low-molecular-weight thiols.

    PubMed

    Shipton, M; Stuchbury, T; Brocklehurst, K

    1977-03-01

    1. Benzofuroxan (benzofurazan 1-oxide, benzo-2-oxa-1,3-diazole N-oxide) was evaluated as a specific chromophoric oxidizing agent for thiol groups. 2. Aliphatic thiol groups both in low-molecular-weight molecules and in the enzymes papain (EC 3.4.22.2), ficin (EC 3.4.22.3) and bromelain (EC 3.4.22.4) readily reduce benzofuroxan to o-benzoquinone dixime; potential competing reactions of amino groups are negligibly slow. 3. The fate of the thiol depends on its structure: a mechanism is proposed in which the thiol and benzofuroxan form an adduct which, if steric factors permit, reacts with another molecule of thiol to form a disulphide; when the thiol is located in the active site of a thiol proteinase and steric factors preclude enzyme dinner formation, the adduct reacts instead with water or HO- to form a sulphenic acid; attack on the sulphur atom of the adduct by either a sulphur or oxygen nucleophile releases o-benzoquinone dioxine. 4. Benzofuroxan contains n o proton-binding sites with pKa values in the range 3-10 and probably none in the range 0-14; o-benzoquinone dioxine undergoes a one-proton ionization with pKa=6.75.5. o-benzoquinone dioxime absorbs strongly at wavelengths greater than 410nm, where absorption by benzofuroxan, proteins and simple thiol compounds is negligible; 416 nm is an isosbestic point (epsilon 416 = 5110 litre. mol-1-cm-1); epsilon430=3740+[1460/(1+[H+]/Ka)] where pKa=6.75. 6. The possibility of acid-base catalysis of the oxidation by active-centre histidine residues of the thiol proteinases is discussed.

  17. Evaluation of benzofuroxan as a chromophoric oxidizing agent for thiol groups by using its reactions with papain, ficin, bromelain and low-molecular-weight thiols.

    PubMed Central

    Shipton, M; Stuchbury, T; Brocklehurst, K

    1977-01-01

    1. Benzofuroxan (benzofurazan 1-oxide, benzo-2-oxa-1,3-diazole N-oxide) was evaluated as a specific chromophoric oxidizing agent for thiol groups. 2. Aliphatic thiol groups both in low-molecular-weight molecules and in the enzymes papain (EC 3.4.22.2), ficin (EC 3.4.22.3) and bromelain (EC 3.4.22.4) readily reduce benzofuroxan to o-benzoquinone dixime; potential competing reactions of amino groups are negligibly slow. 3. The fate of the thiol depends on its structure: a mechanism is proposed in which the thiol and benzofuroxan form an adduct which, if steric factors permit, reacts with another molecule of thiol to form a disulphide; when the thiol is located in the active site of a thiol proteinase and steric factors preclude enzyme dinner formation, the adduct reacts instead with water or HO- to form a sulphenic acid; attack on the sulphur atom of the adduct by either a sulphur or oxygen nucleophile releases o-benzoquinone dioxine. 4. Benzofuroxan contains n o proton-binding sites with pKa values in the range 3-10 and probably none in the range 0-14; o-benzoquinone dioxine undergoes a one-proton ionization with pKa=6.75.5. o-benzoquinone dioxime absorbs strongly at wavelengths greater than 410nm, where absorption by benzofuroxan, proteins and simple thiol compounds is negligible; 416 nm is an isosbestic point (epsilon 416 = 5110 litre. mol-1-cm-1); epsilon430=3740+[1460/(1+[H+]/Ka)] where pKa=6.75. 6. The possibility of acid-base catalysis of the oxidation by active-centre histidine residues of the thiol proteinases is discussed. PMID:851434

  18. Involvement of thiol-based mechanisms in plant development.

    PubMed

    Rouhier, Nicolas; Cerveau, Delphine; Couturier, Jérémy; Reichheld, Jean-Philippe; Rey, Pascal

    2015-08-01

    Increasing knowledge has been recently gained regarding the redox regulation of plant developmental stages. The current state of knowledge concerning the involvement of glutathione, glutaredoxins and thioredoxins in plant development is reviewed. The control of the thiol redox status is mainly ensured by glutathione (GSH), a cysteine-containing tripeptide and by reductases sharing redox-active cysteines, glutaredoxins (GRXs) and thioredoxins (TRXs). Indeed, thiol groups present in many regulatory proteins and metabolic enzymes are prone to oxidation, ultimately leading to post-translational modifications such as disulfide bond formation or glutathionylation. This review focuses on the involvement of GSH, GRXs and TRXs in plant development. Recent studies showed that the proper functioning of root and shoot apical meristems depends on glutathione content and redox status, which regulate, among others, cell cycle and hormone-related processes. A critical role of GRXs in the formation of floral organs has been uncovered, likely through the redox regulation of TGA transcription factor activity. TRXs fulfill many functions in plant development via the regulation of embryo formation, the control of cell-to-cell communication, the mobilization of seed reserves, the biogenesis of chloroplastic structures, the metabolism of carbon and the maintenance of cell redox homeostasis. This review also highlights the tight relationships between thiols, hormones and carbon metabolism, allowing a proper development of plants in relation with the varying environment and the energy availability. GSH, GRXs and TRXs play key roles during the whole plant developmental cycle via their antioxidant functions and the redox-regulation of signaling pathways. This article is part of a Special Issue entitled Redox regulation of differentiation and de-differentiation. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. Mitochondrial Thiols in the Regulation of Cell Death Pathways

    PubMed Central

    Yin, Fei; Sancheti, Harsh

    2012-01-01

    Abstract Significance: Regulation of mitochondrial H2O2 homeostasis and its involvement in the regulation of redox-sensitive signaling and transcriptional pathways is the consequence of the concerted activities of the mitochondrial energy- and redox systems. Recent Advances: The energy component of this mitochondrial energy-redox axis entails the formation of reducing equivalents and their flow through the respiratory chain with the consequent electron leak to generate \\documentclass{aastex}\\usepackage{amsbsy}\\usepackage{amsfonts}\\usepackage{amssymb}\\usepackage{bm}\\usepackage{mathrsfs}\\usepackage{pifont}\\usepackage{stmaryrd}\\usepackage{textcomp}\\usepackage{portland, xspace}\\usepackage{amsmath, amsxtra}\\pagestyle{empty}\\DeclareMathSizes{10}{9}{7}{6}\\begin{document} $${ \\rm O}_2^{ \\cdot - }$$ \\end{document} and H2O2. The mitochondrial redox component entails the thiol-based antioxidant system, largely accounted for by glutathione- and thioredoxin-based systems that support the activities of glutathione peroxidases, peroxiredoxins, and methionine sulfoxide reductase. The ultimate reductant for these systems is NADPH: mitochondrial sources of NADPH are the nicotinamide nucleotide transhydrogenase, isocitrate dehydrogenase-2, and malic enzyme. NADPH also supports the glutaredoxin activity that regulates the extent of S-glutathionylation of mitochondrial proteins in response to altered redox status. Critical Issues: The integrated network of these mitochondrial thiols constitute a regulatory device involved in the maintenance of steady-state levels of H2O2, mitochondrial and cellular redox and metabolic homeostasis, as well as the modulation of cytosolic redox-sensitive signaling; disturbances of this regulatory device affects transcription, growth, and ultimately influences cell survival/death. Future Directions: The modulation of key mitochondrial thiol proteins, which participate in redox signaling, maintenance of the bioenergetic machinery, oxidative

  20. Impairment of thiol-disulfide homeostasis in preeclampsia.

    PubMed

    Korkmaz, Vakkas; Kurdoglu, Zehra; Alisik, Murat; Cetin, Orkun; Korkmaz, Hilal; Surer, Hatice; Erel, Ozcan

    2016-12-01

    To investigate the effects of severity of preeclampsia on thiol-disulfide homeostasis (TDH). A total of 108 participants were divided into three groups: Group 1 was composed of pregnant women with no obstetric complications, Group 2 included pregnant women with mild preeclampsia, and Group 3 consisted of pregnant women with severe preeclampsia. TDH parameters were determined, and comparisons of clinical and routine laboratory test findings were made in all groups. The serum native thiol level was 347.9 ± 27.4 in the control group, 237.2 ± 44.2 in the mild preeclampsia group, and 227.9 ± 53.1 in the severe preeclampsia group (p < 0.001). The serum total thiol level was 376.1 ± 31.9 in the control group, 261.8 ± 49.4 in the mild preeclampsia group, and 248.3 ± 57.4 in the severe preeclampsia group (p < 0.001). The disulfide level was 14.1 ± 5.6 in the control group, 12.3 ± 5.1 in the mild preeclampsia group, and 10.2 ± 4.8 in the severe preeclampsia group (p = 0.001). A significant correlation between impairment in degree of TDH and severity of preeclampsia was observed. TDH was impaired in women with preeclampsia, and this impairment increased with disease severity. Therefore, impaired TDH may have a role in the etiopathogenesis of the disease.

  1. A new three-dimensional silver(I) coordination framework with a diamondoid topology constructed from 2-(pyridin-4-yl)-1H-imidazole-4,5-dicarboxylic acid.

    PubMed

    Deng, Zhi-He; Peng, Zhen-Jian; Huang, Jun

    2013-05-01

    The title compound, poly[[μ4-5-carboxy-4-carboxylato-2-(pyridin-4-yl)-1H-imidazol-1-ido]disilver(I)], [Ag2(C10H5N3O4)]n, was synthesized by reacting silver nitrate with 2-(pyridin-4-yl)-1H-imidazole-4,5-dicarboxylic acid (H3PyIDC) under hydrothermal conditions. The asymmetric unit contains two crystallographically independent Ag(I) cations and one unique HPyIDC(2-) anion. Both Ag(I) cations are three-coordinated in distorted T-shaped coordination geometries. One Ag(I) cation is coordinated by one N and two O atoms from two HPyIDC(2-) anions, while the other is bonded to one O and two N atoms from two HPyIDC(2-) anions. It is interesting to note that the HPyIDC(2-) group acts as a μ4-bridging ligand to link the Ag(I) cations into a three-dimensional framework, which can be simplified as a diamondoid topology. The thermal stability and photoluminescent properties of the title compound have also been studied.

  2. Thiol-Disulfide Exchange in Gram-Positive Firmicutes.

    PubMed

    Davey, Lauren; Halperin, Scott A; Lee, Song F

    2016-11-01

    Extracytoplasmic thiol-disulfide oxidoreductases (TDORs) catalyze the oxidation, reduction, and isomerization of protein disulfide bonds. Although these processes have been characterized in Gram-negative bacteria, the majority of Gram-positive TDORs have only recently been discovered. Results from recent studies have revealed distinct trends in the types of TDOR used by different groups of Gram-positive bacteria, and in their biological functions. Actinobacteria TDORs can be essential for viability, while Firmicute TDORs influence various physiological processes, including protein stability, oxidative stress resistance, bacteriocin production, and virulence. In this review we discuss the diverse extracytoplasmic TDORs used by Gram-positive bacteria, with a focus on Gram-positive Firmicutes.

  3. Functional Conducting Polymers via Thiol-ene Chemistry

    PubMed Central

    Feldman, Kathleen E.; Martin, David C.

    2012-01-01

    We demonstrate here that thiol-ene chemistry can be used to provide side-chain functionalized monomers based on 3,4-propylenedioxythiophene (ProDOT) containing ionic, neutral, hydrophobic, and hydrophilic side chains. All reactions gave high yields and purification could generally be accomplished through precipitation. These monomers were polymerized either chemically or electro-chemically to give soluble materials or conductive films, respectively. This strategy provides for facile tuning of the solubility, film surface chemistry, and film morphology of this class of conducting polymers. PMID:25585932

  4. Amphiphilic silicone architectures via anaerobic thiol-ene chemistry.

    PubMed

    Keddie, Daniel J; Grande, John B; Gonzaga, Ferdinand; Brook, Michael A; Dargaville, Tim R

    2011-11-18

    Despite broad application, few silicone-based surfactants of known structure or, therefore, surfactancy have been prepared because of an absence of selective routes and instability of silicones to acid and base. Herein the synthesis of a library of explicit silicone-poly(ethylene glycol) (PEG) materials is reported. Pure silicone fragments were generated by the B(C(6)F(5))(3)-catalyzed condensation of alkoxysilanes and vinyl-functionalized hydrosilanes. The resulting pure products were coupled to thiol-terminated PEG materials using photogenerated radicals under anaerobic conditions.

  5. Communication: Vacuum ultraviolet photoabsorption of interstellar icy thiols

    NASA Astrophysics Data System (ADS)

    Bhuin, Radha Gobinda; Sivaraman, Bhalamurugan; Lo, Jen-Iu; Sekhar, B. N. Raja; Cheng, Bing-Ming; Pradeep, Thalappil; Mason, Nigel John

    2014-12-01

    Following the recent identification of ethanethiol in the interstellar medium (ISM) we have carried out Vacuum UltraViolet (VUV) spectroscopy studies of ethanethiol (CH3CH2SH) from 10 K until sublimation in an ultrahigh vacuum chamber simulating astrochemical conditions. These results are compared with those of methanethiol (CH3SH), the lower order thiol also reported to be present in the ISM. VUV spectra recorded at higher temperature reveal conformational changes in the ice and phase transitions whilst evidence for dimer production is also presented.

  6. Study of Highly Selective and Efficient Thiol Derivatization using Selenium Reagents by Mass Spectrometry

    SciTech Connect

    Xu, Kehua; Zhang, Yun W.; Tang, Bo; Laskin, Julia; Roach, Patrick J.; Chen, Hao

    2010-08-15

    Biological thiols are critical physiological components and their detection often involves derivatization. This paper reports a systemic mass spectrometry (MS) investigation of the cleavage of Se-N bond by thiol to form a new Se-S bond, the new selenium chemistry for thiol labeling. Our data shows that the reaction is highly selective, rapid, reversible and efficient. For instance, among twenty amino acids, only cysteine was found to be reactive with Se-N containing reagents and the reaction takes place in seconds. By adding dithiothreitol (DTT), the newly formed Se-S bond of peptides/proteins can be reduced back to free thiol. The high selectivity and excellent reversibility of the reaction provide potential of using this chemistry for selective identification of thiol compounds or enriching and purifying thiol peptides/proteins. In addition, the derivatized thiol peptides have interesting dissociation behavior, which is tunable using different selenium reagents. For example, by introducing an adjacent nucleophilic group into the selenium reagent in the case of using ebselen, the reaction product of ebselen with glutathione (GSH) is easy to lose the selenium tag upon collision-induced dissociation (CID), which is useful to "fish out" those peptides containing free cysteine residues by precursor ion scan. By contrast, the selenium tag of N-(phenylseleno) phthalimide reagent can be stable and survive in CID process, which would be of value in pinpointing thiol location using a top-down proteomic approach. Also, the high conversion yield of the reaction allows the counting of total number of thiol in proteins. We believe that ebselen or N-(phenylseleno) phthalimide as tagging thiol-protein reagents will have important applications in both qualitative and quantitative analysis of different thiol-proteins derived from living cells by MS method.

  7. Ceramic blade attachment system

    DOEpatents

    Shaffer, J.E.

    1995-01-10

    A turbine blade having a preestablished rate of thermal expansion is attached to a turbine wheel having a preestablished rate of thermal expansion being greater than the preestablished rate of thermal expansion of the turbine blade. The turbine blade has a root portion having a first groove and a second groove therein. The turbine wheel includes a plurality of openings in which the turbine blade is positioned. Each of the openings has a first groove and a second groove therein. The space or void formed between the first grooves and the second grooves has a plurality of spherical balls positioned therein. The plurality of spherical balls has a preestablished rate of thermal expansion being equal to the preestablished rate of thermal expansion of the turbine blade. 4 figures.

  8. Ceramic blade attachment system

    DOEpatents

    Shaffer, James E.

    1995-01-01

    A turbine blade having a preestablished rate of thermal expansion is attached to a turbine wheel having a preestablished rate of thermal expansion being greater than the preestablished rate of thermal expansion of the turbine blade. The turbine blade has a root portion having a first groove and a second groove therein. The turbine wheel includes a plurality of openings in which the turbine blade is positioned. Each of the openings has a first groove and a second groove therein. The space or void formed between the first grooves and the second grooves has a plurality of spherical balls positioned therein. The plurality of spherical balls has a preestablished rate of thermal expansion being equal to the preestablished rate of thermal expansion of the turbine blade.

  9. Ceramic blade attachment system

    DOEpatents

    Shaffer, James E.

    1995-01-01

    A turbine blade having a preestablished rate of thermal expansion is attached to a turbine disc having a preestablished rate of thermal expansion being greater than the preestablished rate of thermal expansion of the turbine blade and forms a turbine assembly. The turbine blade has a root portion defining a pair of sides having a pair of grooves therein. The turbine assembly includes a pair of flanges between which the turbine blades are positioned. Each of the pair of flanges has a plurality of grooves defined therein. The grooves within the pair of flanges are aligned with the grooves in the blades and have a space formed therebetween. A plurality of spherical balls are positioned within the space. The plurality of spherical balls has a preestablished rate of thermal expansion being equal to the preestablished rate of thermal expansion of the turbine blade.

  10. Ceramic blade attachment system

    DOEpatents

    Shaffer, J.E.

    1995-07-11

    A turbine blade having a preestablished rate of thermal expansion is attached to a turbine disc having a preestablished rate of thermal expansion being greater than the preestablished rate of thermal expansion of the turbine blade and forms a turbine assembly. The turbine blade has a root portion defining a pair of sides having a pair of grooves therein. The turbine assembly includes a pair of flanges between which the turbine blades are positioned. Each of the pair of flanges has a plurality of grooves defined therein. The grooves within the pair of flanges are aligned with the grooves in the blades and have a space formed therebetween. A plurality of spherical balls are positioned within the space. The plurality of spherical balls has a preestablished rate of thermal expansion being equal to the preestablished rate of thermal expansion of the turbine blade. 4 figs.

  11. Molecular Anchors for Self-Assembled Monolayers on ZnO: A Direct Comparison of the Thiol and Phosphic Acid Moieties

    SciTech Connect

    Perkins, C. L.

    2009-01-01

    Two of the most promising schemes for attaching organic molecules to metal oxides are based on the chemistry of the thiol and phosphonic acid moieties. We have made a direct comparison of the efficacy of these two molecular anchors on zinc oxide by comparing the chemical and physical properties of n-hexane derivatives of both. The surface properties of polycrystalline ZnO thin films and ZnO(000)-O crystals modified with 1-hexanethiol and 1-hexanephosphonic acid were examined with a novel quartz crystal microbalance (QCM)-based flow cell reactor, angle-resolved and temperature-dependent photoelectron spectroscopy, and contact angle measurements. A means of using ammonium chloride as a probe of molecule-ZnO interactions is introduced and used to ascertain the relative quality of self-assembled monolayers (SAMs) based on thiols and phosphonic acids. QCM data shows that a phosphonic acid-anchored alkyl chain only six carbons long can provide significant corrosion protection for ZnO against Bronsted acids, reducing the etch rate relative to the bare ZnO surface by a factor of more than nine. In contrast, we find that monolayers from the analogous molecule hexanethiol are more defective as revealed by their higher ionic permeability and lower hydrophobicity. Substrate attenuation X-ray photoelectron spectroscopy (XPS) experiments were used to determine the thickness of SAMs formed by the two hexane derivatives and it was found that SAMs from phosphonic acids were approximately twice as thick as those formed by hexanethiol. The thermal stability of the two linking groups was also explored and we find that previous claims of highly stable alkanethiolate monolayers on ZnO are suspect. Taken as a whole, our results indicate that the phosphonic acid moiety is preferred over thiols for the attachment of short alkyl groups to ZnO.

  12. A mycothiol synthase mutant of Mycobacterium smegmatis produces novel thiols and has an altered thiol redox status.

    PubMed

    Newton, Gerald L; Ta, Philong; Fahey, Robert C

    2005-11-01

    Mycobacteria and other actinomycetes do not produce glutathione but make mycothiol (MSH; AcCys-GlcN-Ins) that has functions similar to those of glutathione and is essential for growth of Mycobacterium tuberculosis. Mycothiol synthase (MshD) catalyzes N acetylation of Cys-GlcN-Ins to produce MSH in Mycobacterium smegmatis mc2155, and Cys-GlcN-Ins is maintained at a low level. The mycothiol synthase mutant, the mshD::Tn5 mutant, produces high levels of Cys-GlcN-Ins along with two novel thiols, N-formyl-Cys-GlcN-Ins and N-succinyl-Cys-GlcN-Ins, and a small amount of MSH. The nonenzymatic reaction of acyl-coenzyme A (CoA) with Cys-GlcN-Ins to produce acyl-Cys-GlcN-Ins is a facile reaction under physiologic conditions, with succinyl-CoA being an order of magnitude more reactive than acetyl-CoA. The uncatalyzed reaction rates are adequate to account for the observed production of N-succinyl-Cys-GlcN-Ins and MSH under physiologic conditions. It was shown that the N-acyl-Cys-GlcN-Ins compounds are maintained in a substantially reduced state in the mutant but that Cys-GlcN-Ins exists in disulfide forms at 5 to 40% at different stages of growth. MSH was able to facilitate reduction of N-succinyl-Cys-GlcN-Ins disulfide through thiol-disulfide exchange, but N-formyl-Cys-GlcN-Ins was ineffective. The oxidized state of Cys-GlcN-Ins in cells appears to result from a high susceptibility to autoxidation and a low capacity of the cell to reduce its disulfide forms. The mutant exhibited no enhanced sensitivity to hydrogen peroxide, tert-butyl hydroperoxide, or cumene hydroperoxide relative to the parent strain, suggesting that the most abundant thiol, N-formyl-Cys-GlcN-Ins, functions as a substitute for MSH.

  13. Non-protein thiol imaging and quantification in live cells with a novel benzofurazan sulfide triphenylphosphonium fluorogenic compound.

    PubMed

    Yang, Yang; Guan, Xiangming

    2017-05-01

    Thiols (-SH) play various roles in biological systems. They are divided into protein thiols (PSH) and non-protein thiols (NPSH). Due to the significant roles thiols play in various physiological/pathological functions, numerous analytical methods have been developed for thiol assays. Most of these methods are developed for glutathione, the major form of NPSH. Majority of these methods require tissue/cell homogenization before analysis. Due to a lack of effective thiol-specific fluorescent/fluorogenic reagents, methods for imaging and quantifying thiols in live cells are limited. Determination of an analyte in live cells can reveal information that cannot be revealed by analysis of cell homogenates. Previously, we reported a thiol-specific thiol-sulfide exchange reaction. Based on this reaction, a benzofurazan sulfide thiol-specific fluorogenic reagent was developed. The reagent was able to effectively image and quantify total thiols (PSH+NPSH) in live cells through fluorescence microscopy. The reagent was later named as GUALY's reagent. Here we would like to report an extension of the work by synthesizing a novel benzofurazan sulfide triphenylphosphonium derivative [(((7,7'-thiobis(benzo[c][1,2,5]oxadiazole-4,4'-sulfonyl))bis(methylazanediyl))bis(butane-4,1-diyl))bis(triphenylphosphonium) (TBOP)]. Like GUALY's reagent, TBOP is a thiol-specific fluorogenic agent that is non-fluorescent but forms fluorescent thiol adducts in a thiol-specific fashion. Different than GUALY's reagent, TBOP reacts only with NPSH but not with PSH. TBOP was effectively used to image and quantify NPSH in live cells using fluorescence microscopy. TBOP is a complementary reagent to GUALY's reagent in determining the roles of PSH, NPSH, and total thiols in thiol-related physiological/pathological functions in live cells through fluorescence microscopy. Graphical Abstract Live cell imaging and quantification of non-protein thiols by TBOP.

  14. Electrodeposition of gold templated by patterned thiol monolayers

    NASA Astrophysics Data System (ADS)

    She, Zhe; Di Falco, Andrea; Hähner, Georg; Buck, Manfred

    2016-06-01

    The electrochemical deposition of Au onto Au substrates modified by self-assembled monolayers (SAMs) was studied by linear sweep voltammetry (LSV), atomic force microscopy (AFM) and scanning electron microscopy (SEM). Patterned SAMs exhibiting electrochemical contrast were prepared by two different methods. One used microcontact printing (μCP) to generate a binary SAM of ω-(4‧-methyl-biphenyl-4-yl)-propane thiol (CH3-C6H4-C6H4-(CH2)3-SH, MBP3) and octadecane thiol (CH3(CH2)17SH, ODT). Templated by the SAM, a gold microelectrode structure was electrodeposited featuring a line 15 μm wide and 3 mm long. After transfer to an epoxy substrate the structure proved to be electrically conductive across the full length. The other patterning method applied electron beam lithography (EBL) where electrochemical contrast was achieved by crosslinking molecules in a single component SAM of MBP3. An electron dose above 250 mC/cm2 results in a high deposition contrast. The choice of parameters for the deposition/lift-off process is found to be more critical for Au compared to Cu studied previously. The origin of the differences and implications for nanoscale patterning are discussed.

  15. The Architecture of Thiol Antioxidant Systems among Invertebrate Parasites.

    PubMed

    Guevara-Flores, Alberto; Martínez-González, José de Jesús; Rendón, Juan Luis; Del Arenal, Irene Patricia

    2017-02-10

    The use of oxygen as the final electron acceptor in aerobic organisms results in an improvement in the energy metabolism. However, as a byproduct of the aerobic metabolism, reactive oxygen species are produced, leaving to the potential risk of an oxidative stress. To contend with such harmful compounds, living organisms have evolved antioxidant strategies. In this sense, the thiol-dependent antioxidant defense systems play a central role. In all cases, cysteine constitutes the major building block on which such systems are constructed, being present in redox substrates such as glutathione, thioredoxin, and trypanothione, as well as at the catalytic site of a variety of reductases and peroxidases. In some cases, the related selenocysteine was incorporated at selected proteins. In invertebrate parasites, antioxidant systems have evolved in a diversity of both substrates and enzymes, representing a potential area in the design of anti-parasite strategies. The present review focus on the organization of the thiol-based antioxidant systems in invertebrate parasites. Differences between these taxa and its final mammal host is stressed. An understanding of the antioxidant defense mechanisms in this kind of parasites, as well as their interactions with the specific host is crucial in the design of drugs targeting these organisms.

  16. From sulfur to homoglutathione: thiol metabolism in soybean.

    PubMed

    Yi, Hankuil; Ravilious, Geoffrey E; Galant, Ashley; Krishnan, Hari B; Jez, Joseph M

    2010-10-01

    Sulfur is an essential plant nutrient and is metabolized into the sulfur-containing amino acids (cysteine and methionine) and into molecules that protect plants against oxidative and environmental stresses. Although studies of thiol metabolism in the model plant Arabidopsis thaliana (thale cress) have expanded our understanding of these dynamic processes, our knowledge of how sulfur is assimilated and metabolized in crop plants, such as soybean (Glycine max), remains limited in comparison. Soybean is a major crop used worldwide for food and animal feed. Although soybeans are protein-rich, they do not contain high levels of the sulfur-containing amino acids, cysteine and methionine. Ultimately, unraveling the fundamental steps and regulation of thiol metabolism in soybean is important for optimizing crop yield and quality. Here we review the pathways from sulfur uptake to glutathione and homoglutathione synthesis in soybean, the potential biotechnology benefits of understanding and modifying these pathways, and how information from the soybean genome may guide the next steps in exploring this biochemical system.

  17. Theoretical estimation of the aqueous pKas of thiols

    NASA Astrophysics Data System (ADS)

    Hunter, Nora E.; Seybold, Paul G.

    2014-02-01

    The ionisation state of a compound is a key parameter influencing the compound's activity as a drug, metabolite, pollutant, or other active chemical agent. Sulfhydrol compounds (thiols) tend to be considerably more acidic than their hydroxyl (alcohol) analogues. In this report, quantum chemical approaches previously used for the estimation of the aqueous pKas of alcohols are applied to the estimation of the acidities of thiols. Acidity estimates obtained from the general-purpose SPARC calculational programme (S.H. Hilal, S.W. Karickhoff, and L.A. Carreira, Quant. Struct.-Act. Relat. 14, 348 (1995)) and the ACD/Labs PhysChem Suite v12 programme package are employed as benchmarks. Quantum chemical calculations were performed using both the semiempirical RM1 method and the density functional theory B3LYP/6-31+G* method. The effectiveness of the SM5.4 and SM8 solvent models in estimating the aqueous-phase acidities was also evaluated. All of the approaches examined demonstrated strong correlations with the experimental acidity values.

  18. A structurally driven analysis of thiol reactivity in mammalian albumins.

    PubMed

    Spiga, Ottavia; Summa, Domenico; Cirri, Simone; Bernini, Andrea; Venditti, Vincenzo; De Chiara, Matteo; Priora, Raffaella; Frosali, Simona; Margaritis, Antonios; Di Giuseppe, Danila; Di Simplicio, Paolo; Niccolai, Neri

    2011-04-01

    Understanding the structural basis of protein redox activity is still an open question. Hence, by using a structural genomics approach, different albumins have been chosen to correlate protein structural features with the corresponding reaction rates of thiol exchange between albumin and disulfide DTNB. Predicted structures of rat, porcine, and bovine albumins have been compared with the experimentally derived human albumin. High structural similarity among these four albumins can be observed, in spite of their markedly different reactivity with DTNB. Sequence alignments offered preliminary hints on the contributions of sequence-specific local environments modulating albumin reactivity. Molecular dynamics simulations performed on experimental and predicted albumin structures reveal that thiolation rates are influenced by hydrogen bonding pattern and stability of the acceptor C34 sulphur atom with donor groups of nearby residues. Atom depth evolution of albumin C34 thiol groups has been monitored during Molecular Dynamic trajectories. The most reactive albumins appeared also the ones presenting the C34 sulphur atom on the protein surface with the highest accessibility. High C34 sulphur atom reactivity in rat and porcine albumins seems to be determined by the presence of additional positively charged amino acid residues favoring both the C34 S⁻ form and the approach of DTNB.

  19. Differential thiol-based switches jumpstart Vibrio cholerae pathogenesis

    PubMed Central

    Liu, Zhi; Wang, Hui; Zhou, Zhigang; Naseer, Nawar; Xiang, Fu; Kan, Biao; Goulian, Mark; Zhu, Jun

    2015-01-01

    Bacterial pathogens utilize gene expression versatility to adapt to environmental changes. Vibrio cholerae, the causative agent of cholera, encounters redox potential changes when it transitions from oxygen-rich aquatic reservoirs to the oxygen-limiting human gastrointestinal tract. We previously showed that the virulence regulator AphB uses thiol-based switches to sense the anoxic host environment and transcriptionally activate the key virulence activator tcpP. Here, by performing a high-throughput transposon sequencing screen in vivo, we identified OhrR as another regulator that enables V. cholerae rapid anoxic adaptation. Like AphB, reduced OhrR binds to and regulates the tcpP promoter. OhrR and AphB displayed differential dynamics in response to redox potential changes: OhrR is reduced more rapidly than AphB. Furthermore, OhrR thiol modification is required for rapid activation of virulence and successful colonization. This reveals a mechanism whereby bacterial pathogens employ posttranslational modifications of multiple transcription factors to sense and adapt to dynamic environmental changes. PMID:26748713

  20. Purification and characterization of a pineapple crown leaf thiol protease.

    PubMed

    Singh, L Rupachandra; Devi, Th Premila; Devi, S Kunjeshwori

    2004-02-01

    A thiol protease was isolated and purified from the crown leaf of pineapple, Ananas comosus (L.) Merr. cv. Queen, by an immunoaffinity procedure. After the purification to electrophoretic homogeneity, the enzyme was characterized with respect to some of its physico-chemical and kinetic properties. The molecular weight of the protease (22.4-22.9 kDa), Km (97 microM) and kcat (8.8 s(-1)) for its esterolytic cleavage of the synthetic protease substrate N(alpha)-CBZ-L-lysine p-nitrophenyl ester, the concentration of its thiol activator L-cysteine required for half maximal activation A0.5 (9.9 microM), optimum pH (6.5) for its proteolytic action on azocasein, T(1/2) (60 degrees C) for inactivation by heating the enzyme (35.5 microg protein/mL) in citrate buffer pH 6.0 for 15 min, and SH-group content (0.98 mol/mol enzyme) were determined. Most of these physicochemical and kinetic properties were found to be similar to those of the already well-characterized stem bromelain (EC 3.4.22.32). Thus, the immunoaffinity purified crown leaf protease appeared to be closely related to stem bromelain.

  1. Thiol surface complexation on growing CdS clusters

    SciTech Connect

    Swayambunathan, V.; Hayes, D.; Schmidt, K.H.; Liao, Y.X.; Meisel, D. )

    1990-05-09

    The growth of small CdS colloidal particles has been initiated by pulse radiolytic release of sulfide from thiol (3-mercapto-1,2-propanediol, RSH) in the presence of Cd{sup 2+} ions. The kinetics and stoichiometry of the ensuring reactions were followed by conductivity, absorption spectroscopy, and light-scattering techniques. The final CdS product has been identified by electron diffraction. The formation of Cd-thiolate complexes at the surface of the particles is indicated by conductivity and by energy dispersive analysis of X-ray (EDAX) results. The rate of formation of CdS clusters is strongly pH dependent due to the pH effect on the stability of Dd{sup 2+}/HS{sup {minus}} complexes. At low pHs (4.0-5.3) the growth mechanism is proposed to be primarily a cluster-molecule process. At this pH range Cd{sup 2+} ions at the CdS particle surface complex with thiolate ions stronger than in the bulk of the solution. The size control of the particles by thiols is proposed to result from a competition of thiolate ions with HS{sup {minus}} ions for cadmium ions at the surface of the growing particles.

  2. Sentence-Level Attachment Prediction

    NASA Astrophysics Data System (ADS)

    Albakour, M.-Dyaa; Kruschwitz, Udo; Lucas, Simon

    Attachment prediction is the task of automatically identifying email messages that should contain an attachment. This can be useful to tackle the problem of sending out emails but forgetting to include the relevant attachment (something that happens all too often). A common Information Retrieval (IR) approach in analyzing documents such as emails is to treat the entire document as a bag of words. Here we propose a finer-grained analysis to address the problem. We aim at identifying individual sentences within an email that refer to an attachment. If we detect any such sentence, we predict that the email should have an attachment. Using part of the Enron corpus for evaluation we find that our finer-grained approach outperforms previously reported document-level attachment prediction in similar evaluation settings.

  3. Elderly-animal postmortem attachment.

    PubMed

    Peretti, P O

    1990-01-01

    Attachment can be strong between people and their pets. The present study was conducted to determine: (1) specific variables associated with the final rite and disposition of the deceased pet, and (2) those criteria associated with emotional and social factors pertaining to elderly-animal postmortem attachment. Results suggested four most frequently stated variables of final rite and disposition, and eight emotional and social factors of elderly-animal postmortem attachment.

  4. Gel Permeation Chromatography Characterization of the Chain Length Distributions in Thiol-Acrylate Photopolymer Networks

    PubMed Central

    Rydholm, Amber E.; Held, Nicole L.; Bowman, Christopher N.; Anseth, Kristi S.

    2008-01-01

    Crosslinked, degradable networks formed from the photopolymerization of thiol and acrylate monomers are explored as potential biomaterials. The degradation behavior and material properties of these networks are influenced by the molecular weight of the nondegradable thiol-polyacrylate backbone chains that form during photopolymerization. Here, gel permeation chromatography was used to characterize the thiol-polyacrylate backbone chain lengths in degraded thiol-acrylate networks. Increasing thiol functionality from 1 to 4 increased the backbone molecular weight (M̄w = 2.3 ± 0.07 × 104 Da for monothiol and 3.6 ± 0.1 × 104 Da for tetrathiol networks). Decreasing thiol functional group concentration from 30 to 10 mol% also increased the backbone lengths (M̄w = 7.3 ± 1.1 × 104 Da for the networks containing 10 mol% thiol groups as compared to 3.6 ± 0.1 × 104 Da for 30 mol% thiol). Finally, the backbone chain lengths were probed at various stages of degradation and an increase in backbone molecular weight was observed as mass loss progressed from 10 to 70%. PMID:19079733

  5. The role of thiols in cellular response to radiation and drugs

    SciTech Connect

    Biaglow, J.E.; Varnes, M.E.; Clark, E.P.; Epp, E.R.

    1983-09-01

    Cellular nonprotein thiols (NPSH) consist of glutathione (GSH) and other low molecular weight species such as cysteine, cysteamine, and coenzyme A. GSH is usually less than the total cellular NPSH, and with thiol reactive agents, such as diethyl maleate (DEM), its rate of depletion is in part dependent upon the cellular capacity for its resynthesis. If resynthesis is blocked by buthionine-S,R-sulfoximine(BSO), the NPSH, including GSH, is depleted more rapidly, Cellular thiol depletion by diamide, N-ethylmaleimide, and BSO may render oxygenated cells more sensitive to radiation. These cells may or may not show a reduction in the oxygen enhancement ratio (OER). Human A549 lung carcinoma cells depleted of their NPSH either by prolonged culture or by BSO treatment do not show a reduced OER but do show increased aerobic responses to radiation. Some nitroheterocyclic radiosensitizing drugs also deplete cellular thiols under aerobic conditions. Such reactivity may be the reason that they show anomalous radiation sensitization (i.e., better than predicted on the basis of electron affinity). Other nitrocompounds, such as misonidazole, are activated under hypoxic conditions to radical intermediates. When cellular thiols are depleted peroxide is formed. Under hypoxic conditions thiols are depleted because metabolically reduced intermediates react with GSH instead of oxygen. Thiol depletion, under hypoxic conditions, may be the reason that misonidazole and other nitrocompounds show an extra enhancement ratio with hypoxic cells. Thiol depletion by DEM or BSO alters the radiation response of hypoxic cells to misonidazole.

  6. Direct Synthesis of Thioethers from Carboxylates and Thiols Catalyzed by FeCl3.

    PubMed

    Venkatesham, Kunuru; Bhujanga Rao, Chitturi; Dokuburra, Chanti Babu; Bunce, Richard A; Venkateswarlu, Yenamandra

    2015-11-20

    A new and efficient method has been developed for the synthesis of thioethers from carboxylates and thiols. The reaction proceeds via a Fe(III)-catalyzed direct displacement of carboxylates from benzylic or allylic esters by heterocyclic thiols. Short reaction times, good to excellent yields of products, and few side reactions are the significant features of the new protocol.

  7. Surfactant-free coating of thiols on gold nanoparticles using sonochemistry: a study of competing processes.

    PubMed

    Pallipurath, Anuradha; Nicoletti, Olivia; Skelton, Jonathan M; Mahajan, Sumeet; Midgley, Paul A; Elliott, Stephen R

    2014-09-01

    A method for the surfactant-free coating of gold nanoparticles with thiols using sonochemistry is presented. The gold nanoparticles were prepared by a modified Zsigmondy method, affording good control over the particle-size distribution, and the thiol coating was performed by the sonication of a biphasic system consisting of a nanoparticle suspension in water and thiols in toluene. The effects of two important reaction parameters on the particle morphology, viz. sonication time and thiol concentration, were investigated in detail using transmission electron microscopy. The effect of the thiol chain length was also studied. We show that the morphology of the coated particles is determined through a competition between two opposing effects: particle fusion, due to the sonication conditions, and digestive ripening, due to the action of the thiols. Additionally, we illustrate the utility of our technique for various applications, including surface-enhanced Raman scattering from bound molecules, and further functionalization using a thiol-exchange reaction. Our technique paves the way for an efficient synthesis of thiol-coated AuNPs of different shapes and sizes, suitable for a range of diverse applications. Copyright © 2014 Elsevier B.V. All rights reserved.

  8. Conservation of thiol-oxidative stress responses regulated by SigR orthologues in actinomycetes

    PubMed Central

    Kim, Min-Sik; Dufour, Yann S.; Yoo, Ji Sun; Cho, Yoo-Bok; Park, Joo-Hong; Nam, Gi-Baeg; Kim, Hae Min; Lee, Kang-Lok; Donohue, Timothy J.; Roe, Jung-Hye

    2015-01-01

    Summary Numerous thiol-reactive compounds cause oxidative stress where cells counteract by activation of survival strategies regulated by thiol-based sensors. In Streptomyces coelicolor, a model actinomycete, a sigma/antisigma pair SigR/RsrA controls the response to thiol-oxidative stress. To unravel its full physiological functions, chromatin immuno-precipitation combined with sequence and transcript analyses were employed to identify 108 SigR target genes in S. coelicolor and to predict orthologous regulons across actinomycetes. In addition to reported genes for thiol homeostasis, protein degradation and ribosome modulation, 64 additional operons were identified suggesting new functions of this global regulator. We demonstrate that SigR maintains the level and activity of the housekeeping sigma factor HrdB during thiol-oxidative stress, a novel strategy for stress responses. We also found that SigR defends cells against UV and thiol-reactive damages, in which repair UvrA takes a part. Using a refined SigR-binding sequence model, SigR orthologues and their targets were predicted in 42 actinomycetes. This revealed a conserved core set of SigR targets to function for thiol homeostasis, protein quality control, possible modulation of transcription and translation, flavin-mediated redox reactions, and Fe-S delivery. The composition of the SigR regulon reveals a robust conserved physiological mechanism to deal with thiol-oxidative stress from bacteria to human. PMID:22651816

  9. Lithium BINOL Phosphate Catalyzed Desymmetrization of meso-Epoxides with Aromatic Thiols

    PubMed Central

    2015-01-01

    A highly enantioselective method for desymmetrization of meso-epoxides using thiols is reported. This is the first example of epoxide activation achieved using metal BINOL phosphates. The reaction has a broad scope in terms of epoxide substrates and aromatic thiol nucleophiles. The resulting β-hydroxyl sulfides are obtained in excellent yield and enantioselectivity. PMID:25317934

  10. Spectrophotometric Determination of Phenolic Antioxidants in the Presence of Thiols and Proteins.

    PubMed

    Avan, Aslı Neslihan; Demirci Çekiç, Sema; Uzunboy, Seda; Apak, Reşat

    2016-08-12

    Development of easy, practical, and low-cost spectrophotometric methods is required for the selective determination of phenolic antioxidants in the presence of other similar substances. As electron transfer (ET)-based total antioxidant capacity (TAC) assays generally measure the reducing ability of antioxidant compounds, thiols and phenols cannot be differentiated since they are both responsive to the probe reagent. In this study, three of the most common TAC determination methods, namely cupric ion reducing antioxidant capacity (CUPRAC), 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt/trolox equivalent antioxidant capacity (ABTS/TEAC), and ferric reducing antioxidant power (FRAP), were tested for the assay of phenolics in the presence of selected thiol and protein compounds. Although the FRAP method is almost non-responsive to thiol compounds individually, surprising overoxidations with large positive deviations from additivity were observed when using this method for (phenols + thiols) mixtures. Among the tested TAC methods, CUPRAC gave the most additive results for all studied (phenol + thiol) and (phenol + protein) mixtures with minimal relative error. As ABTS/TEAC and FRAP methods gave small and large deviations, respectively, from additivity of absorbances arising from these components in mixtures, mercury(II) compounds were added to stabilize the thiol components in the form of Hg(II)-thiol complexes so as to enable selective spectrophotometric determination of phenolic components. This error compensation was most efficient for the FRAP method in testing (thiols + phenols) mixtures.

  11. Immunodetection of thiol proteinase levels in various populations of Artemia cysts and during development.

    PubMed

    Lu, J; Warner, A H

    1991-01-01

    An immunodetection assay on Western blots has been used to determine the thiol proteinase content and composition in cysts from 12 populations of the brine shrimp Artemia. Our results showed no differences in the subunit composition of the thiol proteinase among cysts from eight bisexual strains and four parthenogenic strains, and confirmed an earlier finding that the proteinase is composed of two subunits of 25.9 and 31.5 kilodaltons. In contrast, we found that Artemia cysts from parthenogenic strains contain 17.1 ng/cyst of the thiol proteinase, while cysts from bisexual strains contain 8.2 ng/cyst of the thiol proteinase. Also, there was a good linear correlation (r = 0.863; p less than 0.001) between the thiol proteinase content and cyst mass. Embryo fractionation experiments showed that 82% of the thiol proteinase was in the cytosol, while 14 and 4%, respectively, were in the nuclei/yolk platelets and mitochondria/lysosome fractions. Measurements of the thiol proteinase content of developing Artemia embryos showed that the proteinase content was relatively constant during early development, suggesting that the activity of the thiol proteinase gene(s) may be constitutive and not developmentally regulated in Artemia embryos.

  12. Regioselective hydrothiolation of alkenes bearing heteroatoms with thiols catalyzed by palladium diacetate.

    PubMed

    Tamai, Taichi; Ogawa, Akiya

    2014-06-06

    In sharp contrast to many examples of transition-metal-catalyzed hydrothiolation of alkynes, the corresponding catalytic addition of thiols to alkenes has remained undeveloped. However, a novel Pd-catalyzed addition of thiols to alkenes bearing a heteroatom, such as oxygen and nitrogen, is found to proceed under mild conditions to give the corresponding Markovnikov adducts, regioselectively, in good yields.

  13. Spectrophotometric Determination of Phenolic Antioxidants in the Presence of Thiols and Proteins

    PubMed Central

    Avan, Aslı Neslihan; Demirci Çekiç, Sema; Uzunboy, Seda; Apak, Reşat

    2016-01-01

    Development of easy, practical, and low-cost spectrophotometric methods is required for the selective determination of phenolic antioxidants in the presence of other similar substances. As electron transfer (ET)-based total antioxidant capacity (TAC) assays generally measure the reducing ability of antioxidant compounds, thiols and phenols cannot be differentiated since they are both responsive to the probe reagent. In this study, three of the most common TAC determination methods, namely cupric ion reducing antioxidant capacity (CUPRAC), 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt/trolox equivalent antioxidant capacity (ABTS/TEAC), and ferric reducing antioxidant power (FRAP), were tested for the assay of phenolics in the presence of selected thiol and protein compounds. Although the FRAP method is almost non-responsive to thiol compounds individually, surprising overoxidations with large positive deviations from additivity were observed when using this method for (phenols + thiols) mixtures. Among the tested TAC methods, CUPRAC gave the most additive results for all studied (phenol + thiol) and (phenol + protein) mixtures with minimal relative error. As ABTS/TEAC and FRAP methods gave small and large deviations, respectively, from additivity of absorbances arising from these components in mixtures, mercury(II) compounds were added to stabilize the thiol components in the form of Hg(II)-thiol complexes so as to enable selective spectrophotometric determination of phenolic components. This error compensation was most efficient for the FRAP method in testing (thiols + phenols) mixtures. PMID:27529232

  14. An introduction to thiol redox proteins in the endoplasmic reticulum and a review of current electrochemical methods of detection of thiols.

    PubMed

    Kruusma, Jaanus; Benham, Adam M; Williams, J A Gareth; Kataky, Ritu

    2006-04-01

    This aim of this paper is to expound the complexity of thiol redox systems in the endoplasmic reticulum of eukaryotic cells to the electroanalytical community. A summary of the state of the art in electrochemical methods for detection of thiols gives an insight into the challenges that need to be addressed to bridge the disparity between current analytical techniques and applications in a 'real' biological scenario.

  15. Interferences in place attachment: implications for wilderness

    Treesearch

    Erin K. Sharpe; Alan W. Ewert

    2000-01-01

    Previous research on place attachment has tended to focus on attachment formation, with relatively little attention given to factors that disrupt or interfere with formed place attachments. Interferences to attachments are a worthy research area for two reasons: 1) The factors of place attachment are often more salient when being disrupted, and 2) place attachment...

  16. An overview of frenal attachments

    PubMed Central

    Priyanka, M.; Sruthi, R.; Ramakrishnan, T.; Emmadi, Pamela; Ambalavanan, N.

    2013-01-01

    Frenal attachments are thin folds of mucous membrane with enclosed muscle fibers that attach the lips to the alveolar mucosa and underlying periosteum. Most often, during the oral examination of the patient the dentist gives very little importance to the frenum, for assessing its morpholology and attachment. However, it has been seen that an abnormal frenum can be an indicator of a syndrome. This paper highlights the different frenal attachments seen in association with various syndromic as well as non-syndromic conditions. PMID:23633765

  17. Tethered bilayer lipid membranes on mixed self-assembled monolayers of a novel anchoring thiol: impact of the anchoring thiol density on bilayer formation.

    PubMed

    Basit, Hajra; Van der Heyden, Angéline; Gondran, Chantal; Nysten, Bernard; Dumy, Pascal; Labbé, Pierre

    2011-12-06

    Tethered bilayer lipid membranes (tBLMs) are designed on mixed self-assembled monolayers (SAMs) of a novel synthetic anchoring thiol, 2,3-di-o-palmitoylglycerol-1-tetraethylene glycol mercaptopropanoic acid ester (TEG-DP), and a new short dilution thiol molecule, tetraethylene glycol mercaptopropanoic acid ester (TEG). tBLM formation was accomplished by self-directed fusion of small unilamellar vesicles of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine. The influence of the dilution of the anchoring thiol molecule in the SAM on the vesicle fusion process and on the properties of the resulting tBLMs is studied. It is observed by quartz crystal microbalance that vesicle fusion is a one-step process for a pure TEG-DP SAM as well as for mixed SAMs containing a high concentration of the anchoring thiol. However, upon dilution of the anchoring thiol to moderate concentrations, this process is decelerated and possibly follows a pathway different from that observed on a pure TEG-DP SAM. Electrochemical impedance spectroscopy is used to qualitatively correlate the composition of the SAM to the electrical properties of the tBLM. In this paper we also delineate the necessity of a critical concentration of this anchoring TEG-DP thiol as a requisite for inducing the fusion of vesicles to form a tBLM. © 2011 American Chemical Society

  18. Thiol oxidase ability of copper ion is specifically retained upon chelation by aldose reductase.

    PubMed

    Balestri, Francesco; Moschini, Roberta; Cappiello, Mario; Mura, Umberto; Del-Corso, Antonella

    2017-06-01

    Bovine lens aldose reductase is susceptible to a copper-mediated oxidation, leading to the generation of a disulfide bridge with the concomitant incorporation of two equivalents of the metal and inactivation of the enzyme. The metal complexed by the protein remains redox active, being able to catalyse the oxidation of different physiological thiol compounds. The thiol oxidase activity displayed by the enzymatic form carrying one equivalent of copper ion (Cu1-AR) has been characterized. The efficacy of Cu1-AR in catalysing thiol oxidation is essentially comparable to the free copper in terms of both thiol concentration and pH effect. On the contrary, the two catalysts are differently affected by temperature. The specificity of the AR-bound copper towards thiols is highlighted with Cu1-AR being completely ineffective in promoting the oxidation of both low-density lipoprotein and ascorbic acid.

  19. Widespread occurrence of bacterial thiol methyltransferases and the biogenic emission of methylated sulfur gases.

    PubMed Central

    Drotar, A; Burton, G A; Tavernier, J E; Fall, R

    1987-01-01

    A majority of heterotrophic bacteria isolated from soil, water, sediment, vegetation, and marine algae cultures methylated sulfide, producing methanethiol. This was demonstrated with intact cells by measuring the emission of methanethiol with a sulfur-selective chemiluminescence detector, and in cell extracts by detection of sulfide-dependent thiol methyltransferase activity. Extracts of two Pseudomonas isolates were fractionated by gel-filtration and ion-exchange chromatography, and with sulfide as the substrate a single peak of thiol methyltransferase activity was seen in each case. Extracts of several bacterial strains also contained thiol methyltransferase activity with organic thiols as substrates. Thus, S-adenosylmethionine-dependent thiol methyltransferase activities are widespread in bacteria and may contribute to biogenic emissions of methylated sulfur gases and to the production of methyl thioethers. PMID:3662509

  20. Probing the thiol-gold planar interface by spin polarized tunneling

    SciTech Connect

    Zhang, Xiaohang; McGill, Stephen A.; Xiong, Peng; Wang, Xiaolei; Zhao, Jianhua

    2014-04-14

    Reports of induced magnetism at thiol-gold interface have generated considerable recent interest. In these studies, the sample magnetization was generally measured by superconducting quantum interference device magnetometry which has limitation in determining surface and interface magnetism. In this work, we have fabricated planar tunnel junctions incorporating a thiol-gold interface. An observed room temperature humidity effect together with low temperature inelastic electron tunneling spectroscopy confirmed the existence of a thiol-gold interface in the organic-inorganic hybrid heterostructure. Spin polarized tunneling measurements were performed to probe the spin polarization at the thiol-gold interface; however, the obtained spin polarized tunneling spectra indicate no measurable spin polarization at the thiol-gold interface.

  1. Widespread occurrence of bacterial thiol methyltransferases and the biogenic emission of methylated sulfur gases

    SciTech Connect

    Drotar, A.; Burton, G.A. Jr.; Tavernier, J.E.; Fall, R.

    1987-07-01

    A majority of heterotrophic bacteria isolated from soil, water, sediment, vegetation, and marine algae cultures methylated sulfide, producing methanethiol. This was demonstrated (i) with intact cells by measuring the emission of methanethiol with a sulfur-selective chemiluminescence detector, and (ii) in cell extracts by detection of sulfide-dependent thiol methyltransferase activity. Extracts of two Pseudomonas isolates were fractionated by gel-filtration and ion-exchange chromatography, and with sulfide as the substrate a single peak of thiol methyltransferase activity was seen in each case. Extracts of several bacterial strains also contained thiol methyltransferase activity with organic thiols as substrates. Thus, S-adenosylmethionine-dependent thiol methyltransferase activities are widespread in bacteria and may contribute to biogenic emissions of methylated sulfur gases and to the production of methyl thioethers.

  2. Ester-free Thiol-ene Dental Restoratives – Part A: Resin Development

    PubMed Central

    Podgórski, Maciej; Becka, Eftalda; Claudino, Mauro; Flores, Alexander; Shah, Parag K.; Stansbury, Jeffrey W.; Bowman, Christopher N.

    2015-01-01

    Objectives To detail the development of ester-free thiol-ene dental resins with enhanced mechanical performance, limited potential for water uptake/leachables/degradation and low polymerization shrinkage stress. Methods Thiol-terminated oligomers were prepared via a thiol-Michael reaction and a bulky tetra-allyl monomer containing urethane linkages was synthesized. The experimental oligomers and/or monomers were photopolymerized using visible light activation. Several thiol-ene formulations were investigated and their performance ranked by comparisons of the thermo-mechanical properties, polymerization shrinkage stress, water sorption/solubility, and reactivity with respect to a control comprising a conventional BisGMA/TEGDMA dental resin. Results The ester-free thiol-ene formulations had significantly lower viscosities, water sorption and solubility than the BisGMA/TEGDMA control. Depending on the resin, the limiting functional conversions were equivalent to or greater than that of BisGMA/TEGDMA. At comparable conversions, lower shrinkage stress values were achieved by the thiol-ene systems. The polymerization shrinkage stress was dramatically reduced when the tetra-allyl monomer was used as the ene in ester-free thiol-ene mixtures. Although exhibiting lower Young’s modulus, flexural strength, and glass transition temperatures, the toughness values associated with thiol-ene resins were greater than that of the BisGMA/TEGDMA control. In addition, the thiol-ene polymerization resulted in highly uniform polymer networks as indicated by the narrow tan delta peak widths. Significance Employing the developed thiol-ene resins in dental composites will reduce shrinkage stress and moisture absorption and form tougher materials. Furthermore, their low viscosities are expected to enable higher loadings of functionalized micro/nano-scale filler particles relevant for practical dental systems. PMID:26360013

  3. Dissociative Electron Attachment

    NASA Astrophysics Data System (ADS)

    Arreola, Esmeralda; Esmeralda Arreola Collaboration; Leigh Hargreaves Collaboration

    Since the pioneering work of Boudiaffa et al., it has been understood that electrons, even with energies near or below the ionization threshold, are capable of initiating strand-breaks in human DNA. This discovery raised important questions for cancer treatments, since sub-ionizing electrons are known to be the most copiously produced secondary product of radiation therapy. But even to date these factors are largely excluded from dosimetry calculations. This lack of inclusion is, at least in part, certainly due to the dearth of fundamental data describing low-energy electron interactions with nucleotide molecules that form the basis of DNA. Understanding of how such slow electrons are able to damage DNA remains incomplete, but the strongly peaked nature of Boudiaffa et al.'s data gives strong hints at resonantly driven collision processes. DNA damage is therefore most likely driven by ``dissociative electron attachment'' (DEA). DEA is a rather complicated process to model due to the coupling of electronic and nuclear degrees of freedom in the molecule. At the California State University Fullerton, we are currently commissioning a new spectrometer to study dissociation channels, reaction rates and orientation effects in DEA collisions between slow electrons and nucleotide molecules. At the meeting we will present design parameters and commissioning data for this new apparatus.

  4. Protein Attachment on Nanodiamonds.

    PubMed

    Lin, Chung-Lun; Lin, Cheng-Huang; Chang, Huan-Cheng; Su, Meng-Chih

    2015-07-16

    A recent advance in nanotechnology is the scale-up production of small and nonaggregated diamond nanoparticles suitable for biological applications. Using detonation nanodiamonds (NDs) with an average diameter of ∼4 nm as the adsorbents, we have studied the static attachment of three proteins (myoglobin, bovine serum albumin, and insulin) onto the nanoparticles by optical spectroscopy, mass spectrometry, and dynamic light scattering, and electrophoretic zeta potential measurements. Results show that the protein surface coverage is predominantly determined by the competition between protein-protein and protein-ND interactions, giving each protein a unique and characteristic structural configuration in its own complex. Specifically, both myoglobin and bovine serum albumin show a Langmuir-type adsorption behavior, forming 1:1 complexes at saturation, whereas insulin folds into a tightly bound multimer before adsorption. The markedly different adsorption patterns appear to be independent of the protein concentration and are closely related to the affinity of the individual proteins for the NDs. The present study provides a fundamental understanding for the use of NDs as a platform for nanomedical drug delivery.

  5. (Processing and targeting of the thiol protease aleurain)

    SciTech Connect

    Rogers, J.C.

    1990-01-01

    Our goal for work during the past two years under this Grant was to characterize the barley thiol protease, aleurain, to determine if it is secreted or retained intracellularly in aleurone cells, and to begin to elucidate structural features that might control targeting of the protein to its final destination. We have shown that aleurain is synthesized as a proenzyme with two N-linked oligosaccharide chains, one high mannose-type and one complex-type. Aleurain undergoes processing to mature form by removal of an Nterminal prosegment, and is retained intracellularly; it cannot be detected among proteins secreted from aleurone cells. Treatment of aleurone cells with tunicamycin to prevent glycosylation of aleurain does not prevent processing of the unglycosylated form. The N-terminal portion of aleurain's prosegment is homologous to the comparable region in two yeast vacuolar proteases, where that region is known to contain the signal necessary for targeting the proteases to the vacuole. 18 refs., 7 figs.

  6. Patients with organic acidaemias have an altered thiol status.

    PubMed

    Salmi, Heli; Leonard, James V; Lapatto, Risto

    2012-11-01

    To study whether patients with organic acidaemias have altered glutathione (GSH) levels and thiol redox status. Previously, organic acidaemias have been associated with mitochondrial dysfunction and oxidative stress, suggesting an increased need for antioxidant protection. Furthermore, dietary protein restriction may impair GSH synthesis in these diseases. In children with organic acidaemias, cysteine (CYSH) and GSH concentrations in plasma and erythrocytes as well as erythrocyte GSH peroxidase, GSH reductase, GSH S-transferase and glucose-6-phosphate dehydrogenase activities were studied. In addition, GSH and CYSH concentrations were measured in human fibroblasts exposed to organic acids. Patients with organic acidaemias had lower plasma GSH concentration than their controls. A greater fraction of GSH and CYSH in the patients' plasma was oxidized, suggesting decreased GSH synthesis and increased consumption. Patients with organic acidaemias may have a relative GSH deficiency. With further research, these results could also have therapeutic implications. © 2012 The Author(s)/Acta Paediatrica © 2012 Foundation Acta Paediatrica.

  7. Detection of biological thiols based on a colorimetric method*

    PubMed Central

    Xu, Yuan-yuan; Sun, Yang-yang; Zhang, Yu-juan; Lu, Chen-he; Miao, Jin-feng

    2016-01-01

    Biological thiols (biothiols), an important kind of functional biomolecules, such as cysteine (Cys) and glutathione (GSH), play vital roles in maintaining the stability of the intracellular environment. In past decades, studies have demonstrated that metabolic disorder of biothiols is related to many serious disease processes and will lead to extreme damage in human and numerous animals. We carried out a series of experiments to detect biothiols in biosamples, including bovine plasma and cell lysates of seven different cell lines based on a simple colorimetric method. In a typical test, the color of the test solution could gradually change from blue to colorless after the addition of biothiols. Based on the color change displayed, experimental results reveal that the percentage of biothiols in the embryonic fibroblast cell line is significantly higher than those in the other six cell lines, which provides the basis for the following biothiols-related study. PMID:27704750

  8. Hydrolytically Stable Thiol-ene Networks for Flexible Bioelectronics.

    PubMed

    Reit, Radu; Zamorano, Daniel; Parker, Shelbi; Simon, Dustin; Lund, Benjamin; Voit, Walter; Ware, Taylor H

    2015-12-30

    Hydrolytically stable, tunable modulus polymer networks are demonstrated to survive harsh alkaline environments and offer promise for use in long-term implantable bioelectronic medicines known as electroceuticals. Today's polymer networks (such as polyimides or polysiloxanes) succeed in providing either stiff or soft substrates for bioelectronics devices; however, the capability to significantly tune the modulus of such materials is lacking. Within the space of materials with easily modified elastic moduli, thiol-ene copolymers are a subset of materials that offer a promising solution to build next generation flexible bioelectronics but have typically been susceptible to hydrolytic degradation chronically. In this inquiry, we demonstrate a materials space capable of tuning the substrate modulus and explore the mechanical behavior of such networks. Furthermore, we fabricate an array of microelectrodes that can withstand accelerated aging environments shown to destroy conventional flexible bioelectronics.

  9. Bacillithiol: a key protective thiol in Staphylococcus aureus.

    PubMed

    Perera, Varahenage R; Newton, Gerald L; Pogliano, Kit

    2015-01-01

    Bacillithiol is a low-molecular-weight thiol analogous to glutathione and is found in several Firmicutes, including Staphylococcus aureus. Since its discovery in 2009, bacillithiol has been a topic of interest because it has been found to contribute to resistance during oxidative stress and detoxification of electrophiles, such as the antibiotic fosfomycin, in S. aureus. The rapid increase in resistance of methicillin-resistant Staphylococcus aureus (MRSA) to available therapeutic agents is a great health concern, and many research efforts are focused on identifying new drugs and targets to combat this organism. This review describes the discovery of bacillithiol, studies that have elucidated the physiological roles of this molecule in S. aureus and other Bacilli, and the contribution of bacillithiol to S. aureus fitness during pathogenesis. Additionally, the bacillithiol biosynthesis pathway is evaluated as a novel drug target that can be utilized in combination with existing therapies to treat S. aureus infections.

  10. Towards thiol functionalization of vanadium pentoxide nanotubes using gold nanoparticles

    SciTech Connect

    Lavayen, V.; O'Dwyer, C. . E-mail: codwyer@tyndall.ie; Cardenas, G.; Gonzalez, G.; Sotomayor Torres, C.M.

    2007-04-12

    Template-directed synthesis is a promising route to realize vanadate-based 1-D nanostructures, an example of which is the formation of vanadium pentoxide nanotubes and associated nanostructures. In this work, we report the interchange of long-chained alkyl amines with alkyl thiols. This reaction was followed using gold nanoparticles prepared by the Chemical Liquid Deposition (CLD) method with an average diameter of {approx}0.9nm and a stability of {approx}85 days. V{sub 2}O{sub 5} nanotubes (VOx-NTs) with lengths of {approx}2{mu}m and internal hollow diameters of 20-100nm were synthesized and functionalized in a Au-acetone colloid with a nominal concentration of {approx}4x10{sup -3}mol dm{sup -3}. The interchange reaction with dodecylamine is found only to occur in polar solvents and incorporation of the gold nanoparticles is not observed in the presence of n-decane.

  11. Phenylalkyl isoselenocyanates vs phenylalkyl isothiocyanates: thiol reactivity and its implications

    PubMed Central

    Crampsie, Melissa A.; Pandey, Manoj K.; Desai, Dhimant; Spallholz, Julian; Amin, Shantu; Sharma, Arun K.

    2012-01-01

    Phenylalkyl isoselenocyanate (ISC) compounds were recently designed in our laboratory by incorporating the anticancer element selenium into a panel of phenylalkyl isothiocyanates (ITCs), known to have anticancer properties. A structural activity investigation was carried out to compare the ISC and ITC panels. Cell viability assay and Annexin V staining for apoptosis showed ISC compounds to be more potent in killing A549 lung adenocarcinoma cells. Both ITCs and ISCs were able to deplete reduced glutathione (GSH) in cells, ISCs more rapidly, but ITCs to a greater extent. ISC compounds had a higher rate of reaction to thiol (-SH) groups as determined by pseudo first order kinetics than the corresponding carbon chain length ITC. The equilibrium concentrations of the GSH and protein thiol conjugates did not differ significantly when comparing sulfur to selenium compounds of the same carbon chain length, and did follow the same trend of displaying decreasing reactivity with increasing carbon chain length for both ITCs and ISCs. Furthermore, only ITCs were able to induce cell cycle arrest, suggesting that protein targets inside the cell may differ for the S and Se panels. Finally, the panels were tested for their ability to redox cycle when reacted with GSH to form superoxide and other reactive oxygen species (ROS). ISC compounds showed a much greater ability to redox cycle than corresponding ITCs, and were able to induce higher levels of ROS in A549 cells. Also, the direct proapoptotic effects of ISCs and ITCs were inhibited by GSH and potentiated by depletion of intracellular GSH by buthionine sulfoximine. In conclusion, our studies suggest that the redox-cycling capabilities of ISCs and thus generation of higher levels of ROS may be contributing to the increased cytotoxicity of ISC compounds in A549 cells, compared to that of the corresponding ITCs. PMID:22982772

  12. Proteomic Characterization of Reversible Thiol Oxidations in Proteomes and Proteins.

    PubMed

    Boronat, Susanna; Domènech, Alba; Hidalgo, Elena

    2017-03-01

    Reactive oxygen species are produced during normal metabolism in cells, and their excesses have been implicated in protein damage and toxicity, as well as in the activation of signaling events. In particular, hydrogen peroxide participates in the regulation of different physiological processes as well as in the induction of antioxidant cascades, and often the redox molecular events triggering these pathways are based on reversible cysteine (Cys) oxidation. Recent Advances: Increases in peroxides can cause the accumulation of reversible Cys oxidations in proteomes, which may be either protecting thiols from irreversible oxidations or may just be reporters of future toxicity. It is also becoming clear, however, that only a few proteins, such as the bacterial OxyR or peroxidases, can suffer direct oxidation of their Cys residues by hydrogen peroxide and, therefore, may be the only true sensors initiating signaling events. We will in this study describe some of the methodologies used to characterize at the proteome level reversible thiol oxidations, specifically those combining gel-free approaches with mass spectrometry. In the second part of this review, we will summarize some of the electrophoretic and proteomic techniques used to monitor Cys oxidation at the protein level, needed to confirm that a protein contains redox Cys involved in signaling relays, using as examples some of the best characterized redox sensors such as bacterial OxyR or yeast Tpx1/Pap1. While Cys oxidations are often detected in proteomes and in specific proteins, major efforts have to be made to establish that they are physiologically relevant. Antioxid. Redox Signal. 26, 329-344.

  13. Loss of Thiol Repair Systems in Human Cataractous Lenses

    PubMed Central

    Wei, Min; Xing, Kui-Yi; Fan, Yin-Chuan; Libondi, Teodosio; Lou, Marjorie F.

    2015-01-01

    Purpose. The purpose of this study was to investigate the thiol repair systems of thioltransferase (TTase) and thioredoxin (Trx) and oxidation-damaged proteins in human cataractous lenses. Methods. Cataractous lenses in humans (57–85 years of age) were classified into cortical, nuclear, mixed, mature, and hypermature cataract types by using a lens opacity classification system, and were obtained by extracapsular cataract extraction (ECCE) procedure. Cortical and nuclear cataracts were grouped by decreasing order of visual acuity into optical chart reading (R), counting fingers (CF), hand motion (HM), and light perception (LP). ECCE lens homogenate was analyzed for glutathione (GSH) level and enzyme activities of TTase, glutathione reductase (GR), Trx, and thioredoxin reductase (TR). Cortical and nuclear cataractous lenses (8 of each) with visual acuity better than HM were each dissected into cortical and nuclear portions for measurement of glyceraldehyde 3-phosphate dehydrogenase (G3PD) activity. Clear lenses (in humans 49–71 years of age) were used as control. Results. Compared with control, all cataractous lenses lost more than 80% GSH and 70% GR; TR and Trx activity; and 40% to 70% TTase activity, corroborated with the loss in visual acuity. Among cataracts with R and CF visual acuity, cortical cataract lost more cortical G3PD activity (18% of control) than that of nuclear cataract (50% of control), whereas GSH depletion and TTase inactivation were similar in both cataracts. Conclusions. Thiol repair systems were damaged in all types of cataracts. Cortical and nuclear cataracts showed differential G3PD inactivation in the cortex, implying those 2 type of cataracts might be formed through different mechanisms. PMID:25537203

  14. Polysulfides Link H2S to Protein Thiol Oxidation

    PubMed Central

    Greiner, Romy; Pálinkás, Zoltán; Bäsell, Katrin; Becher, Dörte; Antelmann, Haike; Nagy, Péter

    2013-01-01

    Abstract Aims: Hydrogen sulfide (H2S) is suggested to act as a gaseous signaling molecule in a variety of physiological processes. Its molecular mechanism of action was proposed to involve protein S-sulfhydration, that is, conversion of cysteinyl thiolates (Cys-S−) to persulfides (Cys-S-S−). A central and unresolved question is how H2S—that is, a molecule with sulfur in its lowest possible oxidation state (−2)—can lead to oxidative thiol modifications. Results: Using the lipid phosphatase PTEN as a model protein, we find that the “H2S donor” sodium hydrosulfide (NaHS) leads to very rapid reversible oxidation of the enzyme in vitro. We identify polysulfides formed in NaHS solutions as the oxidizing species, and present evidence that sulfane sulfur is added to the active site cysteine. Polysulfide-mediated oxidation of PTEN was induced by all “H2S donors” tested, including sodium sulfide (Na2S), gaseous H2S, and morpholin-4-ium 4-methoxyphenyl(morpholino) phosphinodithioate (GYY4137). Moreover, we show that polysulfides formed in H2S solutions readily modify PTEN inside intact cells. Innovation: Our results shed light on the previously unresolved question of how H2S leads to protein thiol oxidation, and suggest that polysulfides formed in solutions of H2S mediate this process. Conclusion: This study suggests that the effects that have been attributed to H2S in previous reports may in fact have been mediated by polysulfides. It also supports the notion that sulfane sulfur rather than sulfide is the actual in vivo agent of H2S signaling. Antioxid. Redox Signal. 19, 1749–1765. PMID:23646934

  15. Distinct physiological functions of thiol peroxidase isoenzymes in Saccharomyces cerevisiae.

    PubMed

    Park, S G; Cha, M K; Jeong, W; Kim, I H

    2000-02-25

    A new type of peroxidase ("thiol peroxidase"; TPx) having cysteine as the primary site of catalysis has been discovered from prokaryotes to eukaryotes. In addition to two yeast TPx isoforms (TSA I and TSA II/AHPC1) previously described, three additional TPx homologues were identified by analysis of the open reading frame data base for Saccharomyces cerevisiae. Three novel isoforms showed a distinct thiol peroxidase activity supported by thioredoxin, and appeared to be distinctively localized in cytoplasm, mitochondria, and nucleus. Each isoform was named after its subcellular localization such as cytoplasmic TPx I (cTPx I or TSA I), cTPx II, cTPx III (TSA II/AHPC1), mitochondrial TPx (mTPx), and nuclear TPx (nTPx). Their transcriptional activities suggest that cTPx I and cTPx III are the most predominant isoforms among the five type isoforms. Transcriptional activities of TPx isoenzymes during yeast life span were quite different from each other. Unlike other TPx null mutants, cTPx I null mutant was hypersensitive to various oxidants except for 4-nitroquinoline N-oxide. The null mutant was more resistant toward 4-nitroquinoline N-oxide and acidic culture than its wild type. The severe growth retardation of cTPx II mutant resulted in accumulation of G(1)-phased cells. Based on kinetic properties of five isoforms, their subcellular localizations, and distinct physiology of each null mutant, we discussed the physiological functions of five types of TPx isoenzymes in yeast throughout the full growth cycle.

  16. Surface modification of model hydrogel contact lenses with hyaluronic acid via thiol-ene "click" chemistry for enhancing surface characteristics.

    PubMed

    Korogiannaki, Myrto; Zhang, Jianfeng; Sheardown, Heather

    2017-10-01

    Discontinuation of contact lens wear as a result of ocular dryness and discomfort is extremely common; as many as 26% of contact lens wearers discontinue use within the first year. While patients are generally satisfied with conventional hydrogel lenses, improving on-eye comfort continues to remain a goal. Surface modification with a biomimetic, ocular friendly hydrophilic layer of a wetting agent is hypothesized to improve the interfacial interactions of the contact lens with the ocular surface. In this work, the synthesis and characterization of poly(2-hydroxyethyl methacrylate) surfaces grafted with a hydrophilic layer of hyaluronic acid are described. The immobilization reaction involved the covalent attachment of thiolated hyaluronic acid (20 kDa) on acrylated poly(2-hydroxyethyl methacrylate) via nucleophile-initiated Michael addition thiol-ene "click" chemistry. The surface chemistry of the modified surfaces was analyzed by Fourier transform infrared spectroscopy-attenuated total reflectance and X-ray photoelectron spectroscopy. The appearance of N (1s) and S (2p) peaks on the low resolution X-ray photoelectron spectroscopy spectra confirmed successful immobilization of hyaluronic acid. Grafting hyaluronic acid to the poly(2-hydroxyethyl methacrylate) surfaces decreased the contact angle, the dehydration rate, and the amount of nonspecific sorption of lysozyme and albumin in comparison to pristine hydrogel materials, suggesting the development of more wettable surfaces with improved water-retentive and antifouling properties, while maintaining optical transparency (>92%). In vitro testing also showed excellent viability of human corneal epithelial cells with the hyaluronic acid-grafted poly(2-hydroxyethyl methacrylate) surfaces. Hence, surface modification with hyaluronic acid via thiol-ene "click" chemistry could be useful in improving contact lens surface properties, potentially alleviating symptoms of contact lens related dryness and discomfort during

  17. Mapping Local Protein Electrostatics by EPR of pH-Sensitive Thiol-Specific Nitroxide† ¶

    PubMed Central

    Voinov, Maxim A.; Ruuge, Andres; Reznikov, Vladimir A.; Grigor’ev, Igor A.; Smirnov, Alex I.

    2013-01-01

    A first thiol-specific pH-sensitive nitroxide spin label of the imidazolidine series -methanethiosulfonic acid S-(1-oxyl-2,2,3,5,5-pentamethylimidazolidin-4-ylmethyl) ester (IMTSL) - has been synthesized and characterized. X- (9 GHz) and W-band (94 GHz) EPR spectral parameters of the new spin label in its free form and covalently attached to an amino acid cysteine and a tripeptide glutathione were studied as a function of pH and solvent polarity. pKa value of protonatable tertiary amino group of the spin label was found to be unaffected by other ionizable groups present in side chains of unstructured small peptides. The W-band EPR spectra were shown to allow for pKa determination from precise g-factor measurements. Is has been demonstrated that high accuracy of pKa determination for pH-sensitive nitroxides could be achieved regardless the frequency of measurements or the regime of spin exchange: fast at X-band and slow at W-band. IMTSL was found to react specifically with a model protein - iso-1-cytochrome c from yeast Saccharomyces cerevisiae - giving EPR spectra very similar to those of the most commonly employed cysteine-specific label MTSL. CD data indicated no perturbations to the overall protein structure upon IMTSL labeling. It was found that for IMTSL, giso correlates linearly with Aiso but the slopes are different for the neutral and charged forms of the nitroxide. This finding was attributed to the solvent effects on the spin density at the oxygen atom of the N–O group and on the excitation energy of the oxygen lone-pair orbital. PMID:18426227

  18. Thiol synthesis and arsenic hyperaccumulation in Pteris vittata (Chinese brake fern).

    PubMed

    Zhang, Weihua; Cai, Yong; Downum, Kelsey R; Ma, Lena Q

    2004-10-01

    Pteris vittata (Chinese brake fern) has potential for phytoremediation of As-contaminated sites. In this study, the synthesis of total thiols and acid-soluble thiols in P. vittata was investigated under arsenic exposure. The strong and positive correlation between As concentration and acid-soluble thiols in plant leaflets suggests that acid-soluble thiols may play a role in As detoxification. A major As-induced thiol was purified and characterized. A molecular ion (M + 1) of 540 m/z suggests that the thiol was a phytochelatin (PC) with two base units (PC(2)). However, the ratios of acid-soluble thiols to As in leaflets exposed to As ranged from 0.012 to 0.026, suggesting that only a very small part of As is complexed by PC(2). PCs could play a minor detoxification role in this hyperaccumulator. A PC-independent mechanism appears to be mainly involved in As tolerance, while PC-dependent detoxification seems to be a supplement.

  19. Identification of novel aroma-active thiols in pan-roasted white sesame seeds.

    PubMed

    Tamura, Hitoshi; Fujita, Akira; Steinhaus, Martin; Takahisa, Eisuke; Watanabe, Hiroyuki; Schieberle, Peter

    2010-06-23

    Screening for aroma-active compounds in an aroma distillate obtained from freshly pan-roasted sesame seeds by aroma extract dilution analysis revealed 32 odorants in the FD factor range of 2-2048, 29 of which could be identified. The highest FD factors were found for the coffee-like smelling 2-furfurylthiol, the caramel-like smelling 4-hydroxy-2,5-dimethyl-3(2H)-furanone, the coffee-like smelling 2-thenylthiol (thiophen-2-yl-methylthiol), and the clove-like smelling 2-methoxy-4-vinylphenol. In addition, 9 odor-active thiols with sulfurous, meaty, and/or catty, black-currant-like odors were identified for the first time in roasted sesame seeds. Among them, 2-methyl-1-propene-1-thiol, (Z)-3-methyl-1-butene-1-thiol, (E)-3-methyl-1-butene-1-thiol, (Z)-2-methyl-1-butene-1-thiol, (E)-2-methyl-1-butene-1-thiol, and 4-mercapto-3-hexanone were previously unknown as food constituents. Their structures were confirmed by comparing their mass spectra and retention indices as well as their sensory properties with those of synthesized reference compounds. The relatively unstable 1-alkene-1-thiols represent a new class of food odorants and are suggested as the key contributors to the characteristic, but quickly vanishing, aroma of freshly ground roasted sesame seeds.

  20. Disulfide-Linked Dinitroxides for Monitoring Cellular Thiol Redox Status through Electron Paramagnetic Resonance Spectroscopy.

    PubMed

    Legenzov, Eric A; Sims, Stephen J; Dirda, Nathaniel D A; Rosen, Gerald M; Kao, Joseph P Y

    2015-12-01

    Intracellular thiol-disulfide redox balance is crucial to cell health, and may be a key determinant of a cancer's response to chemotherapy and radiation therapy. The ability to assess intracellular thiol-disulfide balance may thus be useful not only in predicting responsiveness of cancers to therapy, but in assessing predisposition to disease. Assays of thiols in biology have relied on colorimetry or fluorimetry, both of which require UV-visible photons, which do not penetrate the body. Low-frequency electron paramagnetic resonance imaging (EPRI) is an emerging magnetic imaging technique that uses radio waves, which penetrate the body well. Therefore, in combination with tailored imaging agents, EPRI affords the opportunity to image physiology within the body. In this study, we have prepared water-soluble and membrane-permeant disulfide-linked dinitroxides, at natural isotopic abundance, and with D,(15)N-substitution. Thiols such as glutathione cleave the disulfides, with simple bimolecular kinetics, to yield the monomeric nitroxide species, with distinctive changes in the EPR spectrum. Using the D,(15)N-substituted disulfide-dinitroxide and EPR spectroscopy, we have obtained quantitative estimates of accessible intracellular thiol in cultured human lymphocytes. Our estimates are in good agreement with published measurements. This suggests that in vivo EPRI of thiol-disulfide balance is feasible. Finally, we discuss the constraints on the design of probe molecules that would be useful for in vivo EPRI of thiol redox status.

  1. Oxidation of dissolved elemental mercury by thiol compounds under anoxic conditions

    SciTech Connect

    Zheng, Wang; Lin, Hui; Mann, Benjamin F; Liang, Liyuan; Gu, Baohua

    2013-01-01

    Mercuric mercury, Hg(II), forms strong complexes with thiol compounds that commonly dominate Hg(II) speciation in natural freshwater. However, reactions between dissolved elemental Hg(0) and thiols are not well understood although these processes are likely to be important in determining Hg speciation and geochemical cycling in the environment. In this study, reaction rates and mechanisms between dissolved Hg(0) and a number of selected organic ligands with varying molecular structures and sulfur (S) oxidation states were determined to assess the role of these ligands in Hg(0) redox transformation. We found that all thiols caused oxidation of Hg(0) under anoxic conditions but, contrary to expectation, compounds with higher S-oxidation states (e.g., disulfide) than thiols exhibited little or no reactivity with Hg(0) at pH 7. The rate and extent of Hg(0) oxidation varied widely, with smaller aliphatic thiols showing the greatest degree of oxidation. The mechanism of the oxidation is attributed to a two-step process involving adsorption of Hg(0) to thiols followed by the charge transfer from Hg(0) to electron acceptors. These observations demonstrate a unique thiol-induced oxidation pathway of dissolved Hg(0), with important implications for the redox transformation, speciation, and bioavailability of Hg for microbial methylation in anoxic environments.

  2. The influence of oxidation of membrane thiol groups on lysosomal proton permeability.

    PubMed Central

    Wan, F Y; Wang, Y N; Zhang, G J

    2001-01-01

    The influence of oxidation of membrane thiol groups on lysosomal proton permeability was studied by measuring lysosomal pH with FITC-conjugated dextran, determining the membrane potential with 3,3'-dipropylthiadicarbocyanine iodide and monitoring their proton leakage with p-nitrophenol. Residual membrane thiol groups were measured with 5,5'-dithiobis-(2-nitrobenzoic acid). The lysosomal membrane thiol groups were modified by treatment with diamide and dithiothreitol. SDS/PAGE revealed aggregations of the membrane proteins induced by the treatment of lysosomes with diamide. The cross-linkage of proteins could be abolished by subsequent treatment with dithiothreitol, indicating that the proteins were linked via disulphide bonds. Treating the lysosomes with diamide decreased their membrane thiol groups and caused increases in lysosomal pH, membrane potential and proton leakage, which could be reversed by treatment of the lysosomes with dithiothreitol. This indicates that the lysosomal proton permeability can be increased by oxidation of the membrane thiol groups and restored to the normal level by reduction of the groups. Treatment of the lysosomes with N-ethylmaleimide reduced their membrane thiol groups but did not change the lysosomal pH or their degree of proton leakage. It suggests that protein aggregation may be an important mechanism for the increase in lysosomal proton permeability. The results raise the possibility that the proton permeability of lysosomes in vivo may be affected by the redox states of their membrane thiol groups. PMID:11716763

  3. Redox regulation of sperm surface thiols modulates adhesion to the fallopian tube epithelium.

    PubMed

    Talevi, Riccardo; Zagami, Maria; Castaldo, Marianna; Gualtieri, Roberto

    2007-04-01

    Sperm that adhere to the fallopian tube epithelium are of superior quality and adhesion extends their fertile life. It has been postulated that periovulatory signals, as yet undefined, promote sperm release. In the in vitro studies described here, we examined the effects of several antioxidants, reportedly present within oviductal fluid, on the modulation of sperm-oviduct adhesion in bovine species. Results showed that 1) the cell-permeant thiols (penicillamine, beta mercaptoethanol, cysteine, and dithiotreitol), as well as the nonpermeant thiol, reduced glutathione, cause adhering spermatozoa to release from the epithelium; 2) thiol action is exerted on spermatozoa; and 3) oxidized glutathione, as well as the non-thiol antioxidants (dimethylthiourea, trolox, superoxide dismutase, and catalase) have no effect. Sperm surface sulfhydryls labeled with iodoacetamide fluorescein showed that spermatozoa devoid of sulfhydryls on the head surface adhered to the fallopian epithelium in vitro, whereas thiol-induced release increased the exposure of sulfhydryls on the sperm head surface. Finally, analysis of capacitation status demonstrated that uncapacitated spermatozoa adhered to the oviduct, and that thiol-induced release of spermatozoa was accompanied by capacitation. In conclusion, thiol-reducing agents in the oviductal fluid may modulate the redox status of sperm surface proteins, leading to the release of spermatozoa selected and stored through adhesion to the fallopian tube epithelium in the bovine species.

  4. Biscysteine-Bearing Peptide Probes To Reveal Extracellular Thiol-Disulfide Exchange Reactions Promoting Cellular Uptake.

    PubMed

    Li, Tao; Gao, Wei; Liang, Jingjing; Zha, Mirao; Chen, Yaqi; Zhao, Yibing; Wu, Chuanliu

    2017-08-15

    In recent years, delivery systems based on the incorporation of thiols/disulfides have been extensively explored to promote the intracellular delivery of biological cargoes. However, it remains unclear about the detailed processes of thiol-disulfide exchanges taking place on the cell surface and how the exchange reactions promote the cellular uptake of cargoes bearing thiols or disulfide bonds. In this work, we report the rational design of biscysteine motif-containing peptide probes with substantially different ring-closing property and how these peptide probes were employed to explore the thiol-disulfide exchanges on the cell surface. Our results show that extensive thiol-disulfide exchanges between peptides and exofacial protein thiols/disulfides are involved in the cellular uptake of these peptide probes, and importantly glutathione (GSH) exported from the cytosols participates extensively in the exchange reactions. Cysteine-glycine-cysteine (CGC)-containing peptide probes can be more efficiently taken up by cells compared to other probes, and we suggested that the driving force for the superior cellular uptake arises from very likely the unique propensity of the CGC motif in forming doubly bridged disulfide bonds with exofacial proteins. Our probe-based strategy provides firsthand information on the detailed processes of the exchange reactions, which would be of great benefit to the development of delivery systems based on the extracellular thiol-disulfide exchanges for intracellular delivery of biologics.

  5. Effect of Thiol-Binding Reagents on the Metabolism of Thiosulfate and Tetrathionate by Thiobacillus neapolitanus

    PubMed Central

    Trudinger, P. A.

    1965-01-01

    Trudinger, P. A. (Division of Plant Industry, Canberra, Australia). Effect of thiol-binding reagents on the metabolism of thiosulfate and tetrathionate by Thiobacillus neapolitanus. J. Bacteriol. 89:617–625. 1965.—Iodoacetamide, N-ethyl maleimide (NEM), p-chloromercuribenzoate (CMB), Mercurochrome, and HgCl2 inhibited the oxidation of thiosulfate to sulfate by Thiobacillus neapolitanus; tetrathionate accumulated under these conditions. High concentrations of the thiol-binding reagents lowered the rate of oxidation of thiosulfate to tetrathionate; inhibition by CMB was reversed by high concentrations of thiosulfate. Relatively low concentrations of the thiol-binding reagents completely inhibited the oxidation and anaerobic metabolism of tetrathionate. Similar reagents had no effect on a soluble thiosulfate-oxidizing enzyme. Inhibition by thiol-binding reagents was overcome by washing the bacteria with Na2S or thioethanol after their exposure to the inhibitors. Under some conditions, the addition of thiosulfate or tetrathionate to bacterial suspensions before the addition of the thiol-binding reagents prevented the inhibition of thiosulfate and tetrathionate metabolism by these reagents. Thiosulfate catalyzed a rapid chemical breakdown of NEM and reacted with iodoacetamide. A complex between thiosulfate and mercuribenzoate was demonstrated. Three types of thiol group appear to be associated with the metabolism of thiosulfate and tetrathionate; one of these types may be located at the bacterial cell membrane. The results are consistent with the hypothesis that thiols (or disulfide groups) are binding sites for the substrates. PMID:14273636

  6. Modular modification of xylan with UV-initiated thiol-ene reaction.

    PubMed

    Nurmi, Leena; Salminen, Reeta; Setälä, Harri

    2015-03-02

    Birch xylan was functionalized with various thiols through UV initiated radical thiol-ene reaction under mild conditions. Xylan was allylated through etherification with allyl glycidyl ether under alkaline conditions. The allylated xylan was then reacted with thiols containing varying functional groups: trimethylbenzyl mercaptan, dodecanethiol, thioglycolic acid, L-cysteine and cysteamine hydrochloride. The reactions were conducted under homogeneous conditions at room temperature, either in water (hydrophilic thiols) or in DMF (hydrophobic thiols). The effect of reaction parameters to the functionalization efficiency was studied, including, for example, thiol excess, thiol character, initiator amount and reaction mixture concentration. The reactions were fast and 100% conversion of allyl groups was reached in most cases, sometimes already within 10 min. Water as solvent resulted generally in faster reactions when compared to DMF, and it was possible to conduct the aqueous reaction even without added UV initiator. It was also possible to incorporate two functionalities simultaneously during one reaction into the xylan structure. Copyright © 2014 Elsevier Ltd. All rights reserved.

  7. Conductive probe AFM study of Pt-thiol and Au-thiol contacts in metal-molecule-metal systems

    NASA Astrophysics Data System (ADS)

    Kim, Chang Min; Bechhoefer, John

    2013-01-01

    The charge transport mechanism between 1,8-octanedithiol (ODT, C8H16S2H2) and platinum and gold electrodes is studied by breaking bonds between single ODT molecules and atomic metal junctions using conductive probe atomic force microscopy. Histograms of conductance values show peaks that are obscured by background processes that differ from the metal-molecule-metal conduction path of interest. We introduce a new method to reduce greatly such backgrounds by dividing by a 1-octanethiol (OMT, C8H17SH) reference histogram, without data selection. The method reveals three series of conductance values for both platinum and gold contacts, which we associate with geometrically different configurations between thiol and metal atoms. The ordering of conductance values, Pt-ODT-Pt > Pt-ODT-Au> Au-ODT-Au, is consistent with a relative dependence on both the number of electron channels and the density of states.

  8. Determination of thiol functional groups on bacteria and natural organic matter in environmental systems.

    PubMed

    Rao, Balaji; Simpson, Carolyne; Lin, Hui; Liang, Liyuan; Gu, Baohua

    2014-02-01

    Organic thiols (R-SH) are known to react and form complexes with some toxic soft metals such as mercury (Hg) in both biotic and abiotic systems. However, a clear understanding of these interactions is currently limited because quantifying thiols in environmental matrices is difficult due to their low abundance, susceptibility to oxidation, and measurement interference by non-thiol compounds in samples. Here, we report a fluorescence-labeling method using a maleimide containing probe, ThioGlo-1 (TG-1), to determine total thiols directly on bacterial cells and natural organic matter (NOM). We systematically evaluated the optimal thiol labeling conditions and interference from organic compounds such as disulfide, methionine, thiourea, and amine, and inorganic ions such as Na(+), K(+), Ca(2+), Fe(2+), Cl(-), SO4(2-), HCO3(-), and SCN(-), and found that the method is highly sensitive and selective. Only relatively high levels of sulfide (S(2-)) and sulfite (SO3(2-)) significantly interfere with the thiol analysis. The method was successful in determining thiols in a bacterium Geobacter sulfurreducens PCA and its mutants in a phosphate buffered saline solution. The measured value of ~2.1 × 10(4) thiols cell(-1) (or ~0.07 µmol g(-1) wet cells) is in good agreement with that observed during reactions between Hg and PCA cells. Using the standard addition, we determined the total thiols of two reference NOM samples, the reduced Elliot soil humic acid and Suwanee River NOM, to be 3.6 and 0.7 µmol g(-1), respectively, consistent with those obtained based on their reactions with Hg.

  9. Beer thiol-containing compounds and redox stability: kinetic study of 1-hydroxyethyl radical scavenging ability.

    PubMed

    de Almeida, Natália E C; Lund, Marianne N; Andersen, Mogens L; Cardoso, Daniel R

    2013-10-02

    The 1-hydroxyethyl radical is a central intermediate in oxidative reactions occurring in beer. The reactivity of thiol-containing compounds toward 1-hydroxyethyl radical was evaluated in beer model solutions using a competitive kinetic approach, employing the spin-trap 4-POBN as a probe and by using electron paramagnetic resonance to detect the generated 1-hydroxyethyl/4-POBN spin adduct. Thiol-containing compounds were highly reactive toward the 1-hydroxyethyl radical with apparent second-order rate constants close to the diffusion limit in water and ranging from 0.5 × 10⁹ L mol⁻¹ s⁻¹ for the His-Cys-Lys-Phe-Trp-Trp peptide to 6.1 × 10⁹ L mol⁻¹ s⁻¹ for the reduced lipid transfer protein 1 (LTP1) isolated from beer. The reactions gave rise to a moderate kinetic isotope effect (k(H)/k(D) = 2.3) suggesting that reduction of the 1-hydroxyethyl radical by thiol-containing compounds takes place by hydrogen atom abstraction from the RSH group rather than electron transfer. The content of reduced thiols in different beers was determined using a previously established method based on ThioGlo-1 as the thiol derivatization reagent and detection of the derivatized thiols by reverse-phase liquid chromatography coupled to a fluorescence detector. The total level of thiol in beer (oxidized and reduced) was determined after a reduction step employing 3,3',3″-phosphanetriyltripropanoic acid (TCEP) as the disulfide reductant. A good correlation among total protein and total thiol content in different beers was observed. The results suggest a similar ratio between reduced thiols and disulfides in all of the tested beers, which indicates a similar redox state.

  10. Determination of thiol functional groups on bacteria and natural organic matter in environmental systems

    SciTech Connect

    Anandha Rao, Balaji; Lin, Hui; Liang, Liyuan; Gu, Baohua

    2014-01-01

    Organic thiols (R-SH) are known to react and form complexes with some toxic soft metals such as mercury (Hg) in both biotic and abiotic systems. However, a clear understanding of these interactions is currently limited because quantifying thiols in environmental matrices is difficult due to their low abundance, susceptibility to oxidation, and measurement interference by non-thiol compounds in samples. Here, we report a fluorescence-labeling method using a maleimide containing probe, ThioGlo-1 (TG-1), to determine total thiols directly on bacterial cells and natural organic matter (NOM). We systematically evaluated the optimal thiol labeling conditions and interference from organic compounds such as disulfide, methionine, thiourea, and amine, and inorganic ions such as Na+, K+, Ca2+, Fe2+, Cl-, SO42-, HCO3-, and SCN-, and found that the method is highly sensitive and selective. Only relatively high levels of sulfide (S2-) and sulfite (SO32-) significantly interfere with the thiol analysis. The method was successful in determining thiols in a bacterium Geobacter sulfurreducens PCA and its mutants in a phosphate buffered saline solution. The measured value of ~2.1 104 thiols cell-1 (or ~0.07 mol g-1 wet cells) is in good agreement with that observed during reactions between Hg and PCA cells. Using the standard addition, we determined the total thiols of two reference NOM samples, the reduced Elliot soil humic acid and Suwanee River NOM, to be 3.6 and 0.7 mol g-1, respectively, consistent with those obtained based on their reactions with Hg.

  11. Conjugation of glutathione and other thiols with bioreductively activated mitomycin C. Effect of thiols on the reductive activation rate.

    PubMed

    Sharma, M; Tomasz, M

    1994-01-01

    Mitomycin C (MC), a clinically used natural antitumor agent, was shown to form three monoconjugates (11a-13a) and two bisconjugates (14a, 15a) with GSH upon reductive activation by rat liver microsomes, purified NADPH-cytochrome c reductase, or NADH-cytochrome c reductase or chemical reduction using H2/PtO2. Rat liver cytosol/NADH activated MC only at acidic pH (5.8), resulting in the formation of a single GSH-MC monoconjugate, 13a. The reductase responsible for cytosolic activation of MC to form this conjugate was DT-diaphorase. GSH itself did not reduce MC, and unreduced MC did not form conjugates with GSH. A moderate catalytic effect by glutathione S-transferase was demonstrated on the cytosol-activated reaction. Mercaptoethanol and N-acetylcysteine gave analogous sets of five MC-thiol conjugates under cytochrome c reductase or H2/PtO2 activation conditions. The structures of all 15 MC-thiol conjugates (five each with GSH, mercaptoethanol, and N-acetylcysteine, respectively) were determined, using 1H-NMR, UV, and mass spectroscopies, combined with analytical chemical and radiolabeling methods. The mechanism of formation of the conjugates features SN2 displacement of the carbamate of the reduced MC by GS-. The MC-GSH conjugates were noncytotoxic to the tumor cells tested. The conjugation of GSH with activated MC is likely to represent detoxication in mammalian cells. As another effect, GSH accelerates the rate of reduction of MC by "slow" reducing agents such as cytochrome c reductases and H2/PtO2. A mechanism is proposed to explain this effect, which involves further reduction of the initially formed MC semiquinone free radical by GSH.

  12. Hot melt adhesive attachment pad

    NASA Technical Reports Server (NTRS)

    Fox, R. L.; Frizzill, A. W.; Little, B. D.; Progar, D. J.; Coultrip, R. H.; Couch, R. H.; Gleason, J. R.; Stein, B. A.; Buckley, J. D.; St.clair, T. L. (Inventor)

    1984-01-01

    A hot melt adhesive attachment pad for releasably securing distinct elements together is described which is particularly useful in the construction industry or a spatial vacuum environment. The attachment pad consists primarily of a cloth selectively impregnated with a charge of hot melt adhesive, a thermo-foil heater, and a thermo-cooler. These components are securely mounted in a mounting assembly. In operation, the operator activates the heating cycle transforming the hot melt adhesive to a substantially liquid state, positions the pad against the attachment surface, and activates the cooling cycle solidifying the adhesive and forming a strong, releasable bond.

  13. Universal precision sine bar attachment

    NASA Technical Reports Server (NTRS)

    Mann, Franklin D. (Inventor)

    1989-01-01

    This invention relates to an attachment for a sine bar which can be used to perform measurements during lathe operations or other types of machining operations. The attachment can be used for setting precision angles on vises, dividing heads, rotary tables and angle plates. It can also be used in the inspection of machined parts, when close tolerances are required, and in the layout of precision hardware. The novelty of the invention is believed to reside in a specific versatile sine bar attachment for measuring a variety of angles on a number of different types of equipment.

  14. Everything You Want To Know about Attachment.

    ERIC Educational Resources Information Center

    Honig, Alice Sterling

    This paper discusses infant attachment, which it defines as a long-lasting emotional bond revealed when a child under stress seeks out and tries to stay close to a specific figure. The paper addresses: (1) What is attachment? Who are the pioneers in attachment theory?; (2) How do we notice attachment in action?; (3) Is attachment the only…

  15. Visible-Light-Mediated Thiol-Ene Reactions through Organic Photoredox Catalysis.

    PubMed

    Zhao, Gaoyuan; Kaur, Sarbjeet; Wang, Ting

    2017-06-16

    Synthetically useful radical thiol-ene reactions can be initiated by visible-light irradiation in the presence of an organic photocatalyst, 9-mesityl-10-methylacridinum tetrafluoroborate. The key thiyl radical intermediates are generated upon quenching of the photoexcited catalyst with a variety of thiols. The success of this method requires only the use of near-stoichiometric levels of alkene coupling partners. Using these highly efficient metal-free conditions, thiol-ene reactions between carbohydrates and peptides can be accomplished in excellent yields.

  16. Imaging disulfide dinitroxides at 250 MHz to monitor thiol redox status.

    PubMed

    Elajaili, Hanan; Biller, Joshua R; Rosen, Gerald M; Kao, Joseph P Y; Tseytlin, Mark; Buchanan, Laura A; Rinard, George A; Quine, Richard W; McPeak, Joseph; Shi, Yilin; Eaton, Sandra S; Eaton, Gareth R

    2015-11-01

    Measurement of thiol-disulfide redox status is crucial for characterization of tumor physiology. The electron paramagnetic resonance (EPR) spectra of disulfide-linked dinitroxides are readily distinguished from those of the corresponding monoradicals that are formed by cleavage of the disulfide linkage by free thiols. EPR spectra can thus be used to monitor the rate of cleavage and the thiol redox status. EPR spectra of (1)H,(14)N- and (2)H,(15)N-disulfide dinitroxides and the corresponding monoradicals resulting from cleavage by glutathione have been characterized at 250 MHz, 1.04 GHz, and 9 GHz and imaged by rapid-scan EPR at 250 MHz.

  17. Imaging disulfide dinitroxides at 250 MHz to monitor thiol redox status

    NASA Astrophysics Data System (ADS)

    Elajaili, Hanan; Biller, Joshua R.; Rosen, Gerald M.; Kao, Joseph P. Y.; Tseytlin, Mark; Buchanan, Laura A.; Rinard, George A.; Quine, Richard W.; McPeak, Joseph; Shi, Yilin; Eaton, Sandra S.; Eaton, Gareth R.

    2015-11-01

    Measurement of thiol-disulfide redox status is crucial for characterization of tumor physiology. The electron paramagnetic resonance (EPR) spectra of disulfide-linked dinitroxides are readily distinguished from those of the corresponding monoradicals that are formed by cleavage of the disulfide linkage by free thiols. EPR spectra can thus be used to monitor the rate of cleavage and the thiol redox status. EPR spectra of 1H,14N- and 2H,15N-disulfide dinitroxides and the corresponding monoradicals resulting from cleavage by glutathione have been characterized at 250 MHz, 1.04 GHz, and 9 GHz and imaged by rapid-scan EPR at 250 MHz.

  18. Readout fidelity of coaxial holographic digital data page recording in nanoparticle-(thiol-ene) polymer composites

    NASA Astrophysics Data System (ADS)

    Nagaya, Kohta; Hata, Eiji; Tomita, Yasuo

    2016-09-01

    We report on an experimental investigation of nanoparticle-concentration and thiol-to-ene stoichiometric ratio dependences of symbol error rates (SERs) and signal-to-noise ratios (SNRs) of digital data pages recorded at a wavelength of 532 nm in thiol-ene based nanoparticle-polymer composite (NPC) films by using a coaxial holographic digital data storage method. We show that SERs and SNRs at the optimized material condition can be lower than 1 × 10-4 and higher than 10, respectively, without error correction coding. These results show the usefulness of thiol-ene based NPCs as coaxial holographic data storage media.

  19. Modified thiol-ene networks: Tuning the glass transition temperature and energy damping capabilities

    NASA Astrophysics Data System (ADS)

    Sun, Ning; Rafailovich, Miriam; Gersappe, Dilip

    2013-03-01

    Utilizing thiol-ene `click' reactions, it is possible to produce thermoset networks that are highly homogeneous and thus exhibit enhanced energy damping capabilities. This talk will present recent results in the characterization and impact testing of modified thiol-ene networks with tunable physical properties. In particular, we synthesize ternary networks containing (1) bulky side-chain substituents, (2) isocyanate functionality, or (3) dual thiol components to improve control over the glass transition temperature and strain at break. In addition, we present results in the high-impact compression testing to demonstrate the energy damping capabilities of these materials.

  20. Thiol-functionalized magnetite/graphene oxide hybrid as a reusable adsorbent for Hg2+ removal

    NASA Astrophysics Data System (ADS)

    Bao, Jian; Fu, You; Bao, Zhihao

    2013-11-01

    A thiol-functionalized magnetite/graphene oxide (MGO) hybrid as an adsorbent of Hg2+ was successfully synthesized by a two-step reaction. It exhibited a higher adsorption capacity compared to the bare graphene oxide and MGO due to the combined adsorption of thiol groups and magnetite nanocrystals. Its capacity reached 289.9 mg g-1 in a solution with an initial Hg2+ concentration of 100 mg l-1. After being exchanged with H+, the adsorbent could be reused. The adsorption of Hg2+ by the thiol-functionalized MGO fits well with the Freundlich isotherm model and followed pseudo-second-order kinetics.

  1. The effect of a cross-bridging thiol reagent on the catecholamine fluxes of adrenal medulla vesicles

    PubMed Central

    Hasselbach, W.; Taugner, G.

    1970-01-01

    The thiol groups of the vesicular protein of bovine adrenal medulla were allowed to react with the bifunctional thiol reagent bis-(N-maleimidomethyl) ether and with the monofunctional thiol reagent N-ethylmaleimide, and the ATP-dependent and -independent catecholamine fluxes of the modified preparations were studied. 1. During the initial phase of the reaction bis-(N-maleimidomethyl) ether blocks twice as many thiol groups as does N-ethylmaleimide at equimolar concentrations. 2. Labelling of the bis-(N-maleimidomethyl) ether–protein compound with [14C]-cysteine shows that 70–80% of the blocked thiol groups are interconnected by the bifunctional thiol reagent. 3. At a low extent of reaction (1.5mol of thiol groups/106g of protein) the catecholamine efflux is diminished. If more than 2mol of thiol groups/106g of protein are blocked, the efflux is enhanced whichever thiol reagent is applied. 4. If 2–4mol of thiol groups/106g of protein are blocked the inhibition of the catecholamine influx increases linearly with the proportion of the thiol groups blocked. 5. ATP protects the catecholamine influx and the adenosine triphosphatase activity against bis-(N-maleimidomethyl) ether poisoning somewhat less effectively than against N-ethylmaleimide poisoning. PMID:4249860

  2. Interaction of thiols and non-thiol {center_dot}OH scavengers in the modification of radiation-induced DNA damage

    SciTech Connect

    Krisch, R.E.; Ayene, I.S.; Koch, C.J.

    1995-12-31

    Oxygen has long been known to sensitize cells to the lethal effects of ionizing radiation and is widely believed to do so by the fixation of potentially reversible radical damage to cellular DNA. A number of studies have suggested that this widely observed oxygen enhancement of cell killing requires the presence of reduced thiols. Published in vitro studies of the modification of DNA damage by glutathione or other thiols have generally shown peak oxygen enhancement ratios (OERs) much higher than those observed for cell killing. However, these studies measured loss of DNA transforming activity or induction of single-strand DNA breaks (SSBs), related endpoints which are not thought to represent lethal lesions, rather than double-strand breaks (DSBs), which are generally believed to be the dominant lethal lesions from ionizing radiation. In addition, non-thiol scavengers of OH radicals were not generally present. There is also evidence that, in addition to their protective effects, some non-thiol {center_dot}OH scavengers can produce radicals which are damaging to DNA under anoxic conditions. In the present investigation, the authors have adapted a previously used in vitro model system to simultaneously investigate the effects on radiation-induced single- and double-strand DNA breaks of various combinations of glutathione and glycerol, a widely used non-thiol scavenger, in the presence and absence of oxygen.

  3. Preparation and Preliminary Dielectric Characterization of Structured C60-Thiol-Ene Polymer Nanocomposites Assembled Using the Thiol-Ene Click Reaction

    PubMed Central

    Ahmed, Hanaa M.; Windham, Amber D.; Al-Ejji, Maryam M.; Al-Qahtani, Noora H.; Hassan, Mohammad K.; Mauritz, Kenneth A.; Buchanan, Randy K.; Buchanan, J. Paige

    2015-01-01

    Fullerene-containing materials have the ability to store and release electrical energy. Therefore, fullerenes may ultimately find use in high-voltage equipment devices or as super capacitors for high electric energy storage due to this ease of manipulating their excellent dielectric properties and their high volume resistivity. A series of structured fullerene (C60) polymer nanocomposites were assembled using the thiol-ene click reaction, between alkyl thiols and allyl functionalized C60 derivatives. The resulting high-density C60-urethane-thiol-ene (C60-Thiol-Ene) networks possessed excellent mechanical properties. These novel networks were characterized using standard techniques, including infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and thermal gravimetric analysis (TGA). The dielectric spectra for the prepared samples were determined over a broad frequency range at room temperature using a broadband dielectric spectrometer and a semiconductor characterization system. The changes in thermo-mechanical and electrical properties of these novel fullerene-thiol-ene composite films were measured as a function of the C60 content, and samples characterized by high dielectric permittivity and low dielectric loss were produced. In this process, variations in chemical composition of the networks were correlated to performance characteristics. PMID:28793678

  4. Preparation and Preliminary Dielectric Characterization of Structured C60-Thiol-Ene Polymer Nanocomposites Assembled Using the Thiol-Ene Click Reaction.

    PubMed

    Ahmed, Hanaa M; Windham, Amber D; Al-Ejji, Maryam M; Al-Qahtani, Noora H; Hassan, Mohammad K; Mauritz, Kenneth A; Buchanan, Randy K; Buchanan, J Paige

    2015-11-18

    Fullerene-containing materials have the ability to store and release electrical energy. Therefore, fullerenes may ultimately find use in high-voltage equipment devices or as super capacitors for high electric energy storage due to this ease of manipulating their excellent dielectric properties and their high volume resistivity. A series of structured fullerene (C60) polymer nanocomposites were assembled using the thiol-ene click reaction, between alkyl thiols and allyl functionalized C60 derivatives. The resulting high-density C60-urethane-thiol-ene (C60-Thiol-Ene) networks possessed excellent mechanical properties. These novel networks were characterized using standard techniques, including infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and thermal gravimetric analysis (TGA). The dielectric spectra for the prepared samples were determined over a broad frequency range at room temperature using a broadband dielectric spectrometer and a semiconductor characterization system. The changes in thermo-mechanical and electrical properties of these novel fullerene-thiol-ene composite films were measured as a function of the C60 content, and samples characterized by high dielectric permittivity and low dielectric loss were produced. In this process, variations in chemical composition of the networks were correlated to performance characteristics.

  5. Attachment, ethology and adult psychotherapy.

    PubMed

    Sable, Pat

    2004-03-01

    This article discusses Bowlby's development of an ethological-evolutionary perspective, and its implications for psychotherapy with adults. According to Bowlby, attachment behavior is instinctive, having emerged throughout the course of evolution to ensure protection and actual survival. Because the environment affects how attachment behavior unfolds, adverse experiences can divert developmental pathways away from resilience, toward dysfunction and emotional distress. Psychotherapy offers the experience of an attachment relationship. Part of the process involves helping patients understand that feelings such as fear and anxiety are inherent responses to safeguard affectional relationships when they are endangered. As working models are re-appraised and revised, there is emphasis on clarifying the attachment experiences that may have intensified these natural feelings.

  6. Attachment at work and performance.

    PubMed

    Neustadt, Elizabeth A; Chamorro-Premuzic, Tomas; Furnham, Adrian

    2011-09-01

    This paper examines the relations between self-reported attachment orientation at work and personality, self-esteem, trait emotional intelligence (aka emotional self-efficacy), and independently assessed career potential and job performance. Self-report data were collected from 211 managers in an international business in the hospitality industry; independent assessments of these managers' job performance and career potential were separately obtained from the organization. A self-report measure of romantic attachment was adapted for application in the work context; a two-factor solution was found for this measure. Secure/autonomous attachment orientation at work was positively related to self-esteem, trait emotional intelligence, extraversion, agreeableness, and conscientiousness, and also to job performance. Not only was secure/autonomous attachment orientation at work statistically predictive of job performance, but the new measure also made a distinct contribution, beyond conscientiousness, to this prediction.

  7. Social attachments and traumatic stress

    PubMed Central

    Bryant, Richard A.

    2016-01-01

    The extent to which we engage with our social world has been central to our survival as a species and, accordingly, is relevant to how we cope with trauma and adversity. This review summarises current knowledge about the importance of social connections from an evolutionary perspective, as well as integrating this with a discussion of prevailing attachment theories. Experimental research supporting the potential benefit of attachments for managing adversity are presented, along with a review of how these benefits are moderated by individual differences in attachment style. The potential impact of trauma on attachment systems, and the manner in which this can compound trauma stress is discussed. Finally, a broader overview of social network analysis is introduced and it is proposed that a more sociocentric framework of trauma response would promote a fuller understanding of how social processes moderate trauma response. PMID:26996531

  8. Facilitating attachment after international adoption.

    PubMed

    Murphy, Natalie L

    2009-01-01

    Americans have increasingly turned to international adoption (IA) as an alternative way to build a family. Unfortunately, IA families are often being developed under conditions of loss, and sometimes these families struggle to form healthy attachments to each other. Disordered attachment (the failure to form a reciprocal, loving bond between parent and child) can occur, and can have devastating consequences. In some instances, IA children have been relinquished into state foster care systems; other families simply struggle for years caring for a developmentally delayed child who appears to have no emotion for his/her adoptive family. Nurses are likely to have contact with IA families and can use their education about attachment and bonding to help facilitate attachment in these developing families. Swanson's caring theory provides a clinically useful guide to meet this need.

  9. Adult attachment and declining birthrates.

    PubMed

    Draper, Thomas W; Holman, Thomas B; White, Whitney; Grandy, Shannon

    2007-02-01

    Attachment scores for 658 young adults living in the U.S.A. were obtained using the Experiences in Close Relationships scale. The participants came from a subsample of the RELATE data set, who had also filled out the adult attachment measure. Those young adults living in Utah County, Utah, an area of the country with a higher than normal birthrate (88% members of the Church of Jesus Christ of Latter-day Saints), also had higher than average adult attachment scores. While the methodology was not sufficient to assess causal direction nor eliminate the possibility of unidentified influences, an undiscussed psychological factor, adult attachment, may play a role in the numerical declines observed among nonimmigrant communities in the USA and Europe.

  10. Electron attachment to Cl 2

    NASA Astrophysics Data System (ADS)

    McCorkle, D. L.; Christodoulides, A. A.; Christophorou, L. G.

    1984-08-01

    The electron attachment rate constant for Cl 2 as a function of the mean electron energy (0.04-0.78 eV) and temperature (213-323 K) has been measured and is reported; it shows a maximum at near thermal energy and is attributed to dissociative electron attachment via the ground state 2Σ u+ of Cl 2- from the ground state 1Σ g+ of Cl 2.

  11. Magnetic adsorbent of Fe3O4@SiO2 core-shell nanoparticles modified with thiol group for chloroauric ion adsorption

    NASA Astrophysics Data System (ADS)

    Roto, Roto; Yusran, Yusran; Kuncaka, Agus

    2016-07-01

    The magnetic adsorbent of Fe3O4@SiO2 core-shell nanoparticles modified with thiol group was synthesized for chloroauric ([AuCl4]-) adsorption. The Fe3O4 nanoparticles were prepared by co-precipitation method under mechanical stirring and coated with SiO2 by acid hydrolysis of Na2SiO3 under N2 purging. The coating of Fe3O4 nanoparticles with SiO2 prevents particles' agglomeration by forming Fe3O4 Fe3O4 Fe3O4@SiO2 core-shell and avoids dissolution of the Fe3O4 core in the acidic medium. The coated Fe3O4 particle was modified with a thiol group using 3-mercaptopropyltrimethoxysilane via silanization reaction. The results suggest that SiO2-coated Fe3O4 particles have a size of 10-20 nm. The FTIR and EDX data indicate that the thiol groups are successfully attached to the surface of the nanoparticles. The [AuCl4]- ion adsorption by the Fe3O4@SiO2 core-shell nanoparticles followed Langmuir isotherm model with a maximum adsorption capacity of 115 mg/g and free energy (ΔG°) of 24.8 kJ/mol. The thiourea solution can be used to desorb most of the adsorbed [AuCl4]- ion. The adsorption using magnetic compounds provides easy access to the separation for both preparation and recovery.

  12. Synthesis of a novel poly-thiolated magnetic nano-platform for heavy metal adsorption. Role of thiol and carboxyl functions

    NASA Astrophysics Data System (ADS)

    Odio, Oscar F.; Lartundo-Rojas, Luis; Palacios, Elia Guadalupe; Martínez, Ricardo; Reguera, Edilso

    2016-11-01

    We report a novel strategy for the synthesis of magnetic nano-platforms containing free thiol groups. It first involves the synthesis of a poly(acrylic acid) copolymer containing disulfide bridges between the linear chains through di-ester linkages, followed by the anchoring of this new ligand to magnetite nanoparticles using a ligand exchange reaction. Finally, free sbnd SH groups are obtained by treating the resulting disulfide-functionalized magnetic nano-system with tributyl phosphine as reducing agent. The characterization of the resulting 17 nm nanoparticles (Fe3O4@PAA-HEDred) by FTIR and TGA confirms the attachment of the copolymer through iron carboxylates. XRD, TEM and magnetic measurements indicate an increase in the inorganic core diameter and the occurrence of strong magnetic inter-particle interactions during the exchange reaction, although coercitivity and remanence drop to near zero at room temperature. Afterwards, Fe3O4@PAA-HEDred nanoparticles were tested as sorbent for Pb2+ and Cd2+ cations in aqueous media. XPS measurements were performed in order to unravel the role of both carboxyl and thiol functions in the adsorption process. For the sake of comparison, the same study was performed using bare Fe3O4 nanoparticles and a nanosystem with disulfide groups (Fe3O4@DMSA). The joint analysis of the Pb 4f, Cd 3d, Fe 2p and S 2p high resolution spectra for the nanostructured materials indicates that metal-sulfur interactions are dominant if free sbnd SH groups are present, but if not, the main adsorption route entails metal-carboxyl interactions. Even in presence of unbound thiol moieties, carboxyl groups participate due to favoured steric availability.

  13. Atmospheric reactivity of alcohols, thiols and fluoroalcohols with chlorine atoms

    NASA Astrophysics Data System (ADS)

    Garzon Ruiz, Andres

    Alcohols, thiols and fluoroalcohols are volatile organic compounds (VOCs) which are emitted to the atmosphere from both natural (vegetation, oceans, volcanoes, etc.) and anthropogenic sources (fuels, solvents, wastewater, incinerators, refrigerants, etc.). These pollutants can be eliminated from the troposphere by deposition on the terrestrial surface, direct photolysis or reaction with different tropospheric oxidants. Reactions of VOCs with tropospheric oxidants are involved in the well-known atmospheric phenomenon of photochemical smog or the production of tropospheric ozone. The oxidation of these VOCs in the troposphere is mainly initiated by reaction with OH radicals during the daytime and with NO radicals at night. However, in recent years, the oxidation by chlorine atoms (Cl) has gained great importance in the study of atmospheric reactions because they may exert some influence in the boundary layer, particularly in marine and coastal environments. In general, Cl atoms are much more reactive species than OH and NO; radicals and therefore low concentrations of Cl may compete with OH and NO3 in hydrocarbon oxidation processes. The main source of tropospheric Cl atoms is believed to be the photolysis of chlorine-containing molecules generated by heterogeneous reactions of sea salt aerosols. It has also been proposed that Cl atoms, produced in the photolysis of Cl2 emitted from industrial processes, may enhance hydrocarbon oxidation rates and ozone production in urban environments. In this work, a kinetic, theoretical and mechanistic study of the reaction of several alcohols, thiols, and fluoroalcohols with Cl atoms has been carried out. Pulsed laser photolysis-fluorescence resonance (PLP-RF) technique was used for the kinetic study as a function of temperature and pressure. An environmental chamber-Fourier transform infrared (FTIR) system was also employed in the kinetic studies. Tropospheric lifetimes of these pollutants were estimated using obtained kinetic

  14. Mercury Binding Sites in Thiol-Functionalized Mesostructured Silica

    SciTech Connect

    Billinge, Simon J.L.; McKimmey, Emily J.; Shatnawi, Mouath; Kim, HyunJeong; Petkov, Valeri; Wermeille, Didier; Pinnavaia, Thomas J.

    2010-07-13

    Thiol-functionalized mesostructured silica with anhydrous compositions of (SiO{sub 2}){sub 1-x}(LSiO{sub 1.5}){sub x}, where L is a mercaptopropyl group and x is the fraction of functionalized framework silicon centers, are effective trapping agents for the removal of mercuric(II) ions from water. In the present work, we investigate the mercury-binding mechanism for representative thiol-functionalized mesostructures by atomic pair distribution function (PDF) analysis of synchrotron X-ray powder diffraction data and by Raman spectroscopy. The mesostructures with wormhole framework structures and compositions corresponding to x = 0.30 and 0.50 were prepared by direct assembly methods in the presence of a structure-directing amine porogen. PDF analyses of five mercury-loaded compositions with Hg/S ratios of 0.50-1.30 provided evidence for the bridging of thiolate sulfur atoms to two metal ion centers and the formation of chain structures on the pore surfaces. We find no evidence for Hg-O bonds and can rule out oxygen coordination of the mercury at greater than the 10% level. The relative intensities of the PDF peaks corresponding to Hg-S and Hg-Hg atomic pairs indicate that the mercury centers cluster on the functionalized surfaces by virtue of thiolate bridging, regardless of the overall mercury loading. However, the Raman results indicate that the complexation of mercury centers by thiolate depends on the mercury loading. At low mercury loadings (Hg/S {le} 0.5), the dominant species is an electrically neutral complex in which mercury most likely is tetrahedrally coordinated to bridging thiolate ligands, as in Hg(SBu{sup t}){sub 2}. At higher loadings (Hg/S 1.0-1.3), mercury complex cations predominate, as evidenced by the presence of charge-balancing anions (nitrate) on the surface. This cationic form of bound mercury is assigned a linear coordination to two bridging thiolate ligands.

  15. Preparation of reactive three-dimensional microstructures via direct laser writing and thiol-ene chemistry.

    PubMed

    Quick, Alexander S; Fischer, Joachim; Richter, Benjamin; Pauloehrl, Thomas; Trouillet, Vanessa; Wegener, Martin; Barner-Kowollik, Christopher

    2013-02-25

    Three-dimensional microstructures are fabricated employing the direct laser writing process and radical thiol-ene polymerization. The resin system consists of a two-photon photoinitiator and multifunctional thiols and olefins. Woodpile photonic crystals with 22 layers and a rod distance of 2 μm are fabricated. The structures are characterized via scanning electron microscopy and focused ion beam milling. The thiol-ene polymerization during fabrication is verified via infrared spectroscopy. The structures are grafted in a subsequent thiol-Michael addition reaction with different functional maleimides. The success of the grafting reaction is evaluated via laser scanning microscopy and X-ray photoelectron spectroscopy. The grafting density is calculated to be close to 200 molecules μm(-2) .

  16. Controlling Topological Entanglement in Engineered Protein Hydrogels with a Variety of Thiol Coupling Chemistries

    NASA Astrophysics Data System (ADS)

    Tang, Shengchang; Olsen, Bradley

    2014-05-01

    Topological entanglements between polymer chains are achieved in associating protein hydrogels through the synthesis of high molecular weight proteins via chain extension using a variety of thiol coupling chemistries, including disulfide formation, thiol-maleimide, thiol-bromomaleimide and thiol-ene. Coupling of cysteines via disulfide formation results in the most pronounced entanglement effect in hydrogels, while other chemistries provide versatile means of changing the extent of entanglement, achieving faster chain extension, and providing a facile method of controlling the network hierarchy and incorporating stimuli responsivities. The addition of trifunctional coupling agents causes incomplete crosslinking and introduces branching architecture to the protein molecules. The high-frequency plateau modulus and the entanglement plateau modulus can be tuned by changing the ratio of difunctional chain extender to the trifunctional branching unit. Therefore, these chain extension reactions show promise in delicately controlling the relaxation and mechanical properties of engineered protein hydrogels in ways that complement their design through genetic engineering.

  17. One- and two-electron oxidation of thiols: mechanisms, kinetics and biological fates.

    PubMed

    Trujillo, Madia; Alvarez, Beatriz; Radi, Rafael

    2016-01-01

    The oxidation of biothiols participates not only in the defense against oxidative damage but also in enzymatic catalytic mechanisms and signal transduction processes. Thiols are versatile reductants that react with oxidizing species by one- and two-electron mechanisms, leading to thiyl radicals and sulfenic acids, respectively. These intermediates, depending on the conditions, participate in further reactions that converge on different stable products. Through this review, we will describe the biologically relevant species that are able to perform these oxidations and we will analyze the mechanisms and kinetics of the one- and two-electron reactions. The processes undergone by typical low-molecular-weight thiols as well as the particularities of specific thiol proteins will be described, including the molecular determinants proposed to account for the extraordinary reactivities of peroxidatic thiols. Finally, the main fates of the thiyl radical and sulfenic acid intermediates will be summarized.

  18. Controlling topological entanglement in engineered protein hydrogels with a variety of thiol coupling chemistries

    PubMed Central

    Tang, Shengchang; Olsen, Bradley D.

    2014-01-01

    Topological entanglements between polymer chains are achieved in associating protein hydrogels through the synthesis of high molecular weight proteins via chain extension using a variety of thiol coupling chemistries, including disulfide formation, thiol-maleimide, thiol-bromomaleimide and thiol-ene. Coupling of cysteines via disulfide formation results in the most pronounced entanglement effect in hydrogels, while other chemistries provide versatile means of changing the extent of entanglement, achieving faster chain extension, and providing a facile method of controlling the network hierarchy and incorporating stimuli responsivities. The addition of trifunctional coupling agents causes incomplete crosslinking and introduces branching architecture to the protein molecules. The high-frequency plateau modulus and the entanglement plateau modulus can be tuned by changing the ratio of difunctional chain extender to the trifunctional branching unit. Therefore, these chain extension reactions show promise in delicately controlling the relaxation and mechanical properties of engineered protein hydrogels in ways that complement their design through genetic engineering. PMID:24860800

  19. Flavin-catalyzed aerobic oxidation of sulfides and thiols with formic acid/triethylamine.

    PubMed

    Murahashi, Shun-Ichi; Zhang, Dazhi; Iida, Hiroki; Miyawaki, Toshio; Uenaka, Masaaki; Murano, Kenji; Meguro, Kanji

    2014-09-14

    An efficient and practical catalytic method for the aerobic oxidative transformation of sulfides into sulfoxides, and thiols into disulfides with formic acid/TEA in the presence of a new, readily available, and stable flavin catalyst 5d is described.

  20. Novel pyrazoline-based fluorescent probe for detecting thiols and its application in cells.

    PubMed

    Zhang, Rong-Rong; Zhang, Jin-Feng; Wang, Sheng-Qing; Cheng, Yan-Long; Miao, Jun-Ying; Zhao, Bao-Xiang

    2015-02-25

    A new compound, N-(4-(1,5-diphenyl-4,5-dihydro-1H-pyrazol-3-yl)phenyl)-acrylamide (probe L), was designed and synthesized as a highly sensitive and selective fluorescent probe for recognizing and detecting thiol from other amino acids. On being mixed with thiol in buffered DMSO:HEPES=1:1 solution at pH 7.4, the probe exhibited the blue emission at 474 nm. This probe is very sensitive and displayed a linear fluorescence off-on response to thiol. The fluorescence emission of the probe is pH independent in the physiological pH range. Living cell imaging of HeLa cells confirmed its cell permeability and its ability to selectively detect thiol in cells. The structure of the probe was characterized by IR, NMR and HRMS spectroscopy analysis.

  1. Novel pyrazoline-based fluorescent probe for detecting thiols and its application in cells

    NASA Astrophysics Data System (ADS)

    Zhang, Rong-Rong; Zhang, Jin-Feng; Wang, Sheng-Qing; Cheng, Yan-Long; Miao, Jun-Ying; Zhao, Bao-Xiang

    2015-02-01

    A new compound, N-(4-(1,5-diphenyl-4,5-dihydro-1H-pyrazol-3-yl)phenyl)-acrylamide (probe L), was designed and synthesized as a highly sensitive and selective fluorescent probe for recognizing and detecting thiol from other amino acids. On being mixed with thiol in buffered DMSO:HEPES = 1:1 solution at pH 7.4, the probe exhibited the blue emission at 474 nm. This probe is very sensitive and displayed a linear fluorescence off-on response to thiol. The fluorescence emission of the probe is pH independent in the physiological pH range. Living cell imaging of HeLa cells confirmed its cell permeability and its ability to selectively detect thiol in cells. The structure of the probe was characterized by IR, NMR and HRMS spectroscopy analysis.

  2. Transition-metal-free acid-mediated synthesis of aryl sulfides from thiols and thioethers.

    PubMed

    Wagner, Anna M; Sanford, Melanie S

    2014-03-07

    The preparation of diaryl and alkyl aryl sulfides via acid-mediated coupling of thiols and thioethers with diaryliodonium salts is reported. The scope, limitations, and mechanism of the transformation are discussed.

  3. XAFS study on thiol etching of diphosphine-stabilized gold nanoclusters

    NASA Astrophysics Data System (ADS)

    Bao, Jie; Yang, Lina; Huang, Ting; Sun, Zhihu; Yao, Tao; Jiang, Yong; Wei, Shiqiang

    2017-08-01

    Thiol-etching triphenylphosphine (PPh3)-protected Au nanoclusters has been widely used to synthesize thiolated Au nanoclusters, while few studies have been reported on the thiol-etching reaction starting from diphosphine-protected Au clusters. Here the thiol-etching reaction in chloroform (CHCl3) for 1,5-Bis(diphenylphosphino) pentane (L5) protected Au11 nanoclusters is presented, and synchrotron radiation X-ray absorption fine structure, UV-vis absorption and mass spectra are combined to identify the reaction products. It is revealed that a gold(I)-thiolate complex Au2L5(RS) is produced, contrary to the case of thiol-etching PPh3-protected Au clusters where formation of thermodynamically stable Au25 or Au11 clusters is achieved.

  4. Mass Spectrometry in Studies of Protein Thiol Chemistry and Signaling: Opportunities and Caveats

    PubMed Central

    Devarie Baez, Nelmi O.; Reisz, Julie A.; Furdui, Cristina M.

    2014-01-01

    Mass spectrometry (MS) has become a powerful and widely utilized tool in the investigation of protein thiol chemistry, biochemistry, and biology. Very early biochemical studies of metabolic enzymes have brought to light the broad spectrum of reactivity profiles that distinguish cysteine thiols with functions in catalysis and protein stability from other cysteine residues in proteins. The development of MS methods for the analysis of proteins using electrospray ionization (ESI) or matrix-assisted laser desorption/ionization (MALDI) coupled with the emergence of high-resolution mass analyzers have been instrumental in advancing studies of thiol modifications, both in single proteins and within the cellular context. This article reviews MS instrumentation and methods of analysis employed in investigations of thiols and their reactivity toward a range of small biomolecules. A selected number of studies are detailed to highlight the advantages brought about by the MS technologies along with the caveats associated with these analyses. PMID:25261734

  5. Validation of the protective Ostertagia ostertagi ES-thiol antigens with different adjuvantia.

    PubMed

    Geldhof, P; Vercauteren, I; Vercruysse, J; Knox, D P; Van Den Broeck, W; Claerebout, E

    2004-01-01

    Intramuscular immunization of calves with an excretory-secretory antigen fraction enriched for cysteine proteinase activity (ES-thiol) and QuilA as adjuvant induces a protective immune response against the abomasal nematode Ostertagia ostertagi. The objectives of the present study were to confirm the protective capacity of ES-thiol in combination with QuilA, to test Al(OH)(3) as adjuvant for vaccination against O. ostertagi and to look for correlations between protection and immunological effector responses. Calves(seven animals/group) were vaccinated three times intramuscularly with 100 micro g antigen and/or adjuvant (ES-thiol with QuilA, ES-thiol with Al(OH)(3), QuilA alone and Al(OH)(3) alone) and subsequently challenged with a trickled oral infection of 25 000 infective larvae in total over 25 days. Faecal egg counts in the ES-thiol QuilA group were reduced by 56% during the two-month period of the trial compared to the QuilA control group (P < 0.002). Calves immunized with ES-thiol QuilA had significantly smaller adult worms (P < 0.002) and less eggs/female worm (P < 0.05) compared to the QuilA control group. No differences in egg output, worm counts or parameters of worm fitness were observed in the ES-thiol Al(OH)(3) group compared to the Al(OH)(3) control group. Although the protective immune mechanism against O. ostertagi remains unknown, protection in the ES-thiol QuilA group was associated with high levels of parasite-specific antibodies in the abomasal mucosa.

  6. Thiol-Based Redox Modulation of Soluble Guanylyl Cyclase, the Nitric Oxide Receptor

    PubMed Central

    2017-01-01

    Abstract Significance: Soluble guanylyl cyclase (sGC), which produces the second messenger cyclic guanosine 3′, 5′-monophosphate (cGMP), is at the crossroads of nitric oxide (NO) signaling: sGC catalytic activity is both stimulated by NO binding to the heme and inhibited by NO modification of its cysteine (Cys) thiols (S-nitrosation). Modulation of sGC activity by thiol oxidation makes sGC a therapeutic target for pathologies originating from oxidative or nitrosative stress. sGC has an unusually high percentage of Cys for a cytosolic protein, the majority solvent exposed and therefore accessible modulatory targets for biological and pathophysiological signaling. Recent Advances: Thiol oxidation of sGC contributes to the development of cardiovascular diseases by decreasing NO-dependent cGMP production and thereby vascular reactivity. This thiol-based resistance to NO (e.g., increase in peripheral resistance) is observed in hypertension and hyperaldosteronism. Critical Issues: Some roles of specific Cys thiols have been identified in vitro. So far, it has not been possible to pinpoint the roles of specific Cys of sGC in vivo and to investigate the molecular mechanisms in an animal model. Future Directions: The role of Cys as redox sensors, intermediates of activation, and mediators of change in sGC conformation, activity, and dimerization remains largely unexplored. To understand modulation of sGC activity, it is critical to investigate the roles of specific oxidative thiol modifications that are formed during these processes. Where the redox state of sGC thiols contribute to pathologies (vascular resistance and sGC desensitization by NO donors), it becomes crucial to design therapeutic strategies to restore sGC to its normal, physiological thiol redox state. Antioxid. Redox Signal. 26, 137–149. PMID:26906466

  7. The Interaction of thiol drugs and urine pH in the treatment of cystinuria.

    PubMed

    Asplin, Daniel M; Asplin, John R

    2013-06-01

    Pharmacological therapy for cystinuria consists of alkali salts to increase urine pH and thiol drugs to form soluble cysteine-drug complexes. The effect of alkalinizing urine on thiol drug activity has not been well studied. Urine samples were obtained from 5 healthy subjects and pH was adjusted (range 6.0 to 8.0) in each urine aliquot. Urine samples were incubated with cystine crystals at 37C for 5, 15 and 60 minutes, and 48 hours. We compared cystine solubility in urine samples spiked with thiol drugs at a final concentration of 2 mM to that in control urine samples at the various pH levels and time points. In samples incubated for 48 hours, which is the standard time frame for solubility studies, cystine solubility more than doubled with thiol drugs compared to control and did not depend on pH. However, when incubation time was shortened to 5 minutes, representing the dwell time of urine in the renal pelvis, the effect of thiol drugs to solubilize cystine greatly depended on urine pH with less cystine dissolved at lower pH. Increasing urine pH greatly increased the efficacy of thiol drugs to solubilize cystine in a clinically relevant time frame. These findings suggest that to maximize the benefit of thiol drugs alkali therapy should be used in conjunction with thiol drugs with the goal of keeping urine pH at 7.5 or above. Clinical trials are needed to confirm these in vitro findings. Copyright © 2013 American Urological Association Education and Research, Inc. Published by Elsevier Inc. All rights reserved.

  8. Thiol-Based Redox Modulation of Soluble Guanylyl Cyclase, the Nitric Oxide Receptor.

    PubMed

    Beuve, Annie

    2017-01-20

    Soluble guanylyl cyclase (sGC), which produces the second messenger cyclic guanosine 3', 5'-monophosphate (cGMP), is at the crossroads of nitric oxide (NO) signaling: sGC catalytic activity is both stimulated by NO binding to the heme and inhibited by NO modification of its cysteine (Cys) thiols (S-nitrosation). Modulation of sGC activity by thiol oxidation makes sGC a therapeutic target for pathologies originating from oxidative or nitrosative stress. sGC has an unusually high percentage of Cys for a cytosolic protein, the majority solvent exposed and therefore accessible modulatory targets for biological and pathophysiological signaling. Recent Advances: Thiol oxidation of sGC contributes to the development of cardiovascular diseases by decreasing NO-dependent cGMP production and thereby vascular reactivity. This thiol-based resistance to NO (e.g., increase in peripheral resistance) is observed in hypertension and hyperaldosteronism. Some roles of specific Cys thiols have been identified in vitro. So far, it has not been possible to pinpoint the roles of specific Cys of sGC in vivo and to investigate the molecular mechanisms in an animal model. The role of Cys as redox sensors, intermediates of activation, and mediators of change in sGC conformation, activity, and dimerization remains largely unexplored. To understand modulation of sGC activity, it is critical to investigate the roles of specific oxidative thiol modifications that are formed during these processes. Where the redox state of sGC thiols contribute to pathologies (vascular resistance and sGC desensitization by NO donors), it becomes crucial to design therapeutic strategies to restore sGC to its normal, physiological thiol redox state. Antioxid. Redox Signal. 26, 137-149.

  9. Kinetics of the reactions of hypochlorous acid and amino acid chloramines with thiols, methionine, and ascorbate.

    PubMed

    Peskin, A V; Winterbourn, C C

    2001-03-01

    Thiol oxidation by hypochlorous acid and chloramines is a favorable reaction and may be responsible for alterations in regulatory or signaling pathways in cells exposed to neutrophil oxidants. In order to establish the mechanism for such changes, it is necessary to appreciate whether these oxidants are selective for different thiols as compared with other scavengers. We have measured rate constants for reactions of amino acid chloramines with a range of thiols, methionine, and ascorbate, using a combination of stopped-flow and competitive kinetics. For HOCl, rate constants are too fast to measure directly by our system and values relative to reduced glutathione were determined by competition with methionine. For taurine chloramine, the rate constants for reaction with 5-thio-2-nitrobenzoic acid, GSH, methionine, and ascorbate at pH 7.4 were 970, 115, 39, and 13 M(-1) s(-1), respectively. Values for 10 thiols varied by a factor of 20 and showed an inverse relationship to the pK(a) of the thiol group. Rate constants for chloramines of glycine and N-alpha-acetyl-lysine also showed these relationships. Rates increased with decreasing pH, suggesting a mechanism involving acid catalysis. For hypochlorous acid, rates of reaction with 5-thio-2-nitrobenzoic acid, GSH, cysteine, and most of the other thiols were very similar. Relative reactivities varied by less than 5 and there was no dependence on thiol pK(a). Chloramines have the potential to be selective for different cellular thiols depending on their pK(a). For HOCl to be selective, other factors must be important, or its reactions could be secondary to chloramine formation.

  10. Oxidative stress and decreased thiol level in patients with migraine: cross-sectional study.

    PubMed

    Eren, Yasemin; Dirik, Ebru; Neşelioğlu, Salim; Erel, Özcan

    2015-12-01

    Although migraine is a neurological disorder known since long, its physiopathology remains unclear. Recent studies suggest that migraine is associated with oxidative stress; however, they report divergent results. The aim of the present study was to evaluate total antioxidant status (TAS), total oxidant status (TOS), oxidative stress index (OSI), and serum thiol level in migraine patients with or without aura. The study group consisted of 141 migraine patients. The control group included 70 healthy subjects. TAS, TOS, OSI were evaluated using a method developed by Erel. Serum thiol level was measured using the Hu method. No difference was found in TAS, TOS, OSI between the patients and controls. The level of thiol was significantly lower in patients than in controls. Negative correlations were detected between thiol level and Migraine Disability Assessment score in patients. Although TAS, TOS, and OSI were similar to those of the control group, serum thiol level, an important marker of antioxidant capacity, was significantly lower in migraines compared with controls, and caused more serious disability. Novel treatment approaches may be developed based on these data, and compounds containing thiol, such as alpha lipoic acid and N-acetyl cysteine, may be used in prophylaxis.

  11. Emollient, humectant, and fluorescent alpha,beta-unsaturated thiol esters for long-acting skin applications.

    PubMed

    Robinson, Carmen; Hartman, Rosemarie F; Rose, Seth D

    2008-12-01

    We describe compounds in which an emollient or a humectant bears an alpha,beta-unsaturated thiol ester capable of reacting with nucleophilic amino acids in stratum corneum proteins. These compounds should serve as long-lasting moisturizers for skin. The emollient derivatized was octadecyl propanoate, and the humectant was poly(ethylene glycol). These hydrophobic and hydrophilic compounds, as well as a fluorescent, dansyl-containing thiol ester, were found to react within minutes with the thiol N-acetylcysteamine upon addition of a catalytic amount of an organic base in chloroform. The structures of the products resulting from conjugate addition to the unsaturated thiol esters were determined by NMR spectroscopy. In the case of the alpha,beta,gamma,delta-unsaturated (sorboyl) thiol ester, both the 1,4-addition product and the beta,gamma-unsaturated-1,6-addition product formed, followed by diadduct. An in vivo test of the fluorescent alpha,beta-unsaturated thiol ester showed that this compound persisted on skin for 3 weeks vs. 6 days for the non-bonding control compound.

  12. Simple enrichment of thiol-containing biomolecules by using zinc(II)-cyclen-functionalized magnetic beads.

    PubMed

    Fujioka, Haruto; Tsunehiro, Masaya; Kawaguchi, Maho; Kuramoto, Yasuhiro; Kurosaki, Hiromasa; Hieda, Yuhzo; Kinoshita-Kikuta, Emiko; Kinoshita, Eiji; Koike, Tohru

    2014-07-01

    A simple and efficient method based on magnetic-bead technology has been developed for the enrichment of thiol-containing biomolecules, such as l-glutathione and cysteine-containing peptides. The thiol-binding site on the bead is a mononuclear complex of zinc(II) with 1,4,7,10-tetraazacyclododecane (cyclen); this is linked to a hydrophilic cross-linked agarose coating on a particle that has a magnetic core. All steps for the thiol-affinity separation are conducted in aqueous buffers with 0.10 mL of the magnetic beads in a 1.5 mL microtube. The entire separation protocol for thiol-containing compounds, from addition to elution, requires less than one hour per sample, provided the buffers and the zinc(II)-cyclen-functionalized magnetic beads have been prepared in advance. The thiol-affinity magnetic beads are reusable at least 15 times without a decrease in their thiol-binding ability, and they are stable for six months at room temperature.

  13. Yeast genes required for conversion of grape precursors to varietal thiols in wine.

    PubMed

    Santiago, Margarita; Gardner, Richard C

    2015-08-01

    Three varietal thiols are important for the tropical fruit aromas of Sauvignon blanc: 4-mercapto-4-methylpentan-2-one (4MMP), 3-mercaptohexanol (3MH) and its acetylated derivative 3-mercaptohexyl acetate (3MHA). These thiols are produced by yeast during fermentation from precursors in grape juice. Here we identify genes in Saccharomyces cerevisiae that are required for the transport and cleavage of two thiol precursors: cysteine-4MMP and glutathione-3MH. A full-length copy of IRC7 is absolutely required for the cleavage of both precursors in the tested strains; the deleted form of the enzyme found in most yeast strains is incapable of converting these compounds into detectable thiols. By using strains that overexpress full-length IRC7, we further show that the glutathione transporter OPT1 and the transpeptidase CIS2 are also required for conversion of glut-3MH to its varietal thiol. No transporter for cys-4MMP was identified: a strain deleted for all nine known cysteine transport genes was still capable of converting cys-4MMP to its varietal thiol, and was also able to take up cysteine at high concentrations. Based on these results, we conclude that cysteine and glutathione precursors make a relatively minor contribution to 3MH production from most grape juices. © FEMS 2015. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  14. Facile functionalization of PDMS elastomer surfaces using thiol-ene click chemistry.

    PubMed

    Zhang, Jianfeng; Chen, Yang; Brook, Michael A

    2013-10-08

    A variety of methods have been developed for polydimethylsiloxane (PDMS) elastomer surface functionalization, particularly for the improvement of hydrophilicity. However, in addition to difficulties in avoiding undesired physical changes to the modified surface, including surface cracking, "hydrophobic recovery" frequently leads hydrophilically modified surfaces to completely return over time to their hydrophobic nature, with accompanying loss of accessible functional groups. Thiol-ene chemistry provides a mild and robust technology for synthetic elaboration. We demonstrate the introduction of thiol groups onto the PDMS surface via base-catalyzed equilibration of MTS ((MeO)3Si(CH2)3SH). Thiols in the product elastomer were shown to be located primarily at the air interface using EDX, XPS, and fluorescence labeling initially, and after extended periods of time: total thiol concentrations at the surface and in the bulk were established by complementary chemical titrations with DTDP (4,4'-dithiodipyridine) and iodine titrations in different solvents. The surface density of thiols was readily controlled by reaction conditions: the rate of hydrophobic recovery, which led to incomplete loss of accessible functional groups, was determined. Thiol-ene click chemistry was then used to introduce a variety of hydrophilic moieties onto the surface including a silicone surfactant and maleic anhydride, respectively. In the latter case, molecular functionalization with both small (fluorescent labels) and polymeric nucleophiles (poly(ethylene glycol), chitosan) could be subsequently induced by simple ring-opening nucleophilic attack leading to permanently functional surfaces.

  15. Thiol/disulphide homeostasis in Bell's palsy as a novel pathogenetic marker.

    PubMed

    Babademez, M A; Gul, F; Kale, H; Muderris, T; Bayazit, Y; Ergin, M; Erel, O; Kiris, M

    2017-04-01

    The aim of this study was to investigate the relationship between Bell's palsy and a novel oxidative stress parameter, thiol/disulphide homeostasis. A prospective study evaluating oxidative stress in Bell's palsy. This research took place in the department of Otorhinolaryngology, Ataturk Training and Research Hospital. Totally, 77 patients with Bell's palsy and 38 healthy controls were included in this study. The blood levels of total and native thiol and disulphide activity were assessed, and their levels were compared in the patients and controls. There were statistically significant differences between the patients and controls regarding thiol/disulphide parameters. The mean native thiol and total thiol were significantly lower and disulphide levels were higher in the Bell's palsy than controls. On binary logistic regression analysis, the created model showed 45.3% variation. The cut-off value was 18.95 for disulphides. Native and total thiol levels were low in the Bell's palsy. This metabolic disturbance may have a role in the pathogenesis of Bell's palsy. © 2016 John Wiley & Sons Ltd.

  16. Direct observation of pentacene-thiol interaction using x-ray spectroscopy

    NASA Astrophysics Data System (ADS)

    Jia, Zhang; Lee, Vincent; Floreano, Luca; Verdini, Alberto; Cossaro, Albano; Morgante, Alberto; Kymissis, Ioannis

    2010-03-01

    There has been an intense interest in the surface modification of the source-drain electrodes for organic field effect transistors (OFETs) to improve their performance. A number of thiol based self assembled monolayers demonstrated improvements to the contact resistance and channel performance. Morphological improvements at the contacts, a change in the effective work function, and charge transfer between the thiols and the semiconductor have all been credited with the observed performance improvements. Using in-situ semiconductor deposition together with x-ray photoelectron spectroscopy and near-edge x-ray absorption fine structure, we are able to directly probe two technologically relevant OFET stacks. This work directly measures the interaction between pentacene and two thiols which have been associated to contact improvement: an electroneutral thiol (1-hexadecanethiol) and an electronegative thiol (pentafluorobenzenethiol). Based on our results we observe no chemical interaction between pentacene and the thiol. The electrical improvements to transistor performance, based on these systems, can be attributed to work function shifts of the contacts and morphological improvements of the organic semiconductor.

  17. Serum thiols as a biomarker of disease activity in lupus nephritis.

    PubMed

    Lalwani, Pritesh; de Souza, Giselle Katiane Bonfim Bacelar; de Lima, Domingos Savio Nunes; Passos, Luiz Fernando Souza; Boechat, Antonio Luiz; Lima, Emerson Silva

    2015-01-01

    Lupus Nephritis (LN) develops in more than half of the Systemic Lupus Erythematous (SLE) patients. However, lack of reliable, specific biomarkers for LN hampers clinical management of patients and impedes development of new therapeutics. The goal of this study was to investigate whether oxidative stress biomarkers in patients with SLE is predictive of renal pathology. Serum biochemical and oxidative stress markers were measured in patients with inactive lupus, active lupus with and without nephritis and compared to healthy control group. To assess the predictive performance of biomarkers, Receiver Operating Characteristic (ROC) curves were constructed and cut-offs were used to identify SLE patients with nephritis. We observed an increased oxidative stress response in all SLE patients compared to healthy controls. Among the several biomarkers tested, serum thiols had a significant inverse association with SLE Disease Activity Index (SLEDAI). Interestingly, thiols were able too aptly differentiate between SLE patients with and without renal pathology, and serum thiol levels were not affected by immunosuppressive drug therapy. The decreased thiols in SLE correlated significantly with serum creatinine and serum C3 levels. Further retrospective evaluation using serum creatinine or C3 levels in combination with thiol's cutoff values from ROC analysis, we could positively predict chronicity of renal pathology in SLE patients. In summary, serum thiols emerge as an inexpensive and reliable indicator of LN, which may not only help in early identification of renal pathology but also aid in the therapeutic management of the disease, in developing countries with resource poor settings.

  18. Integration of the thiol redox status with cytokine response to physical training in professional basketball players.

    PubMed

    Zembron-Lacny, A; Slowinska-Lisowska, M; Ziemba, A

    2010-01-01

    The present study was designed to evaluate the plasma markers of reactive oxygen species (ROS) activity and cytokines, and their relationship with thiol redox status of basketball players during training. Sixteen professional players of the Polish Basketball Extraleague participated in the study. The study was performed during the preparatory period and the play-off round. Markers of ROS activity (lipid peroxidation TBARS, protein carbonylation PC) and reduced glutathione (GSH) demonstrated regularity over time, i.e. TBARS, PC and GSH were elevated at the beginning and decreased at the end of training periods. Oxidized glutathione (GSSG) was not affected by exercise training. Thiol redox status (GSH(total)-2GSSG/GSSG) correlated with TBARS and PC in both training periods. The level of interleukin-6 (IL-6) was increased and positively correlated with thiol redox (r=0.423) in the preparatory period, whereas tumor necrosis factor alpha (TNFalpha) was increased and inversely correlated with thiol redox (r= 0.509) in the play-off round. The present study showed significant shifts in markers of ROS activity, thiol redox status and inflammatory mediators (IL-6, TNFalpha) following professional sport training as well as correlation between changes in thiol redox and cytokine response.

  19. Chemical introduction of reactive thiols into a viral nanoscaffold: a method that avoids virus aggregation.

    PubMed

    Steinmetz, Nicole F; Evans, David J; Lomonossoff, George P

    2007-07-09

    The use of viral nanoparticles (VNPs) as building blocks for material fabrication has received particular attention in recent years. In earlier studies we showed the applicability of native gel electrophoresis in an agarose matrix as a useful method for the characterization of chemically modified VNPs. Here, we extend these studies and analyze the observed band pattern of intact Cowpea mosaic virus (CPMV) VNPs in agarose gels and show the applicability of native agarose gels for monitoring interparticle linkage of thiol-containing CPMV mutant particles. In addition, we report a protocol that allows the introduction of acetate-protected thiols to CPMV by means of a chemical reaction (rather than genetic modification). The advantage of this approach is that, by incorporating protected thiol groups, the formation of disulfide bonds leading to interparticle linkage is prevented. The resulting thiol-modified CPMV-SH(n) particles are stable, and following deprotection, the introduced thiols are reactive and can be labeled with thiol-selective reagents. They therefore provide a useful additional building block in the CPMV toolbox.

  20. Purification, Characterization, and Effect of Thiol Compounds on Activity of the Erwinia carotovora L-Asparaginase

    PubMed Central

    Warangkar, Suchita C.; Khobragade, Chandrahas N.

    2010-01-01

    L-asparaginase was extracted from Erwinia carotovora and purified by ammonium sulfate fractionation (60–70%), Sephadex G-100, CM cellulose, and DEAE sephadex chromatography. The apparent Mr of enzyme under nondenaturing and denaturing conditions was 150 kDa and 37 ± 0.5 kDa, respectively. L-asparaginase activity was studied in presence of thiols, namely, L-cystine (Cys), L-methionine (Met), N-acetyl cysteine (NAC), and reduced glutathione (GSH). Kinetic parameters in presence of thiols (10–400 μM) showed an increase in Vmax values (2000, 2223, 2380, 2500, and control 1666.7 μmoles mg−1min−1) and a decrease in Km values (0.086, 0.076, 0.062, 0.055 and control 0.098 mM) indicating nonessential mode of activation. KA values displayed propensity to bind thiols. A decrease in Vmax/Km ratio in concentration plots showed inverse relationship between free thiol groups (NAC and GSH) and bound thiol group (Cys and Met). Enzyme activity was enhanced in presence of thiol protecting reagents like dithiothreitol (DTT), 2-mercaptoethanol (2-ME), and GSH, but inhibited by p-chloromercurybenzoate (PCMB) and iodoacetamide (IA). PMID:21048860

  1. Tunable thiol-epoxy shape memory polymer foams

    NASA Astrophysics Data System (ADS)

    Ellson, Gregory; Di Prima, Matthew; Ware, Taylor; Tang, Xiling; Voit, Walter

    2015-05-01

    Shape memory polymers (SMPs) are uniquely suited to a number of applications due to their shape storage and recovery abilities and the wide range of available chemistries. However, many of the desired performance properties are tied to the polymer chemistry which can make optimization difficult. The use of foaming techniques is one way to tune mechanical response of an SMP without changing the polymer chemistry. In this work, a novel thiol-epoxy SMP was foamed using glass microspheres (40 and 50% by volume Q-Cel 6019), using expandable polymer microspheres (1% 930 DU 120), and by a chemical blowing agent (1% XOP-341). Each approach created SMP foam with a differing density and microstructure from the others. Thermal and thermomechanical analysis was performed to observe the behavioral difference between the foaming techniques and to confirm that the glass transition (Tg) was relatively unchanged near 50 °C while the glassy modulus varied from 19.1 to 345 MPa and the rubbery modulus varied from 0.04 to 2.2 MPa. The compressive behavior of the foams was characterized through static compression testing at different temperatures, and cyclic compression testing at Tg. Constrained shape recovery testing showed a range of peak recovery stress from 5 MPa for the syntactic Q-Cel foams to ˜0.1 MPa for the chemically blown XOP-341 foam. These results showed that multiple foaming approaches can be used with a novel SMP to vary the mechanical response independent of Tg and polymer chemistry.

  2. Automated computational screening of the thiol reactivity of substituted alkenes

    NASA Astrophysics Data System (ADS)

    Smith, Jennifer M.; Rowley, Christopher N.

    2015-08-01

    Electrophilic olefins can react with the S-H moiety of cysteine side chains. The formation of a covalent adduct through this mechanism can result in the inhibition of an enzyme. The reactivity of an olefin towards cysteine depends on its functional groups. In this study, 325 reactions of thiol-Michael-type additions to olefins were modeled using density functional theory. All combinations of ethenes with hydrogen, methyl ester, amide, and cyano substituents were included. An automated workflow was developed to perform the construction, conformation search, minimization, and calculation of molecular properties for the reactant, carbanion intermediate, and thioether products for a model reaction of the addition of methanethiol to the electrophile. Known cysteine-reactive electrophiles present in the database were predicted to react exergonically with methanethiol through a carbanion with a stability in the 30-40 kcal mol-1 range. 13 other compounds in our database that are also present in the PubChem database have similar properties. Natural bond orbital parameters were computed and regression analysis was used to determine the relationship between properties of the olefin electronic structure and the product and intermediate stability. The stability of the intermediates is very sensitive to electronic effects on the carbon where the anionic charge is centered. The stability of the products is more sensitive to steric factors.

  3. Thiol passivation of MWIR type II superlattice photodetectors

    NASA Astrophysics Data System (ADS)

    Salihoglu, O.; Muti, A.; Aydinli, A.

    2013-06-01

    Poor passivation on photodetectors can result in catastrophic failure of the device. Abrupt termination of mesa side walls during pixel definition generates dangling bonds that lead to inversion layers and surface traps leading to surface leakage currents that short circuit diode action. Good passivation, therefore, is critical in the fabrication of high performance devices. Silicondioxide has been the main stay of passivation for commercial photodetectors, deposited at high temperatures and high RF powers using plasma deposition techniques. In photodetectors based on III-V compounds, sulphur passivation has been shown to replace oxygen and saturate the dangling bonds. Despite its effectiveness, it degrades over time. More effort is required to create passivation layers which eliminate surface leakage current. In this work, we propose the use of sulphur based octadecanethiol (ODT), CH3(CH2)17SH, as a passivation layer for the InAs/GaSb superlattice photodetectors that acts as a self assembled monolayer (SAM). ODT SAMs consist of a chain of 18 carbon atoms with a sulphur atom at its head. ODT Thiol coating is a simple process that consist of dipping the sample into the solution for a prescribed time. Excellent electrical performance of diodes tested confirm the effectiveness of the sulphur head stabilized by the intermolecular interaction due to van der Walls forces between the long chains of ODT SAM which results in highly stable ultrathin hydrocarbon layers without long term degradation.

  4. Thiol-linked alkylation of RNA to assess expression dynamics.

    PubMed

    Herzog, Veronika A; Reichholf, Brian; Neumann, Tobias; Rescheneder, Philipp; Bhat, Pooja; Burkard, Thomas R; Wlotzka, Wiebke; von Haeseler, Arndt; Zuber, Johannes; Ameres, Stefan L

    2017-09-25

    Gene expression profiling by high-throughput sequencing reveals qualitative and quantitative changes in RNA species at steady state but obscures the intracellular dynamics of RNA transcription, processing and decay. We developed thiol(SH)-linked alkylation for the metabolic sequencing of RNA (SLAM seq), an orthogonal-chemistry-based RNA sequencing technology that detects 4-thiouridine (s(4)U) incorporation in RNA species at single-nucleotide resolution. In combination with well-established metabolic RNA labeling protocols and coupled to standard, low-input, high-throughput RNA sequencing methods, SLAM seq enabled rapid access to RNA-polymerase-II-dependent gene expression dynamics in the context of total RNA. We validated the method in mouse embryonic stem cells by showing that the RNA-polymerase-II-dependent transcriptional output scaled with Oct4/Sox2/Nanog-defined enhancer activity, and we provide quantitative and mechanistic evidence for transcript-specific RNA turnover mediated by post-transcriptional gene regulatory pathways initiated by microRNAs and N(6)-methyladenosine. SLAM seq facilitates the dissection of fundamental mechanisms that control gene expression in an accessible, cost-effective and scalable manner.

  5. Processing and targeting of the thiol protease, aleurain

    SciTech Connect

    Rogers, J.C.

    1989-01-01

    We have identified a cDNA clone from barley aleurone mRNA that encodes a protein with unusual homologies: the C-terminal portion, about 270 amino acids, is 65% identical to the mammalian thiol protease, cathepsin H. This degree of sequence conservation indicates that the enzyme must have some specific function in both plants and mammals that cannot tolerate further divergence. The N-terminal 1/3 of the protein, about 140 amino acids, has no detectable homologies to other known protein sequences; its function is unknown. In aleurone tissue, the mRNA level is increased by gibberellic acid and decreased by abscisic acid, but is expressed apparently constitutively at high levels in leaf and root tissues. The amino acid sequence and cathepsin H homology suggest that the protein will be both secreted into the endoplasmic reticulum and glycosylated. Using our cDNA clone in a bacterial expression system, we have made a fusion protein containing the protease domain of aleurain, and have used it to raise specific antisera in rabbits. These antibodies identify a 32 kd protein in extracts of aleurone layers that is induced with GA treatment but not secreted; a similarly sized protein is specifically identified in extracts of leaf tissue. Experiments are underway to characterize the pattern of expression in different tissues, to identify the subcellular locations of the protein, to characterize processing of the precursor to the 32 kd mature form, and to purify the enzyme from barley. 2 figs.

  6. Processing and targeting of the thiol protease aleurain: Progress report

    SciTech Connect

    Rogers, J.C.

    1988-01-01

    This study addresses the processing and targeting of the thiol protease aleurain in monocots. A probe derived from the aleurain cDNA specific for the 5'-most 400 bp (a region encoding the first 140 amino acids of the preprotein hybridized to at least 3 separate elements in the barley genome; only one represented the aleurain gene. In contrast, a probe specific for the remaining 2/23 of the cDNA (representing the protease domain) hybridized to only a single copy sequence. To know if this pattern pertained in other, closely related, monocots, we probed Southern blots of genomic DNA from maize, rye, oats, sorghum, and pearl millet with each probe. In each instance except for maize DNA, the 5' domain probe hybridizes to several fragments in addition to those identified by the protease domain probe. Presumable the darkest hybridization in each represents the fragment carrying the sequences homologous to barley aleurain. The fragments from a given restriction enzyme identified by the protease domain probe in sorghum, millet, and maize, were indistinguishable in size indicating that the gene sequences, as well as flanking DNA, are so well conserved among the group that the location of the hexanucleotide sequences have not diverged. (3 refs., 3 figs.)

  7. Modular Degradable Hydrogels Based on Thiol-Reactive Oxanorbornadiene Linkers

    PubMed Central

    2016-01-01

    Oxanorbornadiene dicarboxylate (OND) reagents are potent Michael acceptors, the adducts of which undergo fragmentation by retro-Diels–Alder reaction at rates that vary with the substitution pattern on the OND moiety. Rapid conjugate addition between thiol-terminated tetravalent PEG and multivalent ONDs yielded self-supporting hydrogels within 1 min at physiological temperature and pH. Erosion of representative hydrogel formulations occurred with predictable and pH-independent rates on the order of minutes to weeks. These materials could be made non-degradable by epoxidation of the OND linkers without slowing gelation. Hydrogels prepared with OND linkers of equal valence had comparable physical properties, as determined by equilibrium swelling behavior, indicating similar internal network structure. Diffusion and release of entrained cargo varied with both the rate of degradation of PEG-OND hydrogels and the hydrodynamic radius of the entrained species. These results highlight the utility of OND linkers in the preparation of degradable network materials with potential applications in sustained release. PMID:25871459

  8. Subinhibitory bismuth-thiols reduce virulence of Pseudomonas aeruginosa.

    PubMed

    Wu, Chieh-Liang; Domenico, Philip; Hassett, Daniel J; Beveridge, Terry J; Hauser, Alan R; Kazzaz, Jeffrey A

    2002-06-01

    Pseudomonas aeruginosa is a common pathogen in mechanically ventilated patients and produces a wide array of virulence factors. Bismuth-thiols (BTs) are active in vitro against all bacterial lung pathogens, including P. aeruginosa. The objective of these studies was to examine the biochemical and morphologic effects of sublethal BT concentrations on P. aeruginosa and to evaluate virulence in cell culture. Bismuth-dimercaprol, at a fraction of the minimal inhibitory concentration, reduced alginate expression by 67% in P. aeruginosa, whereas subinhibitory bismuth-ethanedithiol (BisEDT) reduced alginate by 92% in P. syringae. BisEDT effects on lipopolysaccharide content and type III secreted cytoxins were examined by sodium dodecyl sulfate polyacrylamide gel electrophoresis. Subinhibitory BisEDT reduced cell-associated lipopolysaccharide, and inhibited processing of the secreted cytotoxic protein ExoU. BisEDT-induced outer membrane blebbing and aggregation of cytoplasmic material was noted in electron microscopy. Virulence of P. aeruginosa was assessed by adherence to epithelial cells and sensitivity to serum killing. BisEDT inhibited adherence of P. aeruginosa to 16HBE14o- cells by 28% and to a collagen matrix by 53%. BisEDT-treated bacteria were also 100-fold more sensitive to serum bactericidal activity. In summary, low BT concentrations affect P. aeruginosa in a variety of ways, the combination of which may help prevent or resolve respiratory tract infection.

  9. Unusual thiol-based redox metabolism of parasitic flukes.

    PubMed

    Tripathi, Timir; Suttiprapa, Sutas; Sripa, Banchob

    2016-05-27

    Parasitic flukes are exposed to free radicals and, to a greater extent, reactive oxygen species (ROS) during their life cycle. Despite being relentlessly exposed to ROS released by activated immune cells, these parasites can survive for many years in the host. Cellular thiol-based redox metabolism plays a crucial role in parasite survival within their hosts. Evidence shows that oxidative stress and redox homeostasis maintenance are important clinical and pathobiochemical as well as effective therapeutic principles in various diseases. The characterization of redox and antioxidant enzymes is likely to yield good target candidates for novel drugs and vaccines. The absence of active catalase in fluke parasites offers great potential for the development of chemotherapeutic agents that act by perturbing the redox equilibrium of the cell. One of the redox-sensitive enzymes, thioredoxin glutathione reductase (TGR), has been accepted as a drug target against blood fluke infections, and related clinical trials are in progress. TGR is the sole enzyme responsible for Trx and GSH reduction in parasitic flukes. The availability of helminth genomes has accelerated the research on redox metabolism of flukes; however, significant achievements have yet to be attained. The present review summarizes current knowledge on the redox and antioxidant system of the parasitic flukes.

  10. Automated computational screening of the thiol reactivity of substituted alkenes.

    PubMed

    Smith, Jennifer M; Rowley, Christopher N

    2015-08-01

    Electrophilic olefins can react with the S-H moiety of cysteine side chains. The formation of a covalent adduct through this mechanism can result in the inhibition of an enzyme. The reactivity of an olefin towards cysteine depends on its functional groups. In this study, 325 reactions of thiol-Michael-type additions to olefins were modeled using density functional theory. All combinations of ethenes with hydrogen, methyl ester, amide, and cyano substituents were included. An automated workflow was developed to perform the construction, conformation search, minimization, and calculation of molecular properties for the reactant, carbanion intermediate, and thioether products for a model reaction of the addition of methanethiol to the electrophile. Known cysteine-reactive electrophiles present in the database were predicted to react exergonically with methanethiol through a carbanion with a stability in the 30-40 kcal mol(-1) range. 13 other compounds in our database that are also present in the PubChem database have similar properties. Natural bond orbital parameters were computed and regression analysis was used to determine the relationship between properties of the olefin electronic structure and the product and intermediate stability. The stability of the intermediates is very sensitive to electronic effects on the carbon where the anionic charge is centered. The stability of the products is more sensitive to steric factors.

  11. Revisiting the reactions of superoxide with glutathione and other thiols.

    PubMed

    Winterbourn, Christine C

    2016-04-01

    The reaction between GSH and superoxide has long been of interest in the free radical biology. Early studies were confusing, as some reports suggested that the reaction could be a major pathway for superoxide removal whereas others questioned whether it happened at all. Further research by several investigators, including Helmut Sies, was required to clarify this complex reaction. We now know that superoxide does react with GSH, but the reaction is relatively slow and occurs mostly by a chain reaction that consumes oxygen and regenerates superoxide. Most of the GSH is converted to GSSG, with a small amount of sulfonic acid. As shown by Sies and colleagues, singlet oxygen is a by-product. Although removal of superoxide by GSH may be a minor pathway, GSH and superoxide have a strong physiological connection. GSH is an efficient free radical scavenger, and when it does so, thiyl radicals are generated. These further react to generate superoxide. Therefore, radical scavenging by GSH and other thiols is a source of superoxide and hydrogen peroxide, and to be an antioxidant pathway, there must be efficient removal of these species.

  12. Low molecular weight thiols in arsenic hyperaccumulator Pteris vittata upon exposure to arsenic and other trace elements.

    PubMed

    Cai, Yong; Su, Jinhui; Ma, Lena Q

    2004-05-01

    Low molecular weight thiol-containing compounds have been reported to play an important role in metal detoxification and accumulation in some higher plants. The formation of these low molecular weight thiols in the recently discovered arsenic hyperaccumulator, Chinese Brake fern (Pteris vittata) upon exposure to arsenic and other trace metals was investigated. In addition to cysteine and glutathione, an unidentified thiol was observed in the plants exposed to arsenic, which was not found in the control. The concentration of the unidentified thiol showed a very strong and positive correlation with arsenic concentration in the leaflets. The unidentified thiol was low in rachises and undetectable in the roots for As-treated plants. Total and acid-soluble thiols were also measured and the results indicated that arsenic mainly stimulated the synthesis of acid-soluble thiol in Chinese Brake. The investigations of other trace elements (Cd, Cu, Cr, Zn, Pb, Hg, and Se) showed that these elements were not accumulated in Chinese Brake to high levels and the synthesis of the unidentified thiol in the plant was not observed. Our study suggests that the unidentified thiol was induced specifically by arsenic and the distribution patterns of the unidentified thiol and arsenic in the plant were consistent, indicating that the synthesis of this compound was related to As exposure.

  13. Thiol-redox antioxidants protect against lung vascular endothelial cytoskeletal alterations caused by pulmonary fibrosis inducer, bleomycin: comparison between classical thiol-protectant, N-acetyl-L-cysteine, and novel thiol antioxidant, N,N'-bis-2-mercaptoethyl isophthalamide.

    PubMed

    Patel, Rishi B; Kotha, Sainath R; Sauers, Lynn A; Malireddy, Smitha; Gurney, Travis O; Gupta, Niladri N; Elton, Terry S; Magalang, Ulysses J; Marsh, Clay B; Haley, Boyd E; Parinandi, Narasimham L

    2012-06-01

    Lung vascular alterations and pulmonary hypertension associated with oxidative stress have been reported to be involved in idiopathic lung fibrosis (ILF). Therefore, here, we hypothesize that the widely used lung fibrosis inducer, bleomycin, would cause cytoskeletal rearrangement through thiol-redox alterations in the cultured lung vascular endothelial cell (EC) monolayers. We exposed the monolayers of primary bovine pulmonary artery ECs to bleomycin (10 µg) and studied the cytotoxicity, cytoskeletal rearrangements, and the macromolecule (fluorescein isothiocyanate-dextran, 70,000 mol. wt.) paracellular transport in the absence and presence of two thiol-redox protectants, the classic water-soluble N-acetyl-L-cysteine (NAC) and the novel hydrophobic N,N'-bis-2-mercaptoethyl isophthalamide (NBMI). Our results revealed that bleomycin induced cytotoxicity (lactate dehydrogenase leak), morphological alterations (rounding of cells and filipodia formation), and cytoskeletal rearrangement (actin stress fiber formation and alterations of tight junction proteins, ZO-1 and occludin) in a dose-dependent fashion. Furthermore, our study demonstrated the formation of reactive oxygen species, loss of thiols (glutathione, GSH), EC barrier dysfunction (decrease of transendothelial electrical resistance), and enhanced paracellular transport (leak) of macromolecules. The observed bleomycin-induced EC alterations were attenuated by both NAC and NBMI, revealing that the novel hydrophobic thiol-protectant, NBMI, was more effective at µM concentrations as compared to the water-soluble NAC that was effective at mM concentrations in offering protection against the bleomycin-induced EC alterations. Overall, the results of the current study suggested the central role of thiol-redox in vascular EC dysfunction associated with ILF.

  14. Thiol-redox antioxidants protect against lung vascular endothelial cytoskeletal alterations caused by pulmonary fibrosis inducer, bleomycin: comparison between classical thiol-protectant, N-acetyl-l-cysteine, and novel thiol antioxidant, N,N′-bis-2-mercaptoethyl isophthalamide

    PubMed Central

    Patel, Rishi B.; Kotha, Sainath R.; Sauers, Lynn A.; Malireddy, Smitha; Gurney, Travis O.; Gupta, Niladri N.; Elton, Terry S.; Magalang, Ulysses J.; Marsh, Clay B.; Haley, Boyd E.; Parinandi, Narasimham L.

    2012-01-01

    Lung vascular alterations and pulmonary hypertension associated with oxidative stress have been reported to be involved in idiopathic lung fibrosis (ILF). Therefore, here, we hypothesize that the widely used lung fibrosis inducer, bleomycin, would cause cytoskeletal rearrangement through thiol-redox alterations in the cultured lung vascular endothelial cell (EC) monolayers. We exposed the monolayers of primary bovine pulmonary artery ECs to bleomycin (10 µg) and studied the cytotoxicity, cytoskeletal rearrangements, and the macromolecule (fluorescein isothiocyanate-dextran, 70,000 mol. wt.) paracellular transport in the absence and presence of two thiol-redox protectants, the classic water-soluble N-acetyl-l-cysteine (NAC) and the novel hydrophobic N,N′-bis-2-mercaptoethyl isophthalamide (NBMI). Our results revealed that bleomycin induced cytotoxicity (lactate dehydrogenase leak), morphological alterations (rounding of cells and filipodia formation), and cytoskeletal rearrangement (actin stress fiber formation and alterations of tight junction proteins, ZO-1 and occludin) in a dose-dependent fashion. Furthermore, our study demonstrated the formation of reactive oxygen species, loss of thiols (glutathione, GSH), EC barrier dysfunction (decrease of transendothelial electrical resistance), and enhanced paracellular transport (leak) of macromolecules. The observed bleomycin-induced EC alterations were attenuated by both NAC and NBMI, revealing that the novel hydrophobic thiol-protectant, NBMI, was more effective at µM concentrations as compared to the water-soluble NAC that was effective at mM concentrations in offering protection against the bleomycin-induced EC alterations. Overall, the results of the current study suggested the central role of thiol-redox in vascular EC dysfunction associated with ILF. PMID:22409285

  15. Activating Attachments Reduces Memories of Traumatic Images

    PubMed Central

    Foord, Rachael

    2016-01-01

    Emotional memories, and especially intrusive memories, are a common feature of many psychological disorders, and are overconsolidated by stress. Attachment theory posits that activation of mental representations of attachment figures can reduce stress and boost coping. This study tested the proposition that attachment activation would reduce consolidation of emotional and intrusive memories. Sixty-seven undergraduate students viewed subliminal presentations of traumatic and neutral images, which were preceded by subliminal presentations of either attachment-related images or non-attachment-related images; free recall and intrusive memories were assessed two days later. Participants with low avoidant attachment tendencies who received the attachment primes recalled fewer memories and reported fewer intrusions than those who received the non-attachment primes. Unexpectedly, those with high anxious attachment tendencies reported fewer memories. These findings generally accord with attachment theory, and suggest that consolidation of emotional memories can be moderated by activation of attachment representations. PMID:27631498

  16. Activating Attachments Reduces Memories of Traumatic Images.

    PubMed

    Bryant, Richard A; Foord, Rachael

    2016-01-01

    Emotional memories, and especially intrusive memories, are a common feature of many psychological disorders, and are overconsolidated by stress. Attachment theory posits that activation of mental representations of attachment figures can reduce stress and boost coping. This study tested the proposition that attachment activation would reduce consolidation of emotional and intrusive memories. Sixty-seven undergraduate students viewed subliminal presentations of traumatic and neutral images, which were preceded by subliminal presentations of either attachment-related images or non-attachment-related images; free recall and intrusive memories were assessed two days later. Participants with low avoidant attachment tendencies who received the attachment primes recalled fewer memories and reported fewer intrusions than those who received the non-attachment primes. Unexpectedly, those with high anxious attachment tendencies reported fewer memories. These findings generally accord with attachment theory, and suggest that consolidation of emotional memories can be moderated by activation of attachment representations.

  17. Electron attachment to PSCl3.

    PubMed

    Knighton, W B; Miller, Thomas M; Grimsrud, E P; Viggiano, A A

    2004-01-01

    Electron attachment to PSCl3 was studied in 133-Pa pressure of helium gas at temperatures from 298-550 K. Measurements of rate constants and branching fractions were made in a flowing-afterglow Langmuir-probe (FALP) apparatus. These experiments yielded an electron attachment rate constant of 5.1 x 10(-8) cm3 s(-1) that was found not to change significantly in the 298-550 K temperature range. This rate constant represents an attachment efficiency of about 14%. Attachment in 133 Pa of He gas yielded only the dissociative ion products PSCl2- and Cl-. The FALP data suggest that there is an activation energy of about 17 meV for production of PSCl2-. Attachment to PSCl3 was also studied at high pressure (9-93 kPa) of N2 in an ion mobility mass spectrometer, at 298 K. In contrast to the low-pressure data, the parent anion product channel (PSCl3-) was observed (along with the dissociative channels), and increased in importance with N2 pressure. Gaussian-3 (G3) calculations were carried out for PSCl3 and PSCl2 neutrals and anions to aid in interpretation of the experimental results. The calculations indicate that the electron affinity EA(PSCl2) is slightly smaller than EA(Cl), which may account for the observed branching fractions for PSCl2- and Cl- in the low-pressure experiments. A natural population analysis was performed to obtain the charges associated with each atom in the molecules in order to estimate how the attached electron is distributed. Comparison is made between the present study of electron attachment to PSCl3 and our earlier work on attachment to POCl3, and G3 calculations are reported here for neutral and anionic POCl2 and POCl3. In contrast to PSCl2, the calculations imply that EA(POCl2) is slightly greater than EA(Cl). For both PSCl3 and POCl3, the calculations show that the dissociative electron attachment process is close to thermoneutral.

  18. Electron attachment to PSCl3

    NASA Astrophysics Data System (ADS)

    Knighton, W. B.; Miller, Thomas M.; Grimsrud, E. P.; Viggiano, A. A.

    2004-01-01

    Electron attachment to PSCl3 was studied in 133-Pa pressure of helium gas at temperatures from 298-550 K. Measurements of rate constants and branching fractions were made in a flowing-afterglow Langmuir-probe (FALP) apparatus. These experiments yielded an electron attachment rate constant of 5.1×10-8cm3 s-1 that was found not to change significantly in the 298-550 K temperature range. This rate constant represents an attachment efficiency of about 14%. Attachment in 133 Pa of He gas yielded only the dissociative ion products PSCl2- and Cl-. The FALP data suggest that there is an activation energy of about 17 meV for production of PSCl2-. Attachment to PSCl3 was also studied at high pressure (9-93 kPa) of N2 in an ion mobility mass spectrometer, at 298 K. In contrast to the low-pressure data, the parent anion product channel (PSCl3-) was observed (along with the dissociative channels), and increased in importance with N2 pressure. Gaussian-3 (G3) calculations were carried out for PSCl3 and PSCl2 neutrals and anions to aid in interpretation of the experimental results. The calculations indicate that the electron affinity EA(PSCl2) is slightly smaller than EA(Cl), which may account for the observed branching fractions for PSCl2- and Cl- in the low-pressure experiments. A natural population analysis was performed to obtain the charges associated with each atom in the molecules in order to estimate how the attached electron is distributed. Comparison is made between the present study of electron attachment to PSCl3 and our earlier work on attachment to POCl3, and G3 calculations are reported here for neutral and anionic POCl2 and POCl3. In contrast to PSCl2, the calculations imply that EA(POCl2) is slightly greater than EA(Cl). For both PSCl3 and POCl3, the calculations show that the dissociative electron attachment process is close to thermoneutral.

  19. Attachment in integrative neuroscientific perspective.

    PubMed

    Hruby, Radovan; Hasto, Jozef; Minarik, Peter

    2011-01-01

    Attachment theory is a very influential general concept of human social and emotional development, which emphasizes the role of early mother-infant interactions for infant's adaptive behavioural and stress copying strategies, personality organization and mental health. Individuals with disrupted development of secure attachment to mother/primary caregiver are at higher risk of developing mental disorders. This theory consists of the complex developmental psycho-neurobiological model of attachment and emerges from principles of psychoanalysis, evolutionary biology, cognitive-developmental psychology, ethology, physiology and control systems theory. The progress of modern neuroscience enables interpretation of neurobiological aspects of the theory as multi-level neural interactions and functional development of important neural structures, effects of neuromediattors, hormones and essential neurobiological processes including emotional, cognitive, social interactions and the special key role of mentalizing. It has multiple neurobiological, neuroendocrine, neurophysiological, ethological, genetic, developmental, psychological, psychotherapeutic and neuropsychiatric consequences and is a prototype of complex neuroscientific concept as interpretation of modern integrated neuroscience.

  20. Size-controlled silver nanoparticles stabilized on thiol-functionalized MIL-53(Al) frameworks

    NASA Astrophysics Data System (ADS)

    Cheng, Xinquan; Liu, Min; Zhang, Anfeng; Hu, Shen; Song, Chunshan; Zhang, Guoliang; Guo, Xinwen

    2015-05-01

    A postsynthetic modification method was used to prepare thiol-functionalized metal-organic frameworks (MOFs) by the amidation of mercaptoacetic acid with the amine group, which is present in the frameworks of NH2-MIL-53(Al). By doing this, the thiol group has been successfully grafted on the MOF, which perfectly combined the highly developed pore structures of the MOF with the strong coordination ability of the thiol group. The resulting thiol-functionalized MIL-53(Al) showed a significantly high adsorption capacity for heavy metal ions like Ag+ (182.8 mg g-1). Even more importantly, these grafted thiol groups can be used as anchoring groups for stabilizing metal nanoparticles (NPs) with controllable sizes. Taking silver as an example, monodispersed Ag NPs encapsulated in the cages of MIL-53(Al) have been prepared by using a two-step procedure. In addition, the particle size of the Ag NPs was adjustable to some extent by controlling the initial loading amount. The average size of the smallest Ag NPs is 3.9 +/- 0.9 nm, which is hard to obtain for Ag NPs because of their strong tendency to aggregate.A postsynthetic modification method was used to prepare thiol-functionalized metal-organic frameworks (MOFs) by the amidation of mercaptoacetic acid with the amine group, which is present in the frameworks of NH2-MIL-53(Al). By doing this, the thiol group has been successfully grafted on the MOF, which perfectly combined the highly developed pore structures of the MOF with the strong coordination ability of the thiol group. The resulting thiol-functionalized MIL-53(Al) showed a significantly high adsorption capacity for heavy metal ions like Ag+ (182.8 mg g-1). Even more importantly, these grafted thiol groups can be used as anchoring groups for stabilizing metal nanoparticles (NPs) with controllable sizes. Taking silver as an example, monodispersed Ag NPs encapsulated in the cages of MIL-53(Al) have been prepared by using a two-step procedure. In addition, the particle

  1. Review of Attachment in psychotherapy.

    PubMed

    Slade, Arietta

    2009-06-01

    Reviews the book, Attachment in psychotherapy by David J. Wallin (see record 2007-05421-000). This intellectual and clinical tour-de-force is what we have been waiting for: a book that is on the one hand a coherent, creative, thoughtful, and remarkably integrated view of contemporary psychoanalysis, with attachment, and attachment processes, at its core, and on the other a reflection on our daily, complex, work with patients. The book has three broad aims: first, to ground the reader in attachment theory and research, second, to broaden the reach of attachment theory by building bridges to other aspects of contemporary psychoanalytic theory and science, and third to apply this broader, deeply psychoanalytic, clinical attachment theory to understanding the dynamics of an individual patient and the dynamics of clinical work. This book should be essential reading for anyone interested in contemporary psychoanalysis. Few writers have the ability to write so directly and clearly about complex science and theory; his scholarship and reach are extraordinary. This book is also a book for therapists at all levels of experience. Throughout every section of the book, Wallin writes about his work with patients, about the therapeutic process, about the therapeutic situation, and about the therapeutic relationship, in all its complexity. In the end, he creates a truly contemporary vision of human development, affect regulation, and relational processes, grounded in the body and in the brain, and in the fundamental relationships that make us who we are, as therapists, as patients, and as human beings. (PsycINFO Database Record (c) 2010 APA, all rights reserved).

  2. Thiol-ene immobilisation of carbohydrates onto glass slides as a simple alternative to gold-thiol monolayers, amines or lipid binding.

    PubMed

    Biggs, Caroline I; Edmondson, Steve; Gibson, Matthew I

    2015-01-01

    Carbohydrate arrays are a vital tool in studying infection, probing the mechanisms of bacterial, viral and toxin adhesion and the development of new treatments, by mimicking the structure of the glycocalyx. Current methods rely on the formation of monolayers of carbohydrates that have been chemically modified with a linker to enable interaction with a functionalised surface. This includes amines, biotin, lipids or thiols. Thiol-addition to gold to form self-assembled monolayers is perhaps the simplest method for immobilisation as thiolated glycans are readily accessible from reducing carbohydrates in a single step, but are limited to gold surfaces. Here we have developed a quick and versatile methodology which enables the use of thiolated carbohydrates to be immobilised as monolayers directly onto acrylate-functional glass slides via a 'thiol-ene'/Michael-type reaction. By combining the ease of thiol chemistry with glass slides, which are compatible with microarray scanners this offers a cost effective, but also useful method to assemble arrays.

  3. 10 CFR 75.15 - Facility attachments.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 10 Energy 2 2010-01-01 2010-01-01 false Facility attachments. 75.15 Section 75.15 Energy NUCLEAR... Accounting and Control for Facilities § 75.15 Facility attachments. (a) The Facility Attachment or Transitional Facility Attachment will document the determinations referred to in § 75.10 and will contain...

  4. Attachment Processes in Eating Disorder and Depression.

    ERIC Educational Resources Information Center

    Cole-Detke, Holland; Kobak, Roger

    1996-01-01

    Examines the relationship between attachment strategies and symptom reporting among college women (N=61). The Adult Attachment Interview (AAI) was administered and interview transcripts were rated with the Attachment Interview Q-Sort. Findings support the hypothesis that secondary or defensive attachment strategies predispose individuals toward…

  5. A Study of Functional Polymer Colloids Prepared Using Thiol-Ene/Yne Click Chemistry

    NASA Astrophysics Data System (ADS)

    Durham, Olivia Z.

    This project demonstrates the first instance of thiol-ene chemistry as the polymerization method for the production of polymer colloids in two-phase heterogeneous suspensions, miniemulsions, and emulsions. This work was also expanded to thiol-yne chemistry for the production of polymer particles containing increased crosslinking density. The utility of thiol-ene and thiol-yne chemistries for polymerization and polymer modification is well established in bulk systems. These reactions are considered 'click' reactions, which can be defined as processes that are both facile and simple, offering high yields with nearly 100% conversion, no side products, easy product separation, compatibility with a diverse variety of commercially available starting materials, and orthogonality with other chemistries. In addition, thiol-ene and thiol-yne chemistry follow a step-growth mechanism for the development of highly uniform polymer networks, where polymer growth is dependent on the coupling of functional groups. These step-growth polymerization systems are in stark contrast to the chain-growth mechanisms of acrylic and styrenic monomers that have dominated the field of conventional heterogeneous polymerizations. Preliminary studies evaluated the mechanism of particle production in suspension and miniemulsion systems. Monomer droplets were compared to the final polymer particles to confirm that particle growth occurred through the polymerization of monomer droplets. Additional parameters examined include homogenization energy (mechanical mixing), diluent species and concentration, and monomer content. These reactions were conducted using photoinitiation to yield particles in a matter of minutes with diameters in the size range of several microns to hundreds of microns in suspensions or submicron particles in miniemulsions. Improved control over the particle size and size distribution was examined through variation of reaction parameters. In addition, a method of seeded suspension

  6. Synthesis of alkenyl sulfides through the iron-catalyzed cross-coupling reaction of vinyl halides with thiols.

    PubMed

    Lin, Yun-Yung; Wang, Yu-Jen; Lin, Che-Hung; Cheng, Jun-Hao; Lee, Chin-Fa

    2012-07-20

    We report here the iron-catalyzed cross-coupling reaction of alkyl vinyl halides with thiols. While many works are devoted to the coupling of thiols with alkyl vinyl iodides, interestingly, the known S-vinylation of vinyl bromides and chlorides is limited to 1-(2-bromovinyl)benzene and 1-(2-chlorovinyl)benzene. Investigation on the coupling reaction of challenging alkyl vinyl bromides and chlorides with thiols is rare. Since the coupling of 1-(2-bromovinyl)benzene and 1-(2-chlorovinyl)benzene with thiols can be performed in the absence of any catalyst, here we focus on the coupling of thiols with alkyl vinyl halides. This system is generally reactive for alkyl vinyl iodides and bromides to provide the products in good yields. 1-(Chloromethylidene)-4-tert-butyl-cyclohexane was also coupled with thiols, giving the targets in moderate yields.

  7. Synthesis of a thiol-β-cyclodextrin, a potential agent for controlling enzymatic browning in fruits and vegetables.

    PubMed

    Manta, Carmen; Peralta-Altier, Gabriela; Gioia, Larissa; Méndez, María F; Seoane, Gustavo; Ovsejevi, Karen

    2013-11-27

    A thiol-β-cyclodextrin was synthesized by a simple and environmentally friendly three-step method comprising epoxy activation of β-cyclodextrin, thiosulfate-mediated oxirane opening, and further reduction of the S-alkyl thiosulfate to a thiol group. The final step was optimized by using thiopropyl-agarose, a solid phase reducing agent with many advantages over soluble ones. β-Cyclodextrin thiolation was confirmed by titration with a thiol-reactive reagent, NMR studies, and MALDI-TOF/TOF. Thiolated cyclodextrin had an average value of one thiol group per molecule. Thiol-β-cyclodextrin proved to be an excellent agent for controlling polyphenol oxidase activity. This copper-containing enzyme is responsible for browning in fruits and vegetables. Under the same conditions, thiol-β-cyclodextrin generated a reductive microenvironment that increased the antibrowning effect on Red Delicious apples compared to unmodified β-cyclodextrin.

  8. Substituent Effects on the Reactivity of Benzoquinone Derivatives with Thiols

    PubMed Central

    Mbiya, Wilbes; Chipinda, Itai; Siegel, Paul D.; Mhike, Morgen; Simoyi, Reuben H.

    2013-01-01

    Benzoquinone (BQ) is an extremely potent electrophilic contact allergen that haptenates endogenous proteins through Michael addition (MA). It is also hypothesized that BQ may haptenate proteins via free radical formation. The objective of this study was to assess the inductive effects (activating and deactivating) of substituents on BQ reactivity and mechanistic pathway of covalent binding to a nucleophilic thiol. The BQ binding of Cys34 on human serum albumin was studied and for reactivity studies, nitrobenzenethiol (NBT) was used as a surrogate for protein binding of the BQ and benzoquinone derivatives (BQD). Stopped flow techniques were used to determine pseudo-first order rate constants (k) of methyl, t-butyl and chlorine substituted BQD reactions with NBT whereas electron pair resonance (EPR) studies were performed to investigate the presence a free radical mediated binding mechanism of BQD. Characterization of adducts was performed using mass spectrometry and nuclear magnetic resonance spectroscopy (NMR). The rate constant values demonstrated the chlorine substituted (activated) BQD to be more reactive toward NBT than the methyl and t-butyl substituted (deactivated) BQD, and this correlated with the respective EPR intensities. The EPR signal, however, was quenched in the presence of NBT suggesting MA as the dominant reaction pathway. MS and NMR results confirmed adduct formation to be a result of MA onto the BQ ring with vinylic substitution also occurring for chlorine substituted derivatives. The binding positions on BQ and NBT:BQ(D) stoichiometric ratios were affected by whether the inductive effects of the substituents on the ring were positive or negative. The reactivity of BQ and BQD is discussed in terms of the potential relationship to potential allergenic potency. PMID:23237669

  9. Catalytic Mechanism of Thiol Peroxidase from Escherichia coli

    PubMed Central

    Baker, Laura M. S.; Poole, Leslie B.

    2013-01-01

    Escherichia coli thiol peroxidase (Tpx, p20, scavengase) is part of an oxidative stress defense system that uses reducing equivalents from thioredoxin (Trx1) and thioredoxin reductase to reduce alkyl hydroperoxides. Tpx contains three Cys residues, Cys95, Cys82, and Cys61, and the latter residue aligns with the N-terminal active site Cys of other peroxidases in the peroxiredoxin family. To identify the catalytically important Cys, we have cloned and purified Tpx and four mutants (C61S, C82S, C95S, and C82S,C95S). In rapid reaction kinetic experiments measuring steady-state turnover, C61S is inactive, C95S retains partial activity, and the C82S mutation only slightly affects reaction rates. Furthermore, a sulfenic acid intermediate at Cys61 generated by cu-mene hydroperoxide (CHP) treatment was detected in UV-visible spectra of 4-nitrobenzo-2-oxa-1,3-diazole-labeled C82S,C95S, confirming the identity of Cys61 as the peroxidatic center. In stopped-flow kinetic studies, Tpx and Trx1 form a Michaelis complex during turnover with a catalytic efficiency of 3.0 × 106 m−1 s−1, and the low Km(9.0 µm) of Tpx for CHP demonstrates substrate specificity toward alkyl hydroperoxides over H2O2 (Km > 1.7 mm). Rapid inactivation of Tpx due to Cys61 over-oxidation is observed during turnover with CHP and a lipid hydroperoxide, 15-hydroperoxyeicosatetraenoic acid, but not H2O2. Unlike most other 2-Cys peroxiredox-ins, which operate by an intersubunit disulfide mechanism, Tpx contains a redox-active intrasubunit disulfide bond yet is homodimeric in solution. PMID:12514184

  10. Oxidative inactivation of brain ecto-5'-nucleotidase by thiols/Fe2+ system.

    PubMed

    Liu, X W; Sok, D E

    2000-11-01

    5'-Nucleotidase, responsible for the conversion of adenosine-5'-monophosphate into adenosine, was purified from bovine brain membranes, and subjected to oxidative inactivation. The 5'-nucleotidase activity decreased slightly after the exposure to either glutathione or Fe2+. The glutathione-mediated inactivation of 5'-nucleotidase was potentiated remarkably by Fe2+, but not Cu2+, in a concentration-dependent manner. Similarly, glutathione exhibited a concentration-dependent enhancement of the Fe2+-mediated inactivation. In comparison, the glutathione/Fe2+ system was much more effective than the ascorbate/Fe2+ system in inactivating the enzyme. In support of an intermediary role of superoxide ions or H2O2 in the action of glutathione/Fe2+ system, superoxide dismutase and catalase expressed a substantial protection against the inactivation by the glutathione/Fe2+ system. Meanwhile, hydroxyl radical scavengers such as mannitol, benzoate or ethanol were incapable of preventing the inactivation, excluding the participation of extraneous hydroxyl radicals. Whereas adenosine 5'-monophosphate as substrate exhibited a modest protection against the glutathione/Fe2+ action, a remarkable protection was expressed by divalent metal ions such as Zn2+ or Mn2+. Structure-activity study with a variety of thiols indicates that the inactivating action of thiols in combination with Fe2+ resides in the free sulfhydryl group and amino group of thiols. Overall, thiols, expressing more inhibitory effect on the activity of 5'-nucleotidase, were found to be more effective in potentiating the Fe2+-mediated inactivation. Further, kinetic analyses indicate that Fe2+ and thiols inhibit the 5'-nucleotidase in a competitive or uncompetitive manner, respectively. These results suggest that ecto-5'-nucleotidase from brain membrane is one of proteins susceptible to thiols/Fe2+-catalyzed oxidation, and the oxidative inactivation may be related to the selective association of Fe2+ and thiols to the

  11. Cysteinylation and homocysteinylation of plasma protein thiols during ageing of healthy human beings

    PubMed Central

    Rossi, R; Giustarini, D; Milzani, A; Dalle-Donne, I

    2009-01-01

    The purpose of the present study was to determine the relative amount of S-thiolated proteins (i.e. S-homocysteinylated, S-cysteinylglycinylated, S-glutathionylated and S-cysteinylated proteins) to the total protein thiols (i.e. the sum of reduced protein sulphydryl groups (PSHs) and protein mixed disulphides with homocysteine [HcySH], cysteinylglycine, cysteine [CysSH] and glutathione) in the plasma of healthy individuals aged 20 to 93. After plasma separation, total protein thiols, S-thiolated proteins, as well as CysSH, cystine, HcySH and homocystine were measured by high-performance liquid chromatography (HPLC) with fluorescence determination of the thiol-monobromobimane conjugate. Determination of plasma levels of protein thiols was performed by spectrophotometry with 5,5′-dithiobis(2-nitrobenzoic acid) as a titrating agent. The present study demonstrates an age-dependent reduction in the amount of PSHs, and an age-dependent increase in cysteinylated and homocysteinylated plasma proteins in healthy human beings. This indicates that the efficiency of the reduced protein thiol pool as an antioxidant defence system decreases with age, possibly causing an increased risk of irreversible oxidation (i.e. further oxidation to sulphinic and sulphonic acids, which are usually not reducible by thiol reducing agents) of sulphydryl groups of plasma proteins. The drop in the plasma level of protein sulphydryl groups suggests depletion and/or impairment of the antioxidant capacity of plasma, likely related to an alteration of the delicate balance between the different redox forms of thiols. PMID:18624771

  12. Thiol-Ene functionalized siloxanes for use as elastomeric dental impression materials

    PubMed Central

    Cole, Megan A.; Jankousky, Katherine C.; Bowman, Christopher N.

    2014-01-01

    Objectives Thiol- and allyl-functionalized siloxane oligomers are synthesized and evaluated for use as a radical-mediated, rapid set elastomeric dental impression material. Thiol-ene siloxane formulations are crosslinked using a redox-initiated polymerization scheme, and the mechanical properties of the thiol-ene network are manipulated through the incorporation of varying degrees of plasticizer and kaolin filler. Formulations with medium and light body consistencies are further evaluated for their ability to accurately replicate features on both the gross and microscopic levels. We hypothesize that thiol-ene functionalized siloxane systems will exhibit faster setting times and greater detail reproduction than commercially available polyvinylsiloxane (PVS) materials of comparable consistencies. Methods Thiol-ene functionalized siloxane mixtures formulated with varying levels of redox initiators, plasticizer, and kaolin filler are made and evaluated for their polymerization speed (FTIR), consistency (ISO4823.9.2), and surface energy (goniometer). Feature replication is evaluated quantitatively by SEM. The Tg, storage modulus, and creep behavior are determined by DMA. Results Increasing redox initiation rate increases the polymerization rate but at high levels also limits working time. Combining 0.86 wt% oxidizing agent with up to 5 wt% plasticizer gave a working time of 3 min and a setting time of 2 min. The selected medium and light body thiol-ene formulations also achieved greater qualitative detail reproduction than the commercial material and reproduced micrometer patterns with 98% accuracy. Significance Improving detail reproduction and setting speed is a primary focus of dental impression material design and synthesis. Radical-mediated polymerizations, particularly thiol-ene reactions, are recognized for their speed, reduced shrinkage, and ‘click’ nature. PMID:24553250

  13. Detecting thiols in a microchip device using micromolded carbon ink electrodes modified with cobalt phthalocyanine.

    PubMed

    Kuhnline, Courtney D; Gangel, Michael G; Hulvey, Matthew K; Martin, R Scott

    2006-02-01

    This paper describes the fabrication and evaluation of a chemically modified carbon ink microelectrode to detect thiols of biological interest. The detection of thiols, such as homocysteine and cysteine, is necessary to monitor various disease states. The biological implications of these thiols generate the need for miniaturized detection systems that enable portable monitoring as well as quantitative results. In this work, we utilize a microchip device that incorporates a micromolded carbon ink electrode modified with cobalt phthalocyanine to detect thiols. Cobalt phthalocyanine (CoPC) is an electrocatalyst that lowers the potential needed for the oxidation of thiols. The CoPC/carbon ink composition was optimized for the micromolding method and the resulting microelectrode was characterized with microchip-based flow injection analysis. It was found that CoPC lowers the overpotential for thiols but, as compared to direct amperometric detection, a pulsed detection scheme was needed to constantly regenerate the electrocatalyst surface, leading to improved peak reproducibility and limits of detection. Using the pulsed method, cysteine exhibited a linear response between 10-250 microM (r(2) = 0.9991) with a limit of detection (S/N = 3) of 7.5 microM, while homocysteine exhibited a linear response between 10-500 microM (r(2) = 0.9967) with a limit of detection of 6.9 microM. Finally, to demonstrate the ability to measure thiols in a biological sample using a microchip device, the CoPC-modified microelectrode was utilized for the detection of cysteine in the presence of rabbit erythrocytes.

  14. Monocyte activation drives preservation of membrane thiols by promoting release of oxidised membrane moieties via extracellular vesicles.

    PubMed

    Szabó-Taylor, K É; Tóth, E Á; Balogh, A M; Sódar, B W; Kádár, L; Pálóczi, K; Fekete, N; Németh, A; Osteikoetxea, X; Vukman, K V; Holub, M; Pállinger, É; Nagy, Gy; Winyard, P G; Buzás, E I

    2017-03-18

    The redox state of cellular exofacial molecules is reflected by the amount of available thiols. Furthermore, surface thiols can be considered as indicators of immune cell activation. One group of thiol containing proteins, peroxiredoxins, in particular, have been associated with inflammation. In this study, we assessed surface thiols of the U937 and Thp1 monocyte cell lines and primary monocytes in vitro upon inflammatory stimulation by irreversibly labelling the cells with a fluorescent derivative of maleimide. We also investigated exofacial thiols on circulating blood mononuclear cells in patients with rheumatoid arthritis and healthy controls. When analysing extracellular vesicles, we combined thiol labelling with the use of antibodies to specific CD markers to exclude extracellular vesicle mimicking signals from thiol containing protein aggregates. Furthermore, differential detergent lysis was applied to confirm the vesicular nature of the detected extracellular events in blood plasma. We found an increase in exofacial thiols on monocytes upon in vitro stimulation by LPS or TNF, both in primary monocytes and monocytic cell lines (p<0.0005). At the same time, newly released extracellular vesicles showed a decrease in their exofacial thiols compared with those from unstimulated cells (p<0.05). We also found a significant elevation of surface thiols on circulating monocytes in rheumatoid arthritis patients (p<0.05) and newly released extracellular vesicles of isolated CD14(+) cells from rheumatoid arthritis patients had decreased thiol levels compared with healthy subjects (p<0.01). Exofacial peroxiredoxin 1 was demonstrated on the surface of primary and cultured monocytes, and the number of peroxiredoxin 1 positive extracellular vesicles was increased in rheumatoid arthritis blood plasma (p<0.05). Furthermore, an overoxidised form of peroxiredoxin was detected in extracellular vesicle-enriched preparations from blood plasma. Our data show that cell surface thiols

  15. To Be Attached and Free.

    ERIC Educational Resources Information Center

    Maier, Henry W.

    1987-01-01

    Reviews recent research showing that child and parent, or caregiver and care receiver in nonfamilial, group settings, need each other reciprocally and need to find mutual fit. Focuses on stress laid on importance of dependence support, attachment behavior, and mutuality of caregiver and care receiver. Discusses effect of day care and significance…

  16. Attachment Representations of Deaf Adults

    ERIC Educational Resources Information Center

    McKinnon, Cathy Chovaz; Moran, Greg; Pederson, David

    2004-01-01

    The primary goal of this study was to examine the feasibility of using the Adult Attachment Interview (AAI) with 50 culturally deaf adults. Modifications to the standard protocol included using a visual-spatial language (American Sign Language) rather than a spoken language (English), as well as coding and procedural variations from the…

  17. Modification of non-protein thiols contents in transgenic tobacco plants producing bacterial enzymes of cysteine biosynthesis pathway.

    PubMed

    Liszewska, F; Blaszczyk, A; Sirko, A

    2001-01-01

    Conditions of achieving the maximal accumulation of sulfhydryl metabolites in the leaves of tobacco were explored. Simultaneous production of bacterial O-acetylserine (thiol)-lyase and serine acetyltransferase resulted in the increased thiols contents as compared to single transformants and controls. However, leaf discs feeding experiments differently affected thiols concentration in different plant groups and suggested that the most promising strategy to obtain plants with a high level of non-protein thiol-containing compounds might be sulfate feeding to plants overproducing serine acetyltransferase.

  18. Visualizing and quantifying oxidized protein thiols in tissue sections: a comparison of dystrophic mdx and normal skeletal mouse muscles.

    PubMed

    Iwasaki, Tomohito; Terrill, Jessica; Shavlakadze, Tea; Grounds, Miranda D; Arthur, Peter G

    2013-12-01

    Reactive oxygen species (ROS) are not only a cause of oxidative stress in a range of disease conditions but are also important regulators of physiological pathways in vivo. One mechanism whereby ROS can regulate cell function is by modification of proteins through the reversible oxidation of their thiol groups. An experimental challenge has been the relative lack of techniques to probe the biological significance of protein thiol oxidation in complex multicellular tissues and organs. We have developed a sensitive and quantitative fluorescence labeling technique to detect and localize protein thiol oxidation in histological tissue sections. In our technique, reduced and oxidized protein thiols are visualized and quantified on two consecutive tissue sections and the extent of protein thiol oxidation is expressed as a percentage of total protein thiols (reduced plus oxidized). We tested the application of this new technique using muscles of dystrophic (mdx) and wild-type C57Bl/10Scsn (C57) mice. In mdx myofibers, protein thiols were consistently more oxidized (19 ± 3%) compared with healthy myofibers (10 ± 1%) in C57 mice. A striking observation was the localization of intensive protein thiol oxidation (70 ± 9%) within myofibers associated with necrotic damage. Oxidative stress is an area of active investigation in many fields of research, and this technique provides a useful tool for locating and further understanding protein thiol oxidation in normal, damaged, and diseased tissues.

  19. Thiol groups controls on arsenite binding by organic matter: new experimental and modeling evidence.

    PubMed

    Catrouillet, Charlotte; Davranche, Mélanie; Dia, Aline; Bouhnik-Le Coz, Martine; Pédrot, Mathieu; Marsac, Rémi; Gruau, Gérard

    2015-12-15

    Although it has been suggested that several mechanisms can describe the direct binding of As(III) to organic matter (OM), more recently, the thiol functional group of humic acid (HA) was shown to be an important potential binding site for As(III). Isotherm experiments on As(III) sorption to HAs, that have either been grafted with thiol or not, were thus conducted to investigate the preferential As(III) binding sites. There was a low level of binding of As(III) to HA, which was strongly dependent on the abundance of the thiols. Experimental datasets were used to develop a new model (the modified PHREEQC-Model VI), which defines HA as a group of discrete carboxylic, phenolic and thiol sites. Protonation/deprotonation constants were determined for each group of sites (pKA=4.28±0.03; ΔpKA=2.13±0.10; pKB=7.11±0.26; ΔpKB=3.52±0.49; pKS=5.82±0.052; ΔpKS=6.12±0.12 for the carboxylic, phenolic and thiols sites, respectively) from HAs that were either grafted with thiol or not. The pKS value corresponds to that of single thiol-containing organic ligands. Two binding models were tested: the Mono model, which considered that As(III) is bound to the HA thiol site as monodentate complexes, and the Tri model, which considered that As(III) is bound as tridentate complexes. A simulation of the available literature datasets was used to validate the Mono model, with logKMS=2.91±0.04, i.e. the monodentate hypothesis. This study highlighted the importance of thiol groups in OM reactivity and, notably, determined the As(III) concentration bound to OM (considering that Fe is lacking or at least negligible) and was used to develop a model that is able to determine the As(III) concentrations bound to OM.

  20. Nebulized and oral thiol derivatives for pulmonary disease in cystic fibrosis.

    PubMed

    Nash, Edward F; Stephenson, Anne; Ratjen, Felix; Tullis, Elizabeth

    2009-01-21

    Cystic fibrosis is an inherited condition resulting in thickened, sticky respiratory secretions. Respiratory failure, due to recurrent pulmonary infection and inflammation, is the most common cause of mortality. Muco-active therapies (e.g. dornase alfa and nebulized hypertonic saline) may decrease sputum viscosity, increase airway clearance of sputum, reduce infection and inflammation and improve lung function. Thiol derivatives, either oral or nebulized, have shown benefit in other respiratory diseases. Their mode of action is likely to differ according to the route of administration. There are several thiol derivatives, and it is unclear which of these may be beneficial in cystic fibrosis. To evaluate the efficacy and safety of nebulized and oral thiol derivatives in people with cystic fibrosis. We searched the Cochrane Cystic Fibrosis and Genetic Disorders Group Trials Register, comprising references identified from comprehensive electronic database searches, hand searches of relevant journals, abstract books and conference proceedings.Most recent search: November 2008. Randomized and quasi-randomized controlled trials comparing nebulized or oral thiol derivatives to placebo or another thiol derivative in people with cystic fibrosis. The authors independently assessed trials for inclusion, analysed methodological quality and extracted data. Searches identified 18 trials; eight (seven older than 10 years) (234 participants) are included. Three trials of nebulized thiol derivatives were identified (one compared 20% n-acetylcysteine to 2% n-acetylcysteine; another compared sodium-2-mercaptoethane sulphonate to 7% hypertonic saline; and another compared glutathione to 4% hypertonic saline). Although generally well-tolerated with no significant adverse effects, there was no evidence of significant clinical benefit in our primary outcomes in participants receiving these treatments.Five studies of oral thiol derivatives were identified. Three studies compared n

  1. Nebulized and oral thiol derivatives for pulmonary disease in cystic fibrosis.

    PubMed

    Tam, Julian; Nash, Edward F; Ratjen, Felix; Tullis, Elizabeth; Stephenson, Anne

    2013-07-12

    Cystic fibrosis is an inherited condition resulting in thickened, sticky respiratory secretions. Respiratory failure, due to recurrent pulmonary infection and inflammation, is the most common cause of mortality. Muco-active therapies (e.g. dornase alfa and nebulized hypertonic saline) may decrease sputum viscosity, increase airway clearance of sputum, reduce infection and inflammation and improve lung function. Thiol derivatives, either oral or nebulized, have shown benefit in other respiratory diseases. Their mode of action is likely to differ according to the route of administration. There are several thiol derivatives, and it is unclear which of these may be beneficial in cystic fibrosis. To evaluate the efficacy and safety of nebulized and oral thiol derivatives in people with cystic fibrosis. We searched the Cochrane Cystic Fibrosis and Genetic Disorders Group Trials Register, comprising references identified from comprehensive electronic database searches, hand searches of relevant journals, abstract books and conference proceedings.Most recent search: 13 June 2013.We also conducted a PubMed search on 26 February 2013 for relevant published articles. Randomized and quasi-randomized controlled trials comparing nebulized or oral thiol derivatives to placebo or another thiol derivative in people with cystic fibrosis. The authors independently assessed trials for inclusion, analysed risk of bias and extracted data. Searches identified 23 trials; nine trials (255 participants) are included, of these seven trials are more than 10 years old. Three trials of nebulized thiol derivatives were identified (one compared 20% N-acetylcysteine to 2% N-acetylcysteine; another compared sodium-2-mercaptoethane sulphonate to 7% hypertonic saline; and another compared glutathione to 4% hypertonic saline). Although generally well-tolerated with no significant adverse effects, there was no evidence of significant clinical benefit in our primary outcomes in participants receiving

  2. Visible light cured thiol-vinyl hydrogels with tunable degradation for 3D cell culture

    PubMed Central

    Hao, Yiting; Shih, Han; Muňoz, Zachary; Kemp, Arika; Lin, Chien-Chi

    2013-01-01

    We report here a synthetically simple yet highly tunable and diverse visible light mediated thiol-vinyl gelation system for fabricating cell-instructive hydrogels. Gelation was achieved via a mixed-mode step-and-chain-growth photopolymerization using functionalized 4-arm poly(ethylene glycol) as backbone macromer, eosin-Y as photosensitizer, and di-thiol containing molecule as dual purpose co-initiator/cross-linker. N-vinylpyrrolidone (NVP) was used to accelerate gelation kinetics and to adjust the stiffness of the hydrogels. Visible light (wavelength: 400–700nm) was used to initiate rapid gelation (gel points: ~20 seconds) that reached completion within a few minutes. The major differences between current thiol-vinyl gelation and prior visible light mediated photopolymerization are that: (1) the co-initiator triethanolamine (TEOA) used in the previous systems was replaced with multifunctional thiols and (2) mixed-mode polymerized gels contain less network heterogeneity. The gelation kinetics and gel properties at the same PEG macromer concentration could be tuned by changing the identity of vinyl groups and di-thiol cross-linkers, as well as concentration of cross-linker and NVP. Specifically, acrylate-modified PEG afforded the fastest gelation rate, followed by acrylamide and methacrylate-functionalized PEG. Increasing NVP concentration also accelerated gelation and led to a higher network cross-linking density. Further, increasing di-thiol peptide concentration in the gel formulation increased hydrogel swelling and decreased gel stiffness. Due to the formation of thiol-ether-ester bonds following thiol-acrylate reaction, the gels degraded hydrolytically following a pseudo first order degradation kinetics. Degradation rate was controlled by adjusting thiol or NVP content in the polymer precursor solution. The cytocompatibility and utility of this hydrogel system were evaluated using in situ encapsulation of human mesenchymal stem cells (hMSC). Encapsulated h

  3. Comparative electron paramagnetic resonance investigation of reduced graphene oxide and carbon nanotubes with different chemical functionalities for quantum dot attachment

    SciTech Connect

    Pham, Chuyen V.; Krueger, Michael E-mail: emre.erdem@physchem.uni-freiburg.de; Eck, Michael; Weber, Stefan; Erdem, Emre E-mail: emre.erdem@physchem.uni-freiburg.de

    2014-03-31

    Electron paramagnetic resonance (EPR) spectroscopy has been applied to different chemically treated reduced graphene oxide (rGO) and multiwalled carbon nanotubes (CNTs). A narrow EPR signal is visible at g = 2.0029 in both GO and CNT-Oxide from carbon-related dangling bonds. EPR signals became broader and of lower intensity after oxygen-containing functionalities were reduced and partially transformed into thiol groups to obtain thiol-functionalized reduced GO (TrGO) and thiol-functionalized CNT (CNT-SH), respectively. Additionally, EPR investigation of CdSe quantum dot-TrGO hybrid material reveals complete quenching of the TrGO EPR signal due to direct chemical attachment and electronic coupling. Our work confirms that EPR is a suitable tool to detect spin density changes in different functionalized nanocarbon materials and can contribute to improved understanding of electronic coupling effects in nanocarbon-nanoparticle hybrid nano-composites promising for various electronic and optoelectronic applications.

  4. Equilibrium mercury isotope fractionation between dissolved Hg(II) species and thiol-bound Hg.

    PubMed

    Wiederhold, Jan G; Cramer, Christopher J; Daniel, Kelly; Infante, Ivan; Bourdon, Bernard; Kretzschmar, Ruben

    2010-06-01

    Stable Hg isotope ratios provide a new tool to trace environmental Hg cycling. Thiols (-SH) are the dominant Hg-binding groups in natural organic matter. Here, we report experimental and computational results on equilibrium Hg isotope fractionation between dissolved Hg(II) species and thiol-bound Hg. Hg(II) chloride and nitrate solutions were equilibrated in parallel batches with varying amounts of thiol resin resulting in different fractions of thiol-bound and free Hg. Mercury isotope ratios in both fractions were analyzed by multiple collector inductively coupled plasma mass spectrometry (MC-ICPMS). Theoretical equilibrium Hg isotope effects by mass-dependent fractionation (MDF) and nuclear volume fractionation (NVF) were calculated for 14 relevant Hg(II) species. The experimental data revealed that thiol-bound Hg was enriched in light Hg isotopes by 0.53 per thousand and 0.62 per thousand (delta(202)Hg) relative to HgCl(2) and Hg(OH)(2), respectively. The computational results were in excellent agreement with the experimental data indicating that a combination of MDF and NVF was responsible for the observed Hg isotope fractionation. Small mass-independent fractionation (MIF) effects (<0.1 per thousand) were observed representing one of the first experimental evidences for MIF of Hg isotopes by NVF. Our results indicate that significant equilibrium Hg isotope fractionation can occur without redox transition, and that NVF must be considered in addition to MDF to explain Hg isotope variations.

  5. S-methyl derivatives from thiol compounds by the pyrolytic reaction with trimethylsulfonium hydroxide.

    PubMed

    Vosmann, K; Klein, E; Weber, N

    1998-10-01

    Base-catalyzed transesterification of acyl lipids with methanol in the presence of trimethylsulfonium hydroxide (TMSH) is an easy and convenient method for the preparation of fatty acid methyl esters for gas chromatography (GC) analyses. Free fatty acids are converted to fatty acid methyl esters by the pyrolytic reaction with TMSH as well. We have found that lipids and other compounds containing thiol groups are also converted easily to the corresponding methyl sulfides (methyl thioethers) by the pyrolytic reaction with TMSH occurring in the injector of the gas chromatograph. For example, alkane thiols such as dodecane thiol and octadecane thiol are converted to the corresponding alkyl methyl sulfides, whereas bis(methylthio) derivatives are formed from alpha,omega-alkane dithiols, e.g., 1,8-octanedithiol, and from 2,3-dimercaptopropan-1-ol (dimercaprol). Furthermore, 3beta-mercaptocholest-5-ene (thiocholesterol) is converted to 3-methylthiocholest-5-ene by the same reaction. The S-methylation reactions which finally lead to the corresponding methylthio derivatives of lipids and other compounds with thiol groups may be of diagnostic value for the structural analysis of such compounds by GC and GC/mass spectrometry.

  6. Heavy metal ion removal by thiol functionalized aluminum oxide hydroxide nanowhiskers

    NASA Astrophysics Data System (ADS)

    Xia, Zhiyong; Baird, Lance; Zimmerman, Natasha; Yeager, Matthew

    2017-09-01

    In this study, we developed a cost effective method of using thiol functionalized γ-aluminum oxide hydroxide (γ-AlOOH) filters for removing three key heavy metals from water: mercury, lead, and cadmium under non-concomitant conditions. Compared to non-thiol treated γ-AlOOH filters, the introduction of thiol functional groups greatly improved the heavy metal removal efficiency under both static and dynamic filtration conditions. The adsorption kinetics of thiol functionalized γ-AlOOH were investigated using the Lagergren first order and pseudo-second order kinetics models; whereas the isothermal adsorption behavior of these membranes was revealed through the Langmuir and Freundlich models. Heavy metal concentration was quantified by Inductively Coupled Plasma-Mass Spectroscopy, and the thiol level on γ-AlOOH surface was measured by a colorimetric assay using Ellman's reagent. X-ray photoelectron spectroscopy was used to further address the surface sulfur state on the membranes after heavy metal exposure. Mechanisms for heavy metal adsorption were also discussed.

  7. Simultaneous assessment of endogenous thiol compounds by LC-MS/MS.

    PubMed

    Sun, Yao; Yao, Tong; Guo, Xiucai; Peng, Ying; Zheng, Jiang

    2016-09-01

    Biological thiol compounds are very important molecules that participate in various physiological events. Alteration in levels of endogenous thiols has been suggested as a biomarker of early stage of pathological changes. We reported a chemical derivatization- and LC-MS/MS-based approach to simultaneously determine thiol compounds including glutathione (GSH), cysteine (Cys), N-acetyl cysteine (NAC), homocysteine (Hcy), and cysteinylglycine (CysGly) in biological samples. Thiol-containing samples were derivatized with monobromobimane (mBrB) at room temperature, followed by LC-MS/MS analysis. Assessment of the analytes with baseline separation was completed within 10min, using a gradient elution on a C18 reversed-phase column. Excellent linearity was observed for all analytes over their concentration ranges of 1-400μM. The lowest limits of detection (S/N=3) in a range from 0.31fmol (for NAC) to 4.98fmol (for CysGly) were achieved. The results indicate that this approach was sensitive, selective, and well suited for high-throughput quantitative determination of the biological thiols.

  8. Thiol peroxidases mediate specific genome-wide regulation of gene expression in response to hydrogen peroxide

    PubMed Central

    Fomenko, Dmitri E.; Koc, Ahmet; Agisheva, Natalia; Jacobsen, Michael; Kaya, Alaattin; Malinouski, Mikalai; Rutherford, Julian C.; Siu, Kam-Leung; Jin, Dong-Yan; Winge, Dennis R.; Gladyshev, Vadim N.

    2011-01-01

    Hydrogen peroxide is thought to regulate cellular processes by direct oxidation of numerous cellular proteins, whereas antioxidants, most notably thiol peroxidases, are thought to reduce peroxides and inhibit H2O2 response. However, thiol peroxidases have also been implicated in activation of transcription factors and signaling. It remains unclear if these enzymes stimulate or inhibit redox regulation and whether this regulation is widespread or limited to a few cellular components. Herein, we found that Saccharomyces cerevisiae cells lacking all eight thiol peroxidases were viable and withstood redox stresses. They transcriptionally responded to various redox treatments, but were unable to activate and repress gene expression in response to H2O2. Further studies involving redox transcription factors suggested that thiol peroxidases are major regulators of global gene expression in response to H2O2. The data suggest that thiol peroxidases sense and transfer oxidative signals to the signaling proteins and regulate transcription, whereas a direct interaction between H2O2 and other cellular proteins plays a secondary role. PMID:21282621

  9. Identification of multiple folding pathways of monellin using pulsed thiol labeling and mass spectrometry.

    PubMed

    Jha, Santosh Kumar; Dasgupta, Amrita; Malhotra, Pooja; Udgaonkar, Jayant B

    2011-04-19

    Protein folding reactions often display multiexponential kinetics of changes in intrinsic optical signals, as a manifestation of heterogeneity, either on one folding pathway or on multiple folding pathways. Delineating the origin of this heterogeneity is difficult because different coexisting structural forms of a protein cannot be easily distinguished by optical probes. In this study, the complex folding reaction of single-chain monellin has been investigated using a pulsed thiol labeling (SX) methodology in conjunction with mass spectrometry, which measures the kinetics of burial of a cysteine side chain thiol during folding. Because it can directly distinguish between unfolded and folded molecules and can measure the disappearance of the former during folding, the pulsed SX methodology is an ideal method for investigating whether multiple pathways are operative during folding. The kinetics of burial of the C42 thiol of monellin was observed to follow biexponential kinetics. To determine whether this was because the fast phase leads to the partial protection of the thiol group in all the molecules or to complete protection in only a fraction of the molecules, the duration and intensity of the labeling pulse were varied. The observation that the extent of labeling did not vary with the duration of the pulse cannot be explained by a simple sequential folding mechanism. Two parallel folding pathways are shown to be operative, with one leading to the formation of thiol-protective structure more rapidly than the other.

  10. Selective Adsorption of Thiols Using Gold Nanoparticles Supported on Metal Oxides.

    PubMed

    Sui, Ruohong; Lesage, Kevin L; Carefoot, Sarah K; Fürstenhaupt, Tobias; Rose, Chelsea J; Marriott, Robert A

    2016-09-13

    Selective capture of thiols from a synthetic hydrogen sulfide containing mixture using supported nanogold materials has been explored for the potential removal of thiols from sour gas production fluids. In this research, TiO2-, Al2O3-, SiO2-, and ZnO-supported gold nanoparticles have been studied for their usage as regeneratable adsorbents to capture CH3SH, C2H5SH, and i-C3H7SH. Au/TiO2 and Au/Al2O3 showed promising properties for removing the thiols efficiently from a gas-phase mixture; however, Au/Al2O3 did catalyze some undesirable side reactions, e.g., carbonyl sulfide formation. It was found that a mild temperature of T = 200 °C was sufficient for regeneration of either Au/TiO2 or Au/Al2O3 adsorbent. The metal oxide mesopores played an important role for accommodating gold particles and chemisorption of the thiols, where smaller pore sizes were found to inhibit the agglomeration/growth of gold particles. The nature of thiol adsorption and the impact of multiple adsorption-desorption cycles on the adsorbents have been studied using electron microscopy, XPS, XRD, GC, and physi/chemiadsorption analyses.

  11. Proteinase from germinating bean cotyledons. Evidence for involvement of a thiol group in catalysis.

    PubMed

    Csoma, C; Polgár, L

    1984-09-15

    To degrade storage proteins germinating seeds synthesize proteinases de novo that can be inhibited by thiol-blocking reagents [Baumgartner & Chrispeels (1977) Eur. J. Biochem. 77, 223-233]. We have elaborated a procedure for isolation of such a proteinase from the cotyledons of Phaseolus vulgaris. The purification procedure involved fractionation of the cotyledon homogenate with acetone and with (NH4)2SO4 and successive chromatographies on DEAE-cellulose, activated thiol-Sepharose Sepharose and Sephacryl S-200. The purified enzyme has an Mr of 23,400, proved to be highly specific for the asparagine side chain and blocking of its thiol group resulted in loss of the catalytic activity. The chemical properties of the thiol group of the bean enzyme were investigated by acylation with t-butyloxycarbonyl-L-asparagine p-nitro-phenyl ester and by alkylations with iodoacetamide and iodoacetate. Deviations from normal pH-rate profile were observed, which indicated that the thiol group is not a simple functional group, but constitutes a part of an interactive system at the active site. The pKa value for acylation and the magnitude of the rate constant for alkylation with iodoacetate revealed that the bean proteinase possesses some properties not shared by papain and the other cysteine proteinases studied to date.

  12. A Central Role for Thiols in Plant Tolerance to Abiotic Stress

    PubMed Central

    Zagorchev, Lyuben; Seal, Charlotte E.; Kranner, Ilse; Odjakova, Mariela

    2013-01-01

    Abiotic stress poses major problems to agriculture and increasing efforts are being made to understand plant stress response and tolerance mechanisms and to develop new tools that underpin successful agriculture. However, the molecular mechanisms of plant stress tolerance are not fully understood, and the data available is incomplete and sometimes contradictory. Here, we review the significance of protein and non-protein thiol compounds in relation to plant tolerance of abiotic stress. First, the roles of the amino acids cysteine and methionine, are discussed, followed by an extensive discussion of the low-molecular-weight tripeptide, thiol glutathione, which plays a central part in plant stress response and oxidative signalling and of glutathione-related enzymes, including those involved in the biosynthesis of non-protein thiol compounds. Special attention is given to the glutathione redox state, to phytochelatins and to the role of glutathione in the regulation of the cell cycle. The protein thiol section focuses on glutaredoxins and thioredoxins, proteins with oxidoreductase activity, which are involved in protein glutathionylation. The review concludes with a brief overview of and future perspectives for the involvement of plant thiols in abiotic stress tolerance. PMID:23549272

  13. Radiosensitization by misonidazole during recovery of cellular thiols following depletion by BSO or DEM

    SciTech Connect

    McNally, N.J.; Soranson, J.A.

    1989-05-01

    V79 cells have been depleted of their endogenous thiols by treatment with 100 microM BSO for 16-18 hr, or 0.5 mM DEM for 1 hr. The recovery of cellular thiols after removal of the drugs was determined by h.p.l.c. or flow cytometry and the sensitizer enhancement ratio for 100 microM misonidazole was measured as a function of time after removal of the drugs. The SER of 1.2 for control (hypoxic) cells increased to 1.8 for BSO treated (hypoxic) cells and 2.2 for DEM treated ones, when thiol levels were below 10% of controls. The SER and thiol levels returned to control values within 5 hr of removing DEM. After BSO there was little change during the first 5 hr and then a gradual return to normal values by 24 hrs. The major fall in the SER after removal of the drugs occurred as the cellular thiols increased to 60% of control values.

  14. Facile and Efficient Synthesis of Carbosiloxane Dendrimers via Orthogonal Click Chemistry Between Thiol and Ene.

    PubMed

    Zhang, Zhida; Feng, Shengyu; Zhang, Jie

    2016-02-01

    A combination of a thiol-Michael addition reaction and a free radical mediated thiol-ene reaction is employed as a facile and efficient approach to carbosiloxane dendrimer synthesis. For the first time, carbosiloxane dendrimers are constructed rapidly by an orthogonal click strategy without protection/deprotection procedures. The chemoselectivity of these two thiol-ene click reactions leads to a design of a new monomer containing both electron-deficient carbon-carbon double bonds and unconjugated carbon-carbon double bonds. Siloxane bonds are introduced as the linker between these two kinds of carbon-carbon double bonds. Starting from a bifunctional thiol core, the dendrimers are constructed by iterative thiol-ene click reactions under different but both mild reaction conditions. After simple purification steps the fifth dendrimer with 54 peripheral functional groups is obtained with an excellent overall yield in a single day. Furthermore, a strong blue glow is observed when the dendrimer is excited by a UV lamp.

  15. Mercury and protein thiols: Stimulation of mitochondrial F1FO-ATPase and inhibition of respiration.

    PubMed

    Nesci, Salvatore; Trombetti, Fabiana; Pirini, Maurizio; Ventrella, Vittoria; Pagliarani, Alessandra

    2016-12-25

    In spite of the known widespread toxicity of mercury, its impact on mitochondrial bioenergetics is a still poorly explored topic. Even if many studies have dealt with mercury poisoning of mitochondrial respiration, as far as we are aware Hg(2+) effects on individual complexes are not so clear. In the present study changes in swine heart mitochondrial respiration and F1FO-ATPase (F-ATPase) activity promoted by micromolar Hg(2+) concentrations were investigated. Hg(2+) was found to inhibit the respiration of NADH-energized mitochondria, whereas it was ineffective when the substrate was succinate. Interestingly, the same micromolar Hg(2+) doses which inhibited the NADH-O2 activity stimulated the F-ATPase, most likely by interacting with adjacent thiol residues. Accordingly, Hg(2+) dose-dependently decreased protein thiols and all the elicited effects on mitochondrial complexes were reversed by the thiol reducing agent DTE. These findings clearly indicate that Hg(2+) interacts with Cys residues of these complexes and differently modulate their functionality by modifying the redox state of thiol groups. The results, which cast light on some implications of metal-thiol interactions up to now not fully explored, may contribute to clarify the molecular mechanisms of mercury toxicity to mitochondria. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

  16. Pore surface engineering in a zirconium metal–organic framework via thiol-ene reaction

    SciTech Connect

    Gui, Bo; Hu, Guiping; Zhou, Tailin; Wang, Cheng

    2015-03-15

    A porous olefin-functionalized Zr(IV)-based metal–organic framework, denoted as UiO-68-allyl, has been constructed. Our results clearly demonstrated that the surface of UiO-68-allyl could be decorated with organic molecule (ethanethiol) via thiol-ene reaction. More importantly, the crystallinity of the framework were maintained during the post-synthetic modification process. However, the microporosity of the framework is retained but the surface area decreased, due to the grafting of ethylthio groups into the pores. From our studies, we can conclude that the strategy of post-synthetic modification of UiO-68-allyl via thiol-ene reaction may be general. Furthermore, we may anchor other desired functional group onto the pore walls in Zr-MOFs via thiol-ene reaction, enabling more potential applications. - graphical abstract: In this manuscript, we reported the post-synthetic modification of an olefin-functionalized Zr(IV)-based metal–organic framework via thiol-ene reaction. - Highlights: • A porous olefin-functionalized Zr(IV)-based metal–organic framework has been constructed. • The surface of olefin-functionalized Zr-MOF could be decorated with organic molecules via thiol-ene reaction. • The crystallinity and permanent porosity of the framework were maintained during the post-synthetic modification process.

  17. The synthesis of novel hybrid thiol-functionalized nano-structured SBA-15

    NASA Astrophysics Data System (ADS)

    Hoang, Van Duc; Phuong Dang, Tuyet; Khieu Dinh, Quang; Phu Nguyen, Huu; Vu, Anh Tuan

    2010-09-01

    Mesoporous thiol-functionalized SBA-15 has been directly synthesized by co-condensation of tetraethyl orthosilicate (TEOS) and 3-mercaptopropyltrimethoxysilane (MPTMS) with triblock copolymer P123 as-structure-directing agent under hydrothermal conditions. Surfactant removal was performed by Soxhlet ethanol extraction. These materials have been characterized by powder x-ray diffraction (XRD), nitrogen adsorption/desorption (BET model), transmission electron microscopy (TEM), thermal analysis, infrared spectroscopy (IR) and energy-dispersive x-ray spectroscopy (EDX). The main parameters, such as the initial molar ratio of MPTMS to TEOS, the time of adding MPTMS to synthesized gel and the Soxhlet ethanol extraction on the thiol functionalized SBA-15 with high thiol content and highly ordered hexagonal mesostructure, were investigated and evaluated. The adsorption capacity of the thiol-functionalized and non-functionalized SBA-15 materials for Pb2+ ion from aqueous solution was tested. It was found that the Pb2+ adsorption capacity of the thiol functionalized SBA-15 is three times higher than that of non-functionalized SBA-15.

  18. Quantification of protein thiols using ThioGlo 1 fluorescent derivatives and HPLC separation.

    PubMed

    Hoff, Signe; Larsen, Flemming H; Andersen, Mogens L; Lund, Marianne N

    2013-04-07

    A method for quantification of total soluble protein-derived thiols in beer was developed based on the formation of fluorescent adducts with the maleimide compound ThioGlo 1. The problem of interference from fluorescent adducts of sulfite and ThioGlo 1 was solved by HPLC separation of the adducts followed by fluorescence detection. Using standard addition of GSH, a detection limit of 0.028 μM thiols was achieved. The application and validation of the method was demonstrated for beers with different color intensities, and the application range is in principle for any biological system containing thiols. However, the quantification of cysteine was complicated by a lower fluorescence response of its ThioGlo 1 adducts. Based on the studies of the responses of a series of cysteine-derived thiols and (1)H NMR studies of the structures of ThioGlo 1 adducts with GSH and cysteine, it was concluded that thiols with a neighboring free amino group yield ThioGlo 1 adducts with a reduced fluorescence intensity.

  19. Thiol-disulfide exchange in peptides derived from human growth hormone.

    PubMed

    Chandrasekhar, Saradha; Epling, Daniel E; Sophocleous, Andreas M; Topp, Elizabeth M

    2014-04-01

    Disulfide bonds stabilize proteins by cross-linking distant regions into a compact three-dimensional structure. They can also participate in hydrolytic and oxidative pathways to form nonnative disulfide bonds and other reactive species. Such covalent modifications can contribute to protein aggregation. Here, we present experimental data for the mechanism of thiol-disulfide exchange in tryptic peptides derived from human growth hormone in aqueous solution. Reaction kinetics was monitored to investigate the effect of pH (6.0-10.0), temperature (4-50°C), oxidation suppressants [ethylenediaminetetraacetic acid (EDTA) and N2 sparging], and peptide secondary structure (amide cyclized vs. open form). The concentrations of free thiol containing peptides, scrambled disulfides, and native disulfide-linked peptides generated via thiol-disulfide exchange and oxidation reactions were determined using reverse-phase HPLC and liquid chromatography-mass spectrometry. Concentration versus time data were fitted to a mathematical model using nonlinear least squares regression analysis. At all pH values, the model was able to fit the data with R(2) ≥ 0.95. Excluding oxidation suppressants (EDTA and N2 sparging) resulted in an increase in the formation of scrambled disulfides via oxidative pathways but did not influence the intrinsic rate of thiol-disulfide exchange. In addition, peptide secondary structure was found to influence the rate of thiol-disulfide exchange.

  20. Comparative proteomic analysis of thiol proteins in the liver after oxidative stress induced by diethylnitrosamine.

    PubMed

    Aparicio-Bautista, Diana I; Pérez-Carreón, Julio I; Gutiérrez-Nájera, Nora; Reyes-Grajeda, Juan P; Arellanes-Robledo, Jaime; Vásquez-Garzón, Verónica R; Jiménez-García, Mónica N; Villa-Treviño, Saúl

    2013-12-01

    Conversion of protein -SH groups to disulfides is an early event during protein oxidation, which has prompted great interest in the study of thiol proteins. Chemical carcinogenesis is strongly associated with the formation of reactive oxygen species (ROS). The goal of this study was to detect thiol proteins that are sensitive to ROS generated during diethylnitrosamine (DEN) metabolism in the rat liver. DEN has been widely used to induce experimental hepatocellular carcinoma. We used modified redox-differential gel electrophoresis (redox-DIGE method) and mass spectrometry MALDI-TOF/TOF to identify differential oxidation protein profiles associated with carcinogen exposure. Our analysis revealed a time-dependent increase in the number of oxidized thiol proteins after carcinogen treatment; some of these proteins have antioxidant activity, including thioredoxin, peroxirredoxin 2, peroxiredoxin 6 and glutathione S-transferase alpha-3. According to functional classifications, the identified proteins in our study included chaperones, oxidoreductases, activity isomerases, hydrolases and other protein-binding partners. This study demonstrates that oxidative stress generated by DEN tends to increase gradually through DEN metabolism, causes time-dependent necrosis in the liver and has an oxidative effect on thiol proteins, thereby increasing the number of oxidized thiol proteins. Furthermore, these events occurred during the hepatocarcinogenesis initiation period.

  1. Redox regulation of Rac1 by thiol oxidation

    PubMed Central

    Hobbs, G. Aaron; Mitchell, Lauren E.; Arrington, Megan E.; Gunawardena, Harsha P.; DeCristo, Molly J.; Loeser, Richard F.; Chen, Xian; Cox, Adrienne D.; Campbell, Sharon L.

    2016-01-01

    The Rac1 GTPase is an essential and ubiquitous protein that signals through numerous pathways to control critical cellular processes, including cell growth, morphology, and motility. Rac1 deletion is embryonic lethal, and its dysregulation or mutation can promote cancer, arthritis, cardiovascular disease, and neurological disorders. Rac1 activity is highly regulated by modulatory proteins and posttranslational modifications. Whereas much attention has been devoted to guanine nucleotide exchange factors that act on Rac1 to promote GTP loading and Rac1 activation, cellular oxidants may also regulate Rac1 activation by promoting guanine nucleotide exchange. Herein, we show that Rac1 contains a redox-sensitive cysteine (Cys18) that can be selectively oxidized at physiological pH because of its lowered pKa. Consistent with these observations, we show that Rac1 is glutathiolated in primary chondrocytes. Oxidation of Cys18 by glutathione greatly perturbs Rac1 guanine nucleotide binding and promotes nucleotide exchange. As aspartate substitutions have been previously used to mimic cysteine oxidation, we characterized the biochemical properties of Rac1C18D. We also evaluated Rac1C18S as a redox-insensitive variant and found that it retains structural and biochemical properties similar to those of Rac1WT but is resistant to thiol oxidation. In addition, Rac1C18D, but not Rac1C18S, shows greatly enhanced nucleotide exchange, similar to that observed for Rac1 oxidation by glutathione. We employed Rac1C18D in cell-based studies to assess whether this fast-cycling variant, which mimics Rac1 oxidation by glutathione, affects Rac1 activity and function. Expression of Rac1C18D in Swiss 3T3 cells showed greatly enhanced GTP-bound Rac1 relative to Rac1WT and the redox-insensitive Rac1C18S variant. Moreover, expression of Rac1C18D in HEK-293T cells greatly promoted lamellipodia formation. Our results suggest that Rac1 oxidation at Cys18 is a novel posttranslational modification that

  2. Competitive reduction of perferrylmyoglobin radicals by protein thiols and plant phenols.

    PubMed

    Jongberg, Sisse; Lund, Marianne N; Skibsted, Leif H; Davies, Michael J

    2014-11-19

    Radical transfer from perferrylmyoglobin to other target species (myofibrillar proteins, MPI) and bovine serum albumin (BSA), extracts from green tea (GTE), maté (ME), and rosemary (RE), and three phenolic compounds, catechin, caffeic acid, and carnosic acid) was investigated by electron paramagnetic resonance (EPR) spectroscopy to determine the concentrations of plant extracts required to protect against protein oxidation. Blocking of MPI thiol groups by N-ethylmaleimide was found to reduce the rate of reaction of MPI with perferrylmyoglobin radicals, signifying the importance of protein thiols as radical scavengers. GTE had the highest phenolic content of the three extracts and was most effective as a radical scavenger. IC50 values indicated that the molar ratio between phenols in plant extract and MPI thiols needs to be >15 in order to obtain efficient protection against protein-to-protein radical transfer in meat. Caffeic acid was found most effective among the plant phenols.

  3. Influence of volatile thiols in the development of blackcurrant aroma in red wine.

    PubMed

    Rigou, Peggy; Triay, Aurélie; Razungles, Alain

    2014-01-01

    A strong blackcurrant aroma was recently perceived in some red wines originating from the same appellation. Varietal thiols such as 4-mercapto-4-methyl-2-pentanone (4MMP), 3-(mercapto)hexyl acetate (3MHA) and 3-mercapto-1-hexanol (3MH) are compounds potentially responsible for the development of this aroma. In order to demonstrate the correlation between thiols concentrations in red wines and blackcurrant aroma intensity, a multiple variable analysis was realised with thiols concentrations obtained by chemical analysis and blackcurrant aroma intensities obtained by descriptive sensory analysis. The 4MMP concentration was very well correlated to the blackcurrant aroma, and 3MHA and 3MH present at high concentrations act as enhancers of the perception of this aroma. This correlation was further supported after performing a sensory comparison by classification test. The different factors that could impact on the development of blackcurrant aroma in red wine were discussed. Copyright © 2013 Elsevier Ltd. All rights reserved.

  4. Pore surface engineering in a zirconium metal-organic framework via thiol-ene reaction

    NASA Astrophysics Data System (ADS)

    Gui, Bo; Hu, Guiping; Zhou, Tailin; Wang, Cheng

    2015-03-01

    A porous olefin-functionalized Zr(IV)-based metal-organic framework, denoted as UiO-68-allyl, has been constructed. Our results clearly demonstrated that the surface of UiO-68-allyl could be decorated with organic molecule (ethanethiol) via thiol-ene reaction. More importantly, the crystallinity of the framework were maintained during the post-synthetic modification process. However, the microporosity of the framework is retained but the surface area decreased, due to the grafting of ethylthio groups into the pores. From our studies, we can conclude that the strategy of post-synthetic modification of UiO-68-allyl via thiol-ene reaction may be general. Furthermore, we may anchor other desired functional group onto the pore walls in Zr-MOFs via thiol-ene reaction, enabling more potential applications.

  5. Novel solid-phase synthesis of thiol-terminated-poly(alpha-amino acid)-drug conjugate.

    PubMed

    Palacios, P; Bussat, P; Bichon, D

    1991-01-01

    A new method using a controlled pore glass solid support for the preparation of a thiol-terminated-polymerdrug, notably poly-L-glutamate-daunomycin having a terminal thiol group, is described. The method consists of first polymerizing an ester-protected glutamic acid onto an amino-disulfide functionalized controlled pore glass support. The ester protecting group is then removed, freeing the gamma-carboxyl groups of the grafted polymer which then allows it to react with daunomycin. Finally, the disulfide bond linking the conjugated polymer-drug to the solid support is broken by thiolysis, thus releasing the desired product. The final product consists of only polymer-drug conjugates with terminal thiol groups (global yield 26%). This novel method is much simpler and more elegant than more conventional preparation methods requiring solution phase techniques.

  6. Hybrid thiol-ene network nanocomposites based on multi(meth)acrylate POSS.

    PubMed

    Li, Liguo; Liang, Rendong; Li, Yajie; Liu, Hongzhi; Feng, Shengyu

    2013-09-15

    First, multi(meth)acrylate functionalized POSS monomers were synthesized in this paper. Secondly, FTIR was used to evaluate the homopolymerization behaviors of multi(meth)acrylate POSS and their copolymerization behaviors in the thiol-ene reactions with octa(3-mercaptopropyl) POSS in the presence of photoinitiator. Results showed that the photopolymerization rate of multimethacrylate POSS was faster than that of multiacrylate POSS. The FTIR results also showed that the copolymerizations were dominant in the thiol-ene reactions with octa(3-mercaptopropyl) POSS, different from traditional (meth)acrylate-thiol system, in which homopolymerizations were predominant. Finally, the resulted hybrid networks based on POSS were characterized by XRD, FE-SEM, DSC, and TGA. The characterization results showed that hybrid networks based on POSS were homogeneous and exhibited high thermal stability.

  7. Stability of binary SAMs formed by omega-acid and alcohol functionalized thiol mixtures.

    PubMed

    Tielens, Frederik; Humblot, Vincent; Pradier, Claire-Marie; Calatayud, Monica; Illas, Francesc

    2009-09-01

    A simple model is presented to describe the mixing process of acid- and alcohol-terminated thiol self-assembled monolayers (SAMs) on Au(111). It was found that the low-concentration acid-terminated SAMs are enriched in acid thiol compared with the original solution from which the SAM is made. Due to the relatively strong interaction between acid and alcohol head groups, homogeneously mixed SAMs showing alcohol/acid pairs are preferred when the acid-terminated thiol fraction in solution is below or equal to 50%. This particular behavior affecting the mixing process is explained using atomistic first-principle thermodynamics. The calculated phase diagram has been discussed and interpreted with the help of XPS.

  8. Hepatic thiol and glutathione efflux under the influence of vasopressin, phenylephrine and adrenaline.

    PubMed Central

    Sies, H; Graf, P

    1985-01-01

    Thiol and glutathione (GSH) efflux across the sinusoidal plasma membrane in isolated perfused rat liver was stimulated by addition of hormones such as vasopressin, phenylephrine and adrenaline, whereas glucagon or dibutyryl cyclic AMP were without effect. Phenylephrine and adrenaline effects were sensitive to prazosin and phentolamine, respectively. The increase in thiol efflux was largely accounted for by an increase in GSH efflux. Thiol efflux and the hormone effects were abolished in GSH-depleted liver. Biliary GSH efflux was diminished upon hormone addition. The newly discovered hormone-dependence of GSH release across the sinusoidal plasma membrane may explain the known loss of GSH during conditions of experimental shock (traumatic or endotoxin) and stress and peripheral inflammation. PMID:3994671

  9. Thiol-ene click reaction as a general route to functional trialkoxysilanes for surface coating applications.

    PubMed

    Tucker-Schwartz, Alexander K; Farrell, Richard A; Garrell, Robin L

    2011-07-27

    Functionalized trialkoxysilanes are widely used to modify the surface properties of materials and devices. It will be shown that the photoinitiated radical-based thiol-ene "click" reaction provides a simple and efficient route to diverse trialkoxysilanes. A total of 15 trialkoxysilanes were synthesized by reacting either alkenes with 3-mercaptopropyltrialkoxysilane or thiols with allyltrialkoxysilanes in the presence of a photoinitiator. The functionalized trialkoxysilanes were obtained in quantitative to near-quantitative yields with high purity. The photochemical reactions can be run neat in standard borosilicate glassware using a low power 15-W blacklight. A wide range of functional groups is tolerated in this approach, and even complex alkenes click with the silane precursors. To demonstrate that these silanes can be used as surface coating agents, several were reacted with iron oxide superparamagnetic nanoparticles and the loadings quantified. The photoinitiated thiol-ene reaction thus offers a facile and efficient method for preparing surface-active functional trialkoxysilanes.

  10. Electrical resistivity of nanoporous gold modified with thiol self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Hakamada, Masataka; Kato, Naoki; Mabuchi, Mamoru

    2016-11-01

    The electrical resistivity of nanoporous gold (NPG) modified with thiol self-assembled monolayers (SAMs) has been measured at 298 K using a four-probe method. We found that the adsorption of thiol SAMs increases the electrical resistivity of NPG by up to 22.2%. Dependence of the electrical resistivity on the atmosphere (air or water) was also observed in SAMs-modified NPG, suggesting that the electronic states of the tail groups affect the electrons of the binding sulfur and adjacent surface gold atoms. The present results suggest that adsorption of thiol molecules can influence the behavior of the conducting electrons in NPG and that modification of NPG with SAMs may be useful for environmental sensing.

  11. Thiolated pyrimidine nucleotides may interfere thiol groups concentrated at lipid rafts of HIV-1 infected cells.

    PubMed

    Kanizsai, Szilvia; Ongrádi, Joseph; Aradi, János; Nagy, Károly

    2014-12-01

    Upon HIV infection, cells become activated and cell surface thiols are present in increased number. Earlier we demonstrated in vitro anti-HIV effect of thiolated pyrimidine nucleotide UD29, which interferes thiol function. To further analyse the redox processes required for HIV-1 entry and infection, toxicity assays were performed using HIV-1 infected monolayer HeLaCD4-LTR/ β-gal cells and suspension H9 T cells treated with several thiolated nucleotide derivatives of UD29. Selective cytotoxicity of thiolated pyrimidines on HIV-1 infected cells were observed. Results indicate that thiolated pyrimidine derivates may interfere with -SH (thiol) groups concentrated in lipid rafts of cell membrane and interacts HIV-1 infected (activated) cells resulting in a selective cytotoxicity of HIV-1 infected cells, and reducing HIV-1 entry.

  12. D-penicillamine and other low molecular weight thiols: review of anticancer effects and related mechanisms.

    PubMed

    Wadhwa, Saurabh; Mumper, Russell J

    2013-08-28

    Low molecular weight thiols (LMWTs) like N-acetyl cysteine, D-penicillamine, captopril, Disulfiram and Amifostine, etc. have been used as chemo-preventive agents. Recent studies have reported cell growth inhibition and cytotoxicity in several different types of cancer cells following treatment with several LMWTs. Cytotoxic and cytostatic effects of LMWTs may involve interaction of the thiol group with cellular lipids, proteins, intermediates or enzymes. Some of the mechanisms that have been proposed include a p53 mediated apoptosis, thiyl radical induced DNA damage, membrane damage through lipid peroxidation, anti-angiogenic effects induced by inhibition of matrix metalloproteinase enzymes and angiostatin generation. LMWTs are strong chelators of transition metals like copper, nickel, zinc, iron and cobalt and may cause metal co-factor depletion resulting in cytotoxicity. Oxidation of thiol group can also generate cytotoxic reactive oxygen species (ROS).

  13. Infant Day Care and Attachment.

    ERIC Educational Resources Information Center

    Caldwell, Bettye M.; And Others

    In a longitudinal study, a group of 41 children from lower class families were examined for differences in child-mother and mother-child attachment patterns at 30 months of age. Twenty-three children had been cared for by their mothers from birth until 30 months of age, and 18 had been enrolled in a day care center for at least 1 year. Data…

  14. Trauma, attachment, and intimate relationships.

    PubMed

    Zurbriggen, Eileen L; Gobin, Robyn L; Kaehler, Laura A

    2012-01-01

    Intimate relationships can both affect and be affected by trauma and its sequelae. This special issue highlights research on trauma, attachment, and intimate relationships. Several themes emerged. One theme is the exploration of the associations between a history of trauma and relational variables, with an emphasis on models using these variables as mediators. Given the significance of secure attachment for healthy relationships, it is not surprising that attachment emerges as another theme of this issue. Moreover, a key component of relationships is trust, and so a further theme of this issue is betrayal trauma (J. J. Freyd, 1996 ). As the work included in this special issue makes clear, intimate relationships of all types are important for the psychological health of those exposed to traumatic events. In order to best help trauma survivors and those close to them, it is imperative that research exploring these issues be presented to research communities, clinical practitioners, and the public in general. This special issue serves as one step toward that objective.

  15. Cellular recovery of glyceraldehyde-3-phosphate dehydrogenase activity and thiol status after exposure to hydroperoxides

    SciTech Connect

    Brodie, A.E.; Reed, D.J. )

    1990-01-01

    The activity of the thiol-dependent enzyme glyceraldehyde-3-phosphate dehydrogenase (GPD), in vertebrate cells, was modulated by a change in the intracellular thiol:disulfide redox status. Human lung carcinoma cells (A549) were incubated with 1-120 mM H2O2, 1-120 mM t-butyl hydroperoxide, 1-6 mM ethacrynic acid, or 0.1-10 mM N-ethylmaleimide for 5 min. Loss of reduced protein thiols, as measured by binding of the thiol reagent iodoacetic acid to GPD, and loss of GPD enzymatic activity occurred in a dose-dependent manner. Incubation of the cells, following oxidative treatment, in saline for 30 min or with 20 mM dithiothreitol (DTT) partially reversed both changes in GPD. The enzymatic recovery of GPD activity was observed either without addition of thiols to the medium or by incubation of a sonicated cell mixture with 2 mM cysteine, cystine, cysteamine, or glutathione (GSH); GSSG had no effect. Treatment of cells with buthionine sulfoximine (BSO) to decrease cellular GSH by varying amounts caused a dose-related increase in sensitivity of GPD activity to inactivation by H2O2 and decreased cellular ability for subsequent recovery. GPD responded in a similar fashion with oxidative treatment of another lung carcinoma cell line (A427) as well as normal lung tissue from human and rat. These findings indicate that the cellular thiol redox status can be important in determining GPD enzymatic activity.

  16. Conferring specificity in redox pathways by enzymatic thiol/disulfide exchange reactions.

    PubMed

    Netto, Luis Eduardo S; de Oliveira, Marcos Antonio; Tairum, Carlos A; da Silva Neto, José Freire

    2016-01-01

    Thiol-disulfide exchange reactions are highly reversible, displaying nucleophilic substitutions mechanism (S(N)2 type). For aliphatic, low molecular thiols, these reactions are slow, but can attain million times faster rates in enzymatic processes. Thioredoxin (Trx) proteins were the first enzymes described to accelerate thiol-disulfide exchange reactions and their high reactivity is related to the high nucleophilicity of the attacking thiol. Substrate specificity in Trx is achieved by several factors, including polar, hydrophobic, and topological interactions through a groove in the active site. Glutaredoxin (Grx) enzymes also contain the Trx fold, but they do not share amino acid sequence similarity with Trx. A conserved glutathione binding site is a typical feature of Grx that can reduce substrates by two mechanisms (mono and dithiol). The high reactivity of Grx enzymes is related to the very acid pK(a) values of reactive Cys that plays roles as good leaving groups. Therefore, although distinct oxidoreductases catalyze similar thiol–disulfide exchange reactions, their enzymatic mechanisms vary. PDI and DsbA are two other oxidoreductases, but they are involved in disulfide bond formation, instead of disulfide reduction, which is related to the oxidative environment where they are found. PDI enzymes and DsbC are endowed with disulfide isomerase activity, which is related with their tetra-domain architecture. As illustrative description of specificity in thiol-disulfide exchange, redox aspects of transcription activation in bacteria, yeast, and mammals are presented in an evolutionary perspective. Therefore, thiol-disulfide exchange reactions play important roles in conferring specificity to pathways, a required feature for signaling.

  17. Redox regulation of mitochondrial proteins and proteomes by cysteine thiol switches.

    PubMed

    Nietzel, Thomas; Mostertz, Jörg; Hochgräfe, Falko; Schwarzländer, Markus

    2017-03-01

    Mitochondria are hotspots of cellular redox biochemistry. Respiration as a defining mitochondrial function is made up of a series of electron transfers that are ultimately coupled to maintaining the proton motive force, ATP production and cellular energy supply. The individual reaction steps involved require tight control and flexible regulation to maintain energy and redox balance in the cell under fluctuating demands. Redox regulation by thiol switching has been a long-standing candidate mechanism to support rapid adjustment of mitochondrial protein function at the posttranslational level. Here we review recent advances in our understanding of cysteine thiol switches in the mitochondrial proteome with a focus on their operation in vivo. We assess the conceptual basis for thiol switching in mitochondria and discuss to what extent insights gained from in vitro studies may be valid in vivo, considering thermodynamic, kinetic and structural constraints. We compare functional proteomic approaches that have been used to assess mitochondrial protein thiol switches, including thioredoxin trapping, redox difference gel electrophoresis (redoxDIGE), isotope-coded affinity tag (OxICAT) and iodoacetyl tandem mass tag (iodoTMT) labelling strategies. We discuss conditions that may favour active thiol switching in mitochondrial proteomes in vivo, and appraise recent advances in dissecting their impact using combinations of in vivo redox sensing and quantitative redox proteomics. Finally we focus on four central facets of mitochondrial biology, aging, carbon metabolism, energy coupling and electron transport, exemplifying the current emergence of a mechanistic understanding of mitochondrial regulation by thiol switching in living plants and animals. Copyright © 2016 Elsevier B.V. and Mitochondria Research Society. All rights reserved.

  18. Coordination chemistry controls the thiol oxidase activity of the B12-trafficking protein CblC.

    PubMed

    Li, Zhu; Shanmuganathan, Aranganathan; Ruetz, Markus; Yamada, Kazuhiro; Lesniak, Nicholas A; Kräutler, Bernhard; Brunold, Thomas C; Koutmos, Markos; Banerjee, Ruma

    2017-06-09

    The cobalamin or B12 cofactor supports sulfur and one-carbon metabolism and the catabolism of odd-chain fatty acids, branched-chain amino acids, and cholesterol. CblC is a B12-processing enzyme involved in an early cytoplasmic step in the cofactor-trafficking pathway. It catalyzes the glutathione (GSH)-dependent dealkylation of alkylcobalamins and the reductive decyanation of cyanocobalamin. CblC from Caenorhabditis elegans (ceCblC) also exhibits a robust thiol oxidase activity, converting reduced GSH to oxidized GSSG with concomitant scrubbing of ambient dissolved O2 The mechanism of thiol oxidation catalyzed by ceCblC is not known. In this study, we demonstrate that novel coordination chemistry accessible to ceCblC-bound cobalamin supports its thiol oxidase activity via a glutathionyl-cobalamin intermediate. Deglutathionylation of glutathionyl-cobalamin by a second molecule of GSH yields GSSG. The crystal structure of ceCblC provides insights into how architectural differences at the α- and β-faces of cobalamin promote the thiol oxidase activity of ceCblC but mute it in wild-type human CblC. The R161G and R161Q mutations in human CblC unmask its latent thiol oxidase activity and are correlated with increased cellular oxidative stress disease. In summary, we have uncovered key architectural features in the cobalamin-binding pocket that support unusual cob(II)alamin coordination chemistry and enable the thiol oxidase activity of ceCblC. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

  19. Janus Gold Nanoparticles from Nanodroplets of Alkyl Thiols: A Molecular Dynamics Study.

    PubMed

    Bhandary, Debdip; Valechi, Vasumathi; Cordeiro, Maria Natália D S; Singh, Jayant K

    2017-03-28

    Janus particles provide an asymmetry in structure, which can impart diverse functionalities leading to immense importance in various applications, ranging from targeted delivery to interfacial phenomena, including catalysis, electronics, and optics. In this work, we present results of a molecular dynamics study of the growth mechanism of coating on gold nanoparticles (AuNPs) from droplets of n-alkyl thiols with different chain lengths (C5 and C11) and terminal groups (CH3 and COOH). The effect of chain lengths and functional groups on the formation of a monolayer of alkyl thiols on AuNPs is investigated. A two-step mechanism, initiated by the binding of the droplet to the nanoparticle surface with a time constant on the order of ∼1 ns, followed by the diffusion-driven growth with a larger time constant (on the order of 100 ns), is shown to capture the growth dynamics of the monolayer. It is observed that the time required for complete wetting increases with an increase in the chain length. Moreover, the monolayer formation is slowed down in the presence of carboxyl groups because of strong hydrogen bonding. The kinetics of the n-alkyl thiols coating on the nanoparticles is found to be independent of the droplet size but carboxyl-terminated thiols spread more with increasing droplet size. Furthermore, different time constants for different chains and functional groups yield Janus coating when two droplets of alkyl thiols with different terminal groups are allowed to form monolayers on the nanoparticle. The Janus balance (β) for different combinations of alkyl thiols and nanoparticle sizes varies in the range of 0.42-0.71.

  20. Engineering volatile thiol release in Saccharomyces cerevisiae for improved wine aroma.

    PubMed

    Swiegers, Jan H; Capone, Dimitra L; Pardon, Kevin H; Elsey, Gordon M; Sefton, Mark A; Francis, I Leigh; Pretorius, Isak S

    2007-07-01

    Volatile thiols, such as 4-mercapto-4-methylpentan-2-one (4MMP), 3-mercaptohexan-1-ol (3MH) and 3-mercaptohexyl acetate (3MHA), are among the most potent aroma compounds found in wine and can have a significant effect on wine quality and consumer preferences. At optimal concentrations in wine, these compounds impart flavours of passionfruit, grapefruit, gooseberry, blackcurrant, lychee, guava and box hedge. The enzymatic release of aromatic thiols from grape-derived, non-volatile cysteinylated precursors (Cys-4MMP and Cys-3MH) and the further modification thereof (conversion of 3MH into 3MHA) during fermentation, enhance the varietal characters of wines such as Sauvignon Blanc. Wine yeast strains have limited and varying capacities to produce aroma-enhancing thiols from their non-volatile counterparts in grape juice. Even under optimal fermentation conditions, the most efficient thiol-releasing Saccharomyces cerevisiae wine strain known realizes less than 5% of the thiol-related flavour potential of grape juice. The objective of this study was to develop a wine yeast able to unleash the untapped thiol aromas in grape juice during winemaking. To achieve this goal, the Escherichia coli tnaA gene, encoding a tryptophanase with strong cysteine-beta-lyase activity, was cloned and overexpressed in a commercial wine yeast strain under the control of the regulatory sequences of the yeast phosphoglycerate kinase I gene (PGK1). This modified strain expressing carbon-sulphur lyase activity released up to 25 times more 4MMP and 3MH in model ferments than the control host strain. Wines produced with the engineered strain displayed an intense passionfruit aroma. This yeast offers the potential to enhance the varietal aromas of wines to predetermined market specifications.

  1. Protein Thiol Oxidation in Murine Airway Epithelial Cells in Response to Naphthalene or Diethyl Maleate

    PubMed Central

    Spiess, Page C.; Morin, Dexter; Williams, Chase R.; Buckpitt, Alan R.

    2010-01-01

    Naphthalene (NA) is a semivolatile aromatic hydrocarbon to which humans are exposed from a variety of sources. NA results in acute cytotoxicity to respiratory epithelium in rodents. Cytochrome P450-dependent metabolic activation to form reactive intermediates and loss of soluble cellular thiols (glutathione) are critical steps in NA toxicity, but the precise mechanisms by which this chemical results in cellular injury remain unclear. Protein thiols are likely targets of reactive NA metabolites. Loss of these, through adduction or thiol oxidation mechanisms, may be important underlying mechanisms for NA toxicity. To address the hypothesis that loss of thiols on specific cellular proteins is critical to NA-induced cytotoxicity, we compared reduced to oxidized thiol ratios in airway epithelial cell proteins isolated from lungs of mice treated with NA or the nontoxic glutathione depletor, diethyl maleate (DEM). At 300 mg/kg doses, NA administration resulted in a greater than 85% loss of glutathione levels in the airway epithelium, which is similar to the loss observed after DEM treatment. Using differential fluorescent maleimide labeling followed by 2DE separation of proteins, we identified more than 35 unique proteins that have treatment-specific differential sulfhydryl oxidation. At doses of NA and DEM that produce similar levels of glutathione depletion, Cy3/Cy5 labeling ratios were statistically different for 16 nonredundant proteins in airway epithelium. Proteins identified include a zinc finger protein, several aldehyde dehydrogenase variants, β-actin, and several other structural proteins. These studies show distinct patterns of protein thiol alterations with the noncytotoxic DEM and the cytotoxic NA. PMID:19843705

  2. Reactions of oxidatively activated arylamines with thiols: reaction mechanisms and biologic implications. An overview.

    PubMed Central

    Eyer, P

    1994-01-01

    Aromatic amines belong to a group of compounds that exert their toxic effects usually after oxidative biotransformation, primarily in the liver. In addition, aromatic amines also undergo extrahepatic activation to yield free arylaminyl radicals. The reactive intermediates are potential promutagens and procarcinogens, and responsible for target tissue toxicity. Since thiols react with these intermediates at high rates, it is of interest to know the underlying reaction mechanisms and the toxicologic implications. Phenoxyl radicals from aminophenols and aminyl radicals from phenylenediamines quickly disproportionate to quinone imines and quinone diimines. Depending on the structure, Michael addition or reduction reactions with thiols may prevail. Products of sequential oxidation/addition reactions (e.g., S-conjugates of aminophenols) are occasionally more toxic than the parent compounds because of their higher autoxidizability and their accumulation in the kidney. Even after covalent binding of quinone imines to protein SH groups, the resulting thioethers are able to autoxidize. The quinoid thioethers can then cross-link the protein by addition to neighboring nucleophiles. The reactions of nitrosoarenes with thiols yield a so-called "semimercaptal" from which various branching reactions detach, depending on substituents. Compounds with strong pi-donors, like 4-nitrosophenetol, give a resonance-stabilized N-(thiol-S-yl)-arylamine cation that may lead to bicyclic products, thioethers, and DNA adducts. Examples of toxicologic implications of the interactions of nitroso compounds with thiols are given for nitrosoimidazoles, heterocyclic nitroso compounds from protein pyrolysates, and nitrosoarenes. These data indicate that interactions of activated arylamines with thiols may not be regarded exclusively as detoxication reactions. PMID:7889834

  3. Coronary Artery Spasm Related to Thiol Oxidation and Senescence Marker Protein-30 in Aging

    PubMed Central

    Yamada, Shinya; Machii, Hirofumi; Mizukami, Hiroyuki; Hoshino, Yasuto; Misaka, Tomofumi; Ishigami, Akihito; Takeishi, Yasuchika

    2013-01-01

    Abstract Background: Senescence marker protein-30 (SMP30) decreases with aging, and SMP30 knockout (KO) mice show a short life with increased oxidant stress. Aims: We assessed the effect of oxidant stress with SMP30 deficiency in coronary artery spasm and clarify its underlying mechanisms. Results: We measured vascular responses to acetylcholine (ACh) and sodium nitroprusside (SNP) of isolated coronary arteries from SMP30 KO and wild-type (WT) mice. In SMP30 KO mice, ACh-induced vasoconstriction occurred, which was changed to vasodilation by dithiothreitol (DTT), a thiol-reducing agent. However, Nω-nitro-l-arginine-methyl ester, nitric oxide (NO) synthase inhibitor, or tetrahydrobiopterin did not change the ACh response. In isolated coronary arteries of WT mice, ACh-induced vasodilation occurred. Inhibition of glutathione reductase by 1, 3-bis(2-chloroethyl)-1-nitrosourea decreased ACh-induced vasodilation (n=10, p<0.01), which was restored by DTT. To evaluate the thiol oxidation, we measured the fluorescence of monochlorobimane (MCB) in coronary arteries, which covalently labels the total. The fluorescence level to MCB decreased in SMP30 KO mice, but with DTT treatment restored to a level comparable to that of WT mice. The reduced glutathione and total thiol levels were also low in the aorta of SMP30 KO mice compared with those of WT mice. Administration of ACh into the aortic sinus in vivo of SMP30 KO mice induced coronary artery spasm. Innovation: The thiol redox state is a key regulator of endothelial NO synthase activity, and thiol oxidation was associated with endothelial dysfunction in the SMP30 deficiency model. Conclusion: These results suggest that chronic thiol oxidation by oxidant stress is a trigger of coronary artery spasm, resulting in impaired endothelium-dependent vasodilation. Antioxid. Redox Signal. 19, 1063–1073. PMID:23320823

  4. Stretching of BDT-gold molecular junctions: thiol or thiolate termination?

    NASA Astrophysics Data System (ADS)

    Souza, Amaury De Melo; Rungger, Ivan; Pontes, Renato Borges; Rocha, Alexandre Reily; da Silva, Antônio José Roque; Schwingenschlöegl, Udo; Sanvito, Stefano

    2014-11-01

    It is often assumed that the hydrogen atoms in the thiol groups of a benzene-1,4-dithiol dissociate when Au-benzene-1,4-dithiol-Au junctions are formed. We demonstrate, by stability and transport property calculations, that this assumption cannot be made. We show that the dissociative adsorption of methanethiol and benzene-1,4-dithiol molecules on a flat Au(111) surface is energetically unfavorable and that the activation barrier for this reaction is as high as 1 eV. For the molecule in the junction, our results show, for all electrode geometries studied, that the thiol junctions are energetically more stable than their thiolate counterparts. Due to the fact that density functional theory (DFT) within the local density approximation (LDA) underestimates the energy difference between the lowest unoccupied molecular orbital and the highest occupied molecular orbital by several electron-volts, and that it does not capture the renormalization of the energy levels due to the image charge effect, the conductance of the Au-benzene-1,4-dithiol-Au junctions is overestimated. After taking into account corrections due to image charge effects by means of constrained-DFT calculations and electrostatic classical models, we apply a scissor operator to correct the DFT energy level positions, and calculate the transport properties of the thiol and thiolate molecular junctions as a function of the electrode separation. For the thiol junctions, we show that the conductance decreases as the electrode separation increases, whereas the opposite trend is found for the thiolate junctions. Both behaviors have been observed in experiments, therefore pointing to the possible coexistence of both thiol and thiolate junctions. Moreover, the corrected conductance values, for both thiol and thiolate, are up to two orders of magnitude smaller than those calculated with DFT-LDA. This brings the theoretical results in quantitatively good agreement with experimental data.

  5. Emanuel Miller Lecture: Attachment Insecurity, Disinhibited Attachment, and Attachment Disorders--Where Do Research Findings Leave the Concepts?

    ERIC Educational Resources Information Center

    Rutter, Michael; Kreppner, Jana; Sonuga-Barke, Edmund

    2009-01-01

    Background: Despite the evidence on anomalous attachment patterns, there has been a tendency to interpret most of these as reflecting differences in security/insecurity. Methods: Empirical research findings are reviewed in relation to attachment/insecurity as evident in both infancy and later childhood, disorganised attachment, inhibited…

  6. Straightforward synthesis of deuterated precursors to demonstrate the biogenesis of aromatic thiols in wine.

    PubMed

    Roland, Aurélie; Schneider, Rémi; Razungles, Alain; Le Guernevé, Christine; Cavelier, Florine

    2010-10-13

    Straightforward synthesis of labeled S-3-(hexan-1-ol)-glutathione and S-4-(4-methylpentan-2-one)-glutathione has been developed through a conjugate addition optimization study. Sauvignon blanc fermentation experiments with the [(2)H(10)] S-4-(4-methylpentan-2-one)-glutathione used as a tracer released the corresponding deuterated thiol, thus proving the direct relationship with the 4-mercapto-4-methylpentan-2-one under enological conditions. The conversion yield of such transformation was estimated to be close to 0.3%, opening an avenue for additional study on varietal thiol biogenesis.

  7. XAFS study on structural order in highly monodispersed thiol-stabilized Au nanoparticles

    NASA Astrophysics Data System (ADS)

    Huang, Y.; Liu, W.; Yang, L.; Huang, T.; Jiang, Y.; Yao, T.; Wei, S.

    2016-05-01

    Understanding the influence of thiol on nanoparticle size and structure is essential for the fundamental and applied researches. Here, using x-ray absorption fine structure (XAFS) spectroscopy, we investigate the structural order of Au nanoparticles (NPs) in the protection of thiol ligands with different contents. We found that besides protecting Au NPs against aggregation and growth, thiolates can effectively eliminate the dangling bonds of unsaturated Au atoms, and thus increase the structural order. This work enriches our knowledge of Au-S interface interaction and guides the way towards preparing size-controllable nanoparticles with specific physical/chemical properties.

  8. Thiol-catalyzed formation of lactate and glycerate from glyceraldehyde. [significance in molecular evolution

    NASA Technical Reports Server (NTRS)

    Weber, A. L.

    1983-01-01

    The rate of lactate formation from glyceraldehyde, catalyzed by N-acetyl-cysteine at ambient temperature in aqueous sodium phosphate (pH 7.0), is more rapid at higher sodium phosphate concentrations and remains essentially the same in the presence and absence of oxygen. The dramatic increase in the rate of glycerate formation that is brought about by this thiol, N-acetylcysteine, is accompanied by commensurate decreases in the rates of glycolate and formate production. It is suggested that the thiol-dependent formation of lactate and glycerate occurs by way of their respective thioesters. Attention is given to the significance of these reactions in the context of molecular evolution.

  9. Thiol activated prodrugs of sulfur dioxide (SO2) as MRSA inhibitors.

    PubMed

    Pardeshi, Kundansingh A; Malwal, Satish R; Banerjee, Ankita; Lahiri, Surobhi; Rangarajan, Radha; Chakrapani, Harinath

    2015-07-01

    Drug resistant infections are becoming common worldwide and new strategies for drug development are necessary. Here, we report the synthesis and evaluation of 2,4-dinitrophenylsulfonamides, which are donors of sulfur dioxide (SO2), a reactive sulfur species, as methicillin-resistant Staphylococcus aureus (MRSA) inhibitors. N-(3-Methoxyphenyl)-2,4-dinitro-N-(prop-2-yn-1-yl)benzenesulfonamide (5e) was found to have excellent in vitro MRSA inhibitory potency. This compound is cell permeable and treatment of MRSA cells with 5e depleted intracellular thiols and enhanced oxidative species both results consistent with a mechanism involving thiol activation to produce SO2.

  10. Evaluation of thiol Raman activities and pKa values using internally referenced Ramanbased pH titration

    NASA Astrophysics Data System (ADS)

    Suwandaratne, Nuwanthi

    Thiols are one of the most important classes of chemicals used broadly in organic synthesis, biological chemistry, and nanosciences. Thiol pKa values are key indicators of thiol reactivity and functionality. This study is an internally-referenced Raman-based pH titration method that enables reliable quantification of thiol pKa values for both mono- and di-thiols in water. The degree of thiol ionization is monitored directly using the peak intensity of the S-H stretching feature relative to an internal reference peak as a function of solution pH. The thiol pKa values and Raman activity relative to its internal reference were then determined by curve-fitting the experimental data with equations derived on the basis of the Henderson-Hasselbalch equation. Using this Raman titration method, first and second thiol pKa values for 1,2-benzenedithol in water were determined for the first time. This method is convenient to implement and its underlying theory is easy to follow.

  11. Increased levels of thiols protect antimony unresponsive Leishmania donovani field isolates against reactive oxygen species generated by trivalent antimony

    PubMed Central

    Mandal, G.; Wyllie, S.; Singh, N.; Sundar, S.; Fairlamb, A.H.; Chatterjee, M.

    2012-01-01

    Summary The current trend of antimony (Sb) unresponsiveness in the Indian subcontinent is a major impediment to effective chemotherapy of visceral leishmaniasis (VL). Although contributory mechanisms studied in laboratory raised Sb-R parasites include an up regulation of drug efflux pumps and increased thiols, their role in clinical isolates is not yet substantiated. Accordingly, our objectives were to study the contributory role of thiols in generation of Sb unresponsiveness in clinical isolates. Promastigotes were isolated from VL patients who were either Sb responsive (n = 2) or unresponsive (n = 3). Levels of thiols as measured by HPLC and flow cytometry showed higher basal levels of thiols and a faster rate of thiol regeneration in Sb unresponsive strains as compared with sensitive strains. The effects of antimony on generation of reactive oxygen species (ROS) in normal and thiol depleted conditions as also their H2O2 scavenging activity indicated that in unresponsive parasites, Sb mediated ROS generation was curtailed which could be reversed by depletion of thiols and was accompanied by a higher H2O2 scavenging activity. Higher levels of thiols in Sb unresponsive field isolates from patients with VL protects parasites from Sb mediated oxidative stress, thereby contributing to the antimony resistance phenotype. PMID:17612420

  12. Attachment theory: progress and future directions.

    PubMed

    Fearon, R M Pasco; Roisman, Glenn I

    2017-06-01

    Attachment is a key subfield in the area of parenting and parent-child relationships research. In this brief overview, we summarise what we consider to be the state-of-the-art of attachment research, focusing primarily on the nature and significance of attachment in infancy and early childhood. We review 4 major topics that are central issues in the scientific literature on attachment: (1) the role of the environment in the development of attachment, (2) the intergenerational transmission of patterns of attachment, (3) the stability of attachment patterns through early adulthood, and (4) the role of attachment in adjustment and maladjustment. We conclude by highlighting several critical unresolved issues and priorities for future research. Copyright © 2017. Published by Elsevier Ltd.

  13. 78 FR 52868 - Pole Attachment Complaint Procedures

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-08-27

    ... From the Federal Register Online via the Government Publishing Office FEDERAL COMMUNICATIONS COMMISSION 47 CFR Part 1 Pole Attachment Complaint Procedures AGENCY: Federal Communications Commission... regulations concerning pole attachments outlined in the DATES section. DATES: Effective August 27, 2013,...

  14. Attaching Chuck Keys to Machine Tools

    NASA Technical Reports Server (NTRS)

    Richardson, V.

    1984-01-01

    Chuck keys attached to portable machine tools by retracting lanyards. Lanyard held taut by recoil caddy attached to tool base. Chuck key available for use when needed and safely secured during operation of tool.

  15. Avoidant attachment and the experience of parenting.

    PubMed

    Rholes, W Steven; Simpson, Jeffry A; Friedman, Mike

    2006-03-01

    Guided by attachment theory, this research investigated connections between avoidant attachment styles and the experience of parenting after the birth of a couple's first child. One hundred and six couples completed a battery of measures approximately 6 weeks before and 6 months after the birth of their first child. As anticipated, parents with more avoidant attachment styles experienced greater stress after the birth of their child and perceived parenting as less satisfying and personally meaningful. Attachment theory maintains that adult attachment styles should affect relationships with adults and with one's children. The present findings provide some of the first evidence that self-reported adult romantic attachment styles, which have been the focus of attachment research by social and personality psychologists, are systematically associated with parent-child relationships. They also provide insight into the processes through which secure and insecure attachment styles might be transmitted from one generation to the next.

  16. Attaching Chuck Keys to Machine Tools

    NASA Technical Reports Server (NTRS)

    Richardson, V.

    1984-01-01

    Chuck keys attached to portable machine tools by retracting lanyards. Lanyard held taut by recoil caddy attached to tool base. Chuck key available for use when needed and safely secured during operation of tool.

  17. [Connections between attachment prototypes and relationship patterns].

    PubMed

    Albani, Cornelia; Blaser, Gerd; Körner, Annett; König, Susanne; Marschke, Franziska; Geissler, Ilka; Brenk, Katja; Geyer, Michael; Strauss, Bernhard

    2002-12-01

    Connections between attachment styles and relationship patterns are studied on 32 female psychotherapy patients. Our study gives first hints to a connection between attachment variables, assessed by the German version of the Adult Attachment Prototype Rating (AAPR) and predominant relationship patterns, assessed by the Core Conflictual Relationship Theme Method (CCRT) developed by Luborsky, if both methods are used independently. Subsamples according to the attachment styles show differences in CCRT variables.

  18. Preparation of a novel carboxyl stationary phase by "thiol-ene" click chemistry for hydrophilic interaction chromatography.

    PubMed

    Peng, Xi-Tian; Liu, Tao; Ji, Shu-Xian; Feng, Yu-Qi

    2013-08-01

    A novel carboxyl-bonded silica stationary phase was prepared by "thiol-ene" click chemistry. The resultant Thiol-Click-COOH phase was evaluated under hydrophilic interaction liquid chromatography (HILIC) mobile phase conditions. A comparison of the chromatographic performance of Thiol-Click-COOH and pure silica columns was performed according to the retention behaviors of analytes and the charged state of the stationary phases. The results indicated that the newly developed Thiol-Click-COOH column has a higher surface charge and stronger hydrophilicity than the pure silica column. Furthermore, the chromatographic behaviors of five nucleosides on the Thiol-Click-COOH phase were investigated in detail. Finally, a good separation of 13 nucleosides and bases, and four water-soluble vitamins was achieved.

  19. Selective chromogenic detection of thiol-containing biomolecules using carbonaceous nanospheres loaded with silver nanoparticles as carrier.

    PubMed

    Hu, Bo; Zhao, Yang; Zhu, Hai-Zhou; Yu, Shu-Hong

    2011-04-26

    Thiol-containing biomolecules show strong affinity with noble metal nanostructures and could not only stably protect them but also control the self-assembly process of these special nanostructures. A highly selective and sensitive chromogenic detection method has been designed for the low and high molecular weight thiol-containing biomolecules, including cysteine, glutathione, dithiothreitol, and bovine serum albumin, using a new type of carbonaceous nanospheres loaded with silver nanoparticles (Ag NPs) as carrier. This strategy relies upon the place-exchange process between the reporter dyes on the surface of Ag NPs and the thiol groups of thiol-containing biomolecules. The concentration of biomolecules can be determined by monitoring with the fluorescence intensity of reporter dyes dispersed in solution. This new chromogenic assay method could selectively detect these biomolecules in the presence of various other amino acids and monosaccharides and even sensitively detect the thiol-containing biomolecules with different molecular weight, even including proteins.

  20. 10 CFR 75.15 - Facility attachments.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 10 Energy 2 2013-01-01 2013-01-01 false Facility attachments. 75.15 Section 75.15 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) SAFEGUARDS ON NUCLEAR MATERIAL-IMPLEMENTATION OF US/IAEA AGREEMENT Material Accounting and Control for Facilities § 75.15 Facility attachments. (a) The Facility Attachment...

  1. 10 CFR 75.15 - Facility attachments.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 10 Energy 2 2012-01-01 2012-01-01 false Facility attachments. 75.15 Section 75.15 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) SAFEGUARDS ON NUCLEAR MATERIAL-IMPLEMENTATION OF US/IAEA AGREEMENT Material Accounting and Control for Facilities § 75.15 Facility attachments. (a) The Facility Attachment...

  2. 10 CFR 75.15 - Facility attachments.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 10 Energy 2 2014-01-01 2014-01-01 false Facility attachments. 75.15 Section 75.15 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) SAFEGUARDS ON NUCLEAR MATERIAL-IMPLEMENTATION OF US/IAEA AGREEMENT Material Accounting and Control for Facilities § 75.15 Facility attachments. (a) The Facility Attachment...

  3. 10 CFR 75.15 - Facility attachments.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 10 Energy 2 2011-01-01 2011-01-01 false Facility attachments. 75.15 Section 75.15 Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) SAFEGUARDS ON NUCLEAR MATERIAL-IMPLEMENTATION OF US/IAEA AGREEMENT Material Accounting and Control for Facilities § 75.15 Facility attachments. (a) The Facility Attachment...

  4. Hot-Melt Adhesive Attachment System

    NASA Technical Reports Server (NTRS)

    Fox, R. L.; Frizzell, A. W.; Little, B. D.; Progar, D. J.; Coultrip, R. H.; Couch, R. H.; Stein, B. A.; Buckley, J. D.; St. Clair, T. L.; Gleason, J. R.

    1983-01-01

    Adhesive system is as effective on Earth as in space. Fiberglass cloth mounted in head assembly. When adhesive reaches melt temperature head is attached to metals composites, ceramics, and other materials. Once attached, head cooled rapidly for quick stick. Used to tether tools or attach temporary scaffolding to walls, buildings, or beams.

  5. Adolescents' Attachment and Coping with Stress

    ERIC Educational Resources Information Center

    Howard, Michelle S.; Medway, Frederic J.

    2004-01-01

    This study examined how high school students cope with stress as a function of their attachment style. Data were gathered from 75 adolescent-parent pairs in Texas and included measures of attachment, coping style, life stress, and whom the respondent would turn to in times of stress. Adolescents' attachment security was positively related to…

  6. 21 CFR 872.3165 - Precision attachment.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Precision attachment. 872.3165 Section 872.3165...) MEDICAL DEVICES DENTAL DEVICES Prosthetic Devices § 872.3165 Precision attachment. (a) Identification. A precision attachment or preformed bar is a device made of austenitic alloys or alloys containing 75...

  7. Attachment in Middle Childhood: Progress and Prospects

    ERIC Educational Resources Information Center

    Bosmans, Guy; Kerns, Kathryn A.

    2015-01-01

    Contrary to the substantial amount of research on infant, preschool, adolescent, and adult attachment, middle childhood has long been neglected by the international attachment research community. In the past two decades, however, there has been a steep increase in research focusing on middle childhood attachment. This article provides an overview…

  8. Attachment in Middle Childhood: Progress and Prospects

    ERIC Educational Resources Information Center

    Bosmans, Guy; Kerns, Kathryn A.

    2015-01-01

    Contrary to the substantial amount of research on infant, preschool, adolescent, and adult attachment, middle childhood has long been neglected by the international attachment research community. In the past two decades, however, there has been a steep increase in research focusing on middle childhood attachment. This article provides an overview…

  9. Easy Attachment Of Panels To A Truss

    NASA Technical Reports Server (NTRS)

    Thomson, Mark; Gralewski, Mark

    1992-01-01

    Conceptual antenna dish, solar collector, or similar structure consists of hexagonal panels supported by truss erected in field. Truss built in increments to maintain access to panel-attachment nodes. Each panel brought toward truss at angle and attached to two nodes. Panel rotated into attachment at third node.

  10. Cesarean Births and Attachment Behaviors of Fathers.

    DTIC Science & Technology

    1984-01-01

    Apgar scores are 7 or greater at both 1 and 5...status, indications for cesarean delivery, anesthesis, and infant’s gestational age, birth weight, and apgar scores . Prior to meeting the father, the...delivery and attachment score ; highest school grade completed and attachment score ; and age and child care experience of the father and attachment score

  11. Attachment: Building Secure Relationships in Early Childhood.

    ERIC Educational Resources Information Center

    Harrison, Linda

    2003-01-01

    Attachment describes the unique human ability to form lasting relationships with others, and to maintain these relationships over time and distance. Research into attachment has shown that children have the potential to form many attachment relationships, and that each relationship can contribute to the child's growing sense of self. This booklet…

  12. Reactive Attachment Disorder: Recommendations for School Counselors.

    ERIC Educational Resources Information Center

    Hayes, Susanna H.

    1997-01-01

    Using a case study, explores a unique counseling relationship. Examines how the quality of parent-child attachment and care of a child during the formative preschool years affects interpersonal relationship skills and school adjustment. Discusses reactive attachment disorders, the pervasiveness of attachment disorders, and recommendations for…

  13. Attachment: Building Secure Relationships in Early Childhood.

    ERIC Educational Resources Information Center

    Harrison, Linda

    2003-01-01

    Attachment describes the unique human ability to form lasting relationships with others, and to maintain these relationships over time and distance. Research into attachment has shown that children have the potential to form many attachment relationships, and that each relationship can contribute to the child's growing sense of self. This booklet…

  14. Attachment Relationships and the Career Exploration Process.

    ERIC Educational Resources Information Center

    Ketterson, Timothy U.; Blustein, David L.

    1997-01-01

    Examines the role of parent-adolescent attachment relationships in the career exploration process. Results, based on 137 college students, indicate that attachment to parents is positively associated with environmental exploration. However, parental attachment did not influence traditionality of exploration. Age played a significant role in career…

  15. Easy Attachment Of Panels To A Truss

    NASA Technical Reports Server (NTRS)

    Thomson, Mark; Gralewski, Mark

    1992-01-01

    Conceptual antenna dish, solar collector, or similar structure consists of hexagonal panels supported by truss erected in field. Truss built in increments to maintain access to panel-attachment nodes. Each panel brought toward truss at angle and attached to two nodes. Panel rotated into attachment at third node.

  16. Genetic and Environmental Influence on Attachment Disorganization

    ERIC Educational Resources Information Center

    Spangler, Gottfried; Johann, Monika; Ronai, Zsolt; Zimmermann, Peter

    2009-01-01

    Background: Empirical studies demonstrate that maternal sensitivity is associated with attachment security in infancy, while maternal frightening/frightened behavior is related to attachment disorganization. However, attachment disorganization is also predicted by individual dispositions in infancy. Indeed, recent studies indicate a link between…

  17. Attachment Representation of Institutionalized Children in Japan

    ERIC Educational Resources Information Center

    Katsurada, Emiko

    2007-01-01

    This exploratory study represents one of the first attachment investigations of Japanese children who have been institutionalized. Mental representation of attachment was assessed using George and Solomon's (1990, 1996, 2000) Attachment Doll Play Classification System of the Bretherton et al. (1990) doll play story stems. Participants were 32…

  18. Attachment Relationships: Self-Disclosure and Trust.

    ERIC Educational Resources Information Center

    Pistole, M. Carole

    1993-01-01

    Examined differences in trust and self-disclosure associated with secure, anxious/ambivalent, and avoidant attachment. Findings from 98 undergraduate students revealed that, in general, subjects who reported themselves as securely attached also reported, in comparison with avoidant attachment, higher levels of trust in partner, amount of…

  19. 21 CFR 872.3165 - Precision attachment.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Precision attachment. 872.3165 Section 872.3165...) MEDICAL DEVICES DENTAL DEVICES Prosthetic Devices § 872.3165 Precision attachment. (a) Identification. A precision attachment or preformed bar is a device made of austenitic alloys or alloys containing 75...

  20. Genetic and Environmental Influence on Attachment Disorganization

    ERIC Educational Resources Information Center

    Spangler, Gottfried; Johann, Monika; Ronai, Zsolt; Zimmermann, Peter

    2009-01-01

    Background: Empirical studies demonstrate that maternal sensitivity is associated with attachment security in infancy, while maternal frightening/frightened behavior is related to attachment disorganization. However, attachment disorganization is also predicted by individual dispositions in infancy. Indeed, recent studies indicate a link between…