Charge-transfer-directed radical substitution enables para-selective C-H functionalization

NASA Astrophysics Data System (ADS)

Boursalian, Gregory B.; Ham, Won Seok; Mazzotti, Anthony R.; Ritter, Tobias

2016-08-01

Efficient C-H functionalization requires selectivity for specific C-H bonds. Progress has been made for directed aromatic substitution reactions to achieve ortho and meta selectivity, but a general strategy for para-selective C-H functionalization has remained elusive. Herein we introduce a previously unappreciated concept that enables nearly complete para selectivity. We propose that radicals with high electron affinity elicit arene-to-radical charge transfer in the transition state of radical addition, which is the factor primarily responsible for high positional selectivity. We demonstrate with a simple theoretical tool that the selectivity is predictable and show the utility of the concept through a direct synthesis of aryl piperazines. Our results contradict the notion, widely held by organic chemists, that radical aromatic substitution reactions are inherently unselective. The concept of radical substitution directed by charge transfer could serve as the basis for the development of new, highly selective C-H functionalization reactions.

Application of the MNA design method to a nonlinear turbofan engine. [multivariable Nyquist array method

NASA Technical Reports Server (NTRS)

Leininger, G. G.

1981-01-01

Using nonlinear digital simulation as a representative model of the dynamic operation of the QCSEE turbofan engine, a feedback control system is designed by variable frequency design techniques. Transfer functions are generated for each of five power level settings covering the range of operation from approach power to full throttle (62.5% to 100% full power). These transfer functions are then used by an interactive control system design synthesis program to provide a closed loop feedback control using the multivariable Nyquist array and extensions to multivariable Bode diagrams and Nichols charts.

Synthesis of coupled resonator optical waveguides by cavity aggregation.

PubMed

Muñoz, Pascual; Doménech, José David; Capmany, José

2010-01-18

In this paper, the layer aggregation method is applied to coupled resonator optical waveguides. Starting from the frequency transfer function, the method yields the coupling constants between the resonators. The convergence of the algorithm developed is examined and the related parameters discussed.

A Novel Leu92 Mutant of HIV-1 Reverse Transcriptase with a Selective Deficiency in Strand Transfer Causes a Loss of Viral Replication.

PubMed

Herzig, Eytan; Voronin, Nickolay; Kucherenko, Nataly; Hizi, Amnon

2015-08-01

The process of reverse transcription (RTN) in retroviruses is essential to the viral life cycle. This key process is catalyzed exclusively by the viral reverse transcriptase (RT) that copies the viral RNA into DNA by its DNA polymerase activity, while concomitantly removing the original RNA template by its RNase H activity. During RTN, the combination between DNA synthesis and RNA hydrolysis leads to strand transfers (or template switches) that are critical for the completion of RTN. The balance between these RT-driven activities was considered to be the sole reason for strand transfers. Nevertheless, we show here that a specific mutation in HIV-1 RT (L92P) that does not affect the DNA polymerase and RNase H activities abolishes strand transfer. There is also a good correlation between this complete loss of the RT's strand transfer to the loss of the DNA clamp activity of the RT, discovered recently by us. This finding indicates a mechanistic linkage between these two functions and that they are both direct and unique functions of the RT (apart from DNA synthesis and RNA degradation). Furthermore, when the RT's L92P mutant was introduced into an infectious HIV-1 clone, it lost viral replication, due to inefficient intracellular strand transfers during RTN, thus supporting the in vitro data. As far as we know, this is the first report on RT mutants that specifically and directly impair RT-associated strand transfers. Therefore, targeting residue Leu92 may be helpful in selectively blocking this RT activity and consequently HIV-1 infectivity and pathogenesis. Reverse transcription in retroviruses is essential for the viral life cycle. This multistep process is catalyzed by viral reverse transcriptase, which copies the viral RNA into DNA by its DNA polymerase activity (while concomitantly removing the RNA template by its RNase H activity). The combination and balance between synthesis and hydrolysis lead to strand transfers that are critical for reverse transcription completion. We show here for the first time that a single mutation in HIV-1 reverse transcriptase (L92P) selectively abolishes strand transfers without affecting the enzyme's DNA polymerase and RNase H functions. When this mutation was introduced into an infectious HIV-1 clone, viral replication was lost due to an impaired intracellular strand transfer, thus supporting the in vitro data. Therefore, finding novel drugs that target HIV-1 reverse transcriptase Leu92 may be beneficial for developing new potent and selective inhibitors of retroviral reverse transcription that will obstruct HIV-1 infectivity. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

Synthesis of Natural Electric and Magnetic Time Series Using Impulse Responses of Inter-station Transfer Functions and a Reference

NASA Astrophysics Data System (ADS)

Wang, H.; Cheng, J.

2017-12-01

A method to Synthesis natural electric and magnetic Time series is proposed whereby the time series of local site are derived using an Impulse Response and a reference (STIR). The method is based on the assumption that the external source of magnetic fields are uniform, and the electric and magnetic fields acquired at the surface satisfy a time-independent linear relation in frequency domain.According to the convolution theorem, we can synthesize natural electric and magnetic time series using the impulse responses of inter-station transfer functions with a reference. Applying this method, two impulse responses need to be estimated: the quasi-MT impulse response tensor and the horizontal magnetic impulse response tensor. These impulse response tensors relate the local horizontal electric and magnetic components with the horizontal magnetic components at a reference site, respectively. Some clean segments of times series are selected to estimate impulse responses by using least-square (LS) method. STIR is similar with STIN (Wang, 2017), but STIR does not need to estimate the inter-station transfer functions, and the synthesized data are more accurate in high frequency, where STIN fails when the inter-station transfer functions are contaminated severely. A test with good quality of MT data shows that synthetic time-series are similar to natural electric and magnetic time series. For contaminated AMT example, when this method is used to remove noise present at the local site, the scatter of MT sounding curves are clear reduced, and the data quality are improved. *This work is funded by National Key R&D Program of China(2017YFC0804105),National Natural Science Foundation of China (41604064, 51574250), State Key Laboratory of Coal Resources and Safe Mining ,China University of Mining & Technology,(SKLCRSM16DC09)

Direct Aldehyde C-H Arylation and Alkylation via the Combination of Nickel, Hydrogen Atom Transfer, and Photoredox Catalysis.

PubMed

Zhang, Xiaheng; MacMillan, David W C

2017-08-23

A mechanism that enables direct aldehyde C-H functionalization has been achieved via the synergistic merger of photoredox, nickel, and hydrogen atom transfer catalysis. This mild, operationally simple protocol transforms a wide variety of commercially available aldehydes, along with aryl or alkyl bromides, into the corresponding ketones in excellent yield. This C-H abstraction coupling technology has been successfully applied to the expedient synthesis of the medicinal agent haloperidol.

Graphene Derivative in Magnetically Recoverable Catalyst Determines Catalytic Properties in Transfer Hydrogenation of Nitroarenes to Anilines with 2-Propanol.

PubMed

Das, Vijay Kumar; Mazhar, Sumaira; Gregor, Lennon; Stein, Barry D; Morgan, David Gene; Maciulis, Nicholas A; Pink, Maren; Losovyj, Yaroslav; Bronstein, Lyudmila M

2018-06-14

Here, we report transfer hydrogenation of nitroarenes to aminoarenes using 2-propanol as a hydrogen source and Ag-containing magnetically recoverable catalysts based on partially reduced graphene oxide (pRGO) sheets. X-ray diffraction and X-ray photoelectron spectroscopy data demonstrated that, during the one-pot catalyst synthesis, formation of magnetite nanoparticles (NPs) is accompanied by the reduction of graphene oxide (GO) to pRGO. The formation of Ag 0 NPs on top of magnetite nanoparticles does not change the pRGO structure. At the same time, the catalyst structure is further modified during the transfer hydrogenation, leading to a noticeable increase of sp 2 carbons. These carbons are responsible for the adsorption of substrate and intermediates, facilitating a hydrogen transfer from Ag NPs and creating synergy between the components of the catalyst. The nitroarenes with electron withdrawing and electron donating substituents allow for excellent yields of aniline derivatives with high regio and chemoselectivity, indicating that the reaction is not disfavored by these functionalities. The versatility of the catalyst synthetic protocol was demonstrated by a synthesis of an Ru-containing graphene derivative based catalyst, also allowing for efficient transfer hydrogenation. Easy magnetic separation and stable catalyst performance in the transfer hydrogenation make this catalyst promising for future applications.

How to precisely measure the volume velocity transfer function of physical vocal tract models by external excitation

PubMed Central

Mainka, Alexander; Kürbis, Steffen; Birkholz, Peter

2018-01-01

Recently, 3D printing has been increasingly used to create physical models of the vocal tract with geometries obtained from magnetic resonance imaging. These printed models allow measuring the vocal tract transfer function, which is not reliably possible in vivo for the vocal tract of living humans. The transfer functions enable the detailed examination of the acoustic effects of specific articulatory strategies in speaking and singing, and the validation of acoustic plane-wave models for realistic vocal tract geometries in articulatory speech synthesis. To measure the acoustic transfer function of 3D-printed models, two techniques have been described: (1) excitation of the models with a broadband sound source at the glottis and measurement of the sound pressure radiated from the lips, and (2) excitation of the models with an external source in front of the lips and measurement of the sound pressure inside the models at the glottal end. The former method is more frequently used and more intuitive due to its similarity to speech production. However, the latter method avoids the intricate problem of constructing a suitable broadband glottal source and is therefore more effective. It has been shown to yield a transfer function similar, but not exactly equal to the volume velocity transfer function between the glottis and the lips, which is usually used to characterize vocal tract acoustics. Here, we revisit this method and show both, theoretically and experimentally, how it can be extended to yield the precise volume velocity transfer function of the vocal tract. PMID:29543829

A versatile platform for precise synthesis of asymmetric molecular brush in one shot.

PubMed

Xu, Binbin; Feng, Chun; Huang, Xiaoyu

2017-08-24

Asymmetric molecular brushes emerge as a unique class of nanostructured polymers, while their versatile synthesis keeps a challenge for chemists. Here we show the synthesis of well-defined asymmetric molecular double-brushes comprising two different side chains linked to the same repeat unit along the backbone by one-pot concurrent atom transfer radical polymerization (ATRP) and Cu-catalyzed azide/alkyne cycloaddition (CuAAC) reaction. The double-brushes are based on a poly(Br-acrylate-alkyne) homopolymer possessing an alkynyl for CuAAC reaction and a 2-bromopropionate initiating group for ATRP in each repeat unit. The versatility of this one-shot approach is demonstrated by CuAAC reaction of alkynyl/poly(ethylene oxide)-N 3 and ATRP of various monomers. We also show the quantitative conversion of pentafluorophenyl ester groups to amide groups in side chains, allowing for the further fabrication of diverse building blocks. This work provides a versatile platform for facile synthesis of Janus-type double-brushes with structural and functional control, in a minimum number of reactions.Producing well-defined polymer compositions and structures facilitates their use in many different applications. Here the authors show the synthesis of well-defined asymmetric double-brushes by a one-pot concurrent atom transfer radical polymerization and Cu-catalyzed Click reaction.

Artificial photosynthesis using chlorophyll based carotenoid quinone triads: A brief synopsis of research progress as of 31 December 1986

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gust, D.; Moore, T.A.

1986-12-31

The design, synthesis and study of a series of carotenoid-chlorophyll-quinone triad molecules which mimic some of the basic photochemistry and photophysics of natural photosynthesis is sought. The first members of this series have now been prepared, and have been found to mimic photosynthetic charge separation, carotenoid antenna function, and carotenoid photoprotection from singlet oxygen damage. Although the triad molecules mimic the general principle of multistep electron transfer which is found in natural photosynthesis, the details of photosynthetic electron transfer differ in the triads, in that the first electron transfer step involves electron donation from the excited state donor, followed bymore » reduction of the resulting donor radical cation by the carotenoid. In photosynthesis, the electron is moved through several acceptors before the chlorophyll radical cation is reduced. Therefore, our recent work has concentrated on the design and synthesis of new model systems which better mimic certain aspects of natural photosynthesis.« less

ORP5/ORP8 localize to endoplasmic reticulum-mitochondria contacts and are involved in mitochondrial function.

PubMed

Galmes, Romain; Houcine, Audrey; van Vliet, Alexander R; Agostinis, Patrizia; Jackson, Catherine L; Giordano, Francesca

2016-06-01

The oxysterol-binding protein (OSBP)-related proteins ORP5 and ORP8 have been shown recently to transport phosphatidylserine (PS) from the endoplasmic reticulum (ER) to the plasma membrane (PM) at ER-PM contact sites. PS is also transferred from the ER to mitochondria where it acts as precursor for mitochondrial PE synthesis. Here, we show that, in addition to ER-PM contact sites, ORP5 and ORP8 are also localized to ER-mitochondria contacts and interact with the outer mitochondrial membrane protein PTPIP51. A functional lipid transfer (ORD) domain was required for this localization. Interestingly, ORP5 and ORP8 depletion leads to defects in mitochondria morphology and respiratory function. © 2016 The Authors.

Insights in the Diffusion Controlled Interfacial Flow Synthesis of Au Nanostructures in a Microfluidic System.

PubMed

Kulkarni, Amol A; Sebastian Cabeza, Victor

2017-12-19

Continuous segmented flow interfacial synthesis of Au nanostructures is demonstrated in a microchannel reactor. This study brings new insights into the growth of nanostructures at continuous interfaces. The size as well as the shape of the nanostructures showed significant dependence on the reactant concentrations, reaction time, temperature, and surface tension, which actually controlled the interfacial mass transfer. The microchannel reactor assisted in achieving a high interfacial area, as well as uniformity in mass transfer effects. Hexagonal nanostructures were seen to be formed in synthesis times as short as 10 min. The wettability of the channel showed significant effect on the particle size as well as the actual shape. The hydrophobic channel yielded hexagonal structures of relatively smaller size than the hydrophilic microchannel, which yielded sharp hexagonal bipyramidal particles (diagonal distance of 30 nm). The evolution of particle size and shape for the case of hydrophilic microchannel is also shown as a function of the residence time. The interfacial synthesis approach based on a stable segmented flow promoted an excellent control on the reaction extent, reduction in axial dispersion as well as the particle size distribution.

New Era of Lipid-Lowering Drugs

PubMed Central

Rye, Kerry-Anne

2016-01-01

There are several established lipid-modifying agents, including statins, fibrates, niacin, and ezetimibe, that have been shown in randomized clinical outcome trials to reduce the risk of having an atherosclerotic cardiovascular event. However, in many people, the risk of having an event remains unacceptably high despite treatment with these established agents. This has stimulated the search for new therapies designed to reduce residual cardiovascular risk. New approaches that target atherogenic lipoproteins include: 1) inhibition of proprotein convertase subtilisin/kexin type 9 to increase removal of atherogenic lipoproteins from plasma; 2) inhibition of the synthesis of apolipoprotein (apo) B, the main protein component of atherogenic lipoproteins; 3) inhibition of microsomal triglyceride transfer protein to block the formation of atherogenic lipoproteins; 4) inhibition of adenosine triphosphate citrate lyase to inhibit the synthesis of cholesterol; 5) inhibition of the synthesis of lipoprotein(a), a factor known to cause atherosclerosis; 6) inhibition of apoC-III to reduce triglyceride-rich lipoproteins and to enhance high-density lipoprotein (HDL) functionality; and 7) inhibition of cholesteryl ester transfer protein, which not only reduces the concentration of atherogenic lipoproteins but also increases the level and function of the potentially antiatherogenic HDL fraction. Other new therapies that specifically target HDLs include infusions of reconstituted HDLs, HDL delipidation, and infusions of apoA-I mimetic peptides that mimic some of the functions of HDLs. This review describes the scientific basis and rationale for developing these new therapies and provides a brief summary of established therapies. PMID:26983688

Technology transfer by means of fault tree synthesis

NASA Astrophysics Data System (ADS)

Batzias, Dimitris F.

2012-12-01

Since Fault Tree Analysis (FTA) attempts to model and analyze failure processes of engineering, it forms a common technique for good industrial practice. On the contrary, fault tree synthesis (FTS) refers to the methodology of constructing complex trees either from dentritic modules built ad hoc or from fault tress already used and stored in a Knowledge Base. In both cases, technology transfer takes place in a quasi-inductive mode, from partial to holistic knowledge. In this work, an algorithmic procedure, including 9 activity steps and 3 decision nodes is developed for performing effectively this transfer when the fault under investigation occurs within one of the latter stages of an industrial procedure with several stages in series. The main parts of the algorithmic procedure are: (i) the construction of a local fault tree within the corresponding production stage, where the fault has been detected, (ii) the formation of an interface made of input faults that might occur upstream, (iii) the fuzzy (to count for uncertainty) multicriteria ranking of these faults according to their significance, and (iv) the synthesis of an extended fault tree based on the construction of part (i) and on the local fault tree of the first-ranked fault in part (iii). An implementation is presented, referring to 'uneven sealing of Al anodic film', thus proving the functionality of the developed methodology.

Pedestrian and bicycle facilities in California : a technical reference and technology transfer synthesis for Caltrans planners and engineers.

DOT National Transportation Integrated Search

2005-07-01

The primary purpose of Pedestrian and Bicycle Facilities in CaliforniaA : Technical Reference and Technology Transfer Synthesis for Caltrans Planners : and Engineers (Technical Reference) is to provide Caltrans staff : with a synthesis of in...

Ion/Ion Reactions with "Onium" Reagents: An Approach for the Gas-phase Transfer of Organic Cations to Multiply-Charged Anions

NASA Astrophysics Data System (ADS)

Gilbert, Joshua D.; Prentice, Boone M.; McLuckey, Scott A.

2015-05-01

The use of ion/ion reactions to effect gas-phase alkylation is demonstrated. Commonly used fixed-charge "onium" cations are well-suited for ion/ion reactions with multiply deprotonated analytes because of their tendency to form long-lived electrostatic complexes. Activation of these complexes results in an SN2 reaction that yields an alkylated anion with the loss of a neutral remnant of the reagent. This alkylation process forms the basis of a general method for alkylation of deprotonated analytes generated via electrospray, and is demonstrated on a variety of anionic sites. SN2 reactions of this nature are demonstrated empirically and characterized using density functional theory (DFT). This method for modification in the gas phase is extended to the transfer of larger and more complex R groups that can be used in later gas-phase synthesis steps. For example, N-cyclohexyl- N'-(2-morpholinoethyl)carbodiimide (CMC) is used to transfer a carbodiimide functionality to a peptide anion containing a carboxylic acid. Subsequent activation yields a selective reaction between the transferred carbodiimide group and a carboxylic acid, suggesting the carbodiimide functionality is retained through the transfer process. Many different R groups are transferable using this method, allowing for new possibilities for charge manipulation and derivatization in the gas phase.

Expeditious diastereoselective synthesis of elaborated ketones via remote Csp3-H functionalization

NASA Astrophysics Data System (ADS)

Shu, Wei; Lorente, Adriana; Gómez-Bengoa, Enrique; Nevado, Cristina

2017-01-01

The quest for selective C-H functionalization reactions, able to provide new strategic opportunities for the rapid assembly of molecular complexity, represents a major focus of the chemical community. Examples of non-directed, remote Csp3-H activation to forge complex carbon frameworks remain scarce due to the kinetic stability and thus intrinsic challenge associated to the chemo-, regio- and stereoselective functionalization of aliphatic C-H bonds. Here we describe a radical-mediated, directing-group-free regioselective 1,5-hydrogen transfer of unactivated Csp3-H bonds followed by a second Csp2-H functionalization to produce, with exquisite stereoselectivity, a variety of elaborated fused ketones. This study demonstrates that aliphatic acids can be strategically harnessed as 1,2-diradical synthons and that secondary aliphatic C-H bonds can be engaged in stereoselective C-C bond-forming reactions, highlighting the potential of this protocol for target-oriented natural product and pharmaceutical synthesis.

Mechanistic models as a transferable framework for projecting effects of habitat change on production and delivery of ecosystem services

EPA Science Inventory

Drawing a link between habitat change and the production and delivery of ecosystem services is a priority in coastal estuarine ecosystems. Mechanistic modeling tools are highly functional for exploring this link because they allow for the synthesis of multiple ecological and beh...

Single crystal functional oxides on silicon

PubMed Central

Bakaul, Saidur Rahman; Serrao, Claudy Rayan; Lee, Michelle; Yeung, Chun Wing; Sarker, Asis; Hsu, Shang-Lin; Yadav, Ajay Kumar; Dedon, Liv; You, Long; Khan, Asif Islam; Clarkson, James David; Hu, Chenming; Ramesh, Ramamoorthy; Salahuddin, Sayeef

2016-01-01

Single-crystalline thin films of complex oxides show a rich variety of functional properties such as ferroelectricity, piezoelectricity, ferro and antiferromagnetism and so on that have the potential for completely new electronic applications. Direct synthesis of such oxides on silicon remains challenging because of the fundamental crystal chemistry and mechanical incompatibility of dissimilar interfaces. Here we report integration of thin (down to one unit cell) single crystalline, complex oxide films onto silicon substrates, by epitaxial transfer at room temperature. In a field-effect transistor using a transferred lead zirconate titanate layer as the gate insulator, we demonstrate direct reversible control of the semiconductor channel charge with polarization state. These results represent the realization of long pursued but yet to be demonstrated single-crystal functional oxides on-demand on silicon. PMID:26853112

Synthesis of a probe for monitoring HSV1-tk reporter gene expression using chemical exchange saturation transfer MRI

PubMed Central

Bar-Shir, Amnon; Liu, Guanshu; Greenberg, Marc M; Bulte, Jeff W M; Gilad, Assaf A

2013-01-01

In experiments involving transgenic animals or animals treated with transgenic cells, it is important to have a method to monitor the expression of the relevant genes longitudinally and noninvasively. An MRI-based reporter gene enables monitoring of gene expression in the deep tissues of living subjects. This information can be co-registered with detailed high-resolution anatomical and functional information. We describe here the synthesis of the reporter probe, 5-methyl-5,6-dihydrothymidine (5-MDHT), which can be used for imaging of the herpes simplex virus type 1 thymidine kinase (HSV1-tk) reporter gene expression in rodents by MRI. The protocol also includes data acquisition and data processing routines customized for chemical exchange saturation transfer (CEST) contrast mechanisms. The dihydropyrimidine 5-MDHT is synthesized through a catalytic hydrogenation of the 5,6-double bond of thymidine to yield 5,6-dihydrothymidine, which is methylated on the C-5 position of the resulting saturated pyrimidine ring. The synthesis of 5-MDHT can be completed within 5 d, and the compound is stable for more than 1 year. PMID:24177294

Initiation of viral RNA-dependent RNA polymerization.

PubMed

van Dijk, Alberdina A; Makeyev, Eugene V; Bamford, Dennis H

2004-05-01

This review summarizes the combined insights from recent structural and functional studies of viral RNA-dependent RNA polymerases (RdRPs) with the primary focus on the mechanisms of initiation of RNA synthesis. Replication of RNA viruses has traditionally been approached using a combination of biochemical and genetic methods. Recently, high-resolution structures of six viral RdRPs have been determined. For three RdRPs, enzyme complexes with metal ions, single-stranded RNA and/or nucleoside triphosphates have also been solved. These advances have expanded our understanding of the molecular mechanisms of viral RNA synthesis and facilitated further RdRP studies by informed site-directed mutagenesis. What transpires is that the basic polymerase right hand shape provides the correct geometrical arrangement of substrate molecules and metal ions at the active site for the nucleotidyl transfer catalysis, while distinct structural elements have evolved in the different systems to ensure efficient initiation of RNA synthesis. These elements feed the template, NTPs and ions into the catalytic cavity, correctly position the template 3' terminus, transfer the products out of the catalytic site and orchestrate the transition from initiation to elongation.

Microscale Synthesis of Chiral Alcohols via Asymmetric Catalytic Transfer Hydrogenation

ERIC Educational Resources Information Center

Peeters, Christine M.; Deliever, Rik; De Vos, Dirk

2009-01-01

Synthesis of pure enantiomers is a key issue in industry, especially in areas connected to life sciences. Catalytic asymmetric synthesis has emerged as a powerful and practical tool. Here we describe an experiment on racemic reduction and asymmetric reduction via a catalytic hydrogen transfer process. Acetophenone and substituted acetophenones are…

Chemical Constraints Governing the Origin of Metabolism: The Thermodynamic Landscape of Carbon Group Transformations

NASA Technical Reports Server (NTRS)

Weber, Arthur L.; Fonda, Mark (Technical Monitor)

2001-01-01

The thermodynamics of organic chemistry under mild aqueous conditions was examined in order to begin to understand its influence on the structure and operation of metabolism and its antecedents. Free energies were estimated for four types reactions of biochemical importance carbon-carbon bond cleavage and synthesis, hydrogen transfer between carbon groups, dehydration of alcohol groups, and aldo-keto isomerization. The energies were calculated for mainly aliphatic groups composed of carbon, hydrogen, and oxygen. The energy values showed that (1) when carbon-carbon bond cleavage involves two different types of functional groups, transfer of the shared electron-pair to the more reduced carbon group is energetically favored over transfer to the more oxidized carbon group, and (2) the energy of carbon-carbon bond transformation is strongly dependent on the type of functional group that donates the shared electron-pair during cleavage, and the group that accepts the shared electron-pair during synthesis, and (3) the energetics of C-C bond transformation is determined primarily by the half-reaction energies of the couples: carbonyl/carboxylic acid, carboxylic acid/carbon dioxide, alcohol/carbonyl, and hydrocarbon/alcohol. The energy of hydrogen-transfer between carbon groups was found to depend on the functional group class of both the hydrogen-donor and hydrogen-acceptor. From these and other observations we concluded that the chemistry of the origin of metabolism (and to a lesser degree modem metabolism) is strongly constrained by the (1) limited disproportionation energy of organic substrates that can be dissipated in a few irreversible reactions, (2) the energy-dominance of few half-reaction couples in carbon-carbon bond transformation that establishes whether a chemical reaction is energetically irreversible, reversible or unfeasible, and (3) the dependence of the transformation-energy on the oxidation state of carbon groups (functional group type) which is contingent on prior reactions in the synthetic pathway.

Functional Association between Regulatory RNAs and the Annexins

PubMed Central

Monastyrskaya, Katia

2018-01-01

Cells respond to pathophysiological states by activation of stress-induced signalling. Regulatory non-coding microRNAs (miRNAs) often form stable feed-forward loops which ensure prolongation of the signal, contributing to sustained activation. Members of the annexin protein family act as sensors for Ca2+, pH, and lipid second messengers, and regulate various signalling pathways. Recently, annexins were reported to participate in feedback loops, suppressing miRNA synthesis and attenuating stress-induced dysregulation of gene expression. They can directly or indirectly associate with RNAs, and are transferred between the cells in exosomes and shed microvesicles. The ability of annexins to recruit other proteins and miRNAs into exosomes implicates them in control of cell–cell interactions, affecting the adaptive responses and remodelling processes during disease. The studies summarized in this Review point to an emerging role of annexins in influencing the synthesis, localisation, and transfer of regulatory RNAs. PMID:29462943

Transfer-free synthesis of multilayer graphene using a single-step process in an evaporator and formation confirmation by laser mode-locking.

PubMed

Kim, Won-Jun; Debnath, Pulak C; Lee, Junsu; Lee, Ju Han; Lim, Dae-Soon; Song, Yong-Won

2013-09-13

Multilayer graphene is synthesized by a simplified process employing an evaporator in which a target substrate is deposited with a Ni catalyst layer before being heated to grow graphene directly. Carbon atoms adsorbed onto the surface of the Ni source as impurities from the atmosphere are incorporated into the catalyst layer during the deposition, and diffuse toward the catalyst/substrate interface, where they crystallize as graphene with a thickness of less than 2 nm. The need for a transfer process and external carbon supply is eliminated. The graphene is characterized by conventional analysis approaches, including nano-scale visualization and Raman spectroscopy, and utilizing photonics, graphene-functionalized passive laser mode-locking is demonstrated to confirm the successful synthesis of the graphene layer, resulting in an operating center wavelength of 1569.4 nm, a pulse duration of 1.35 ps, and a repetition rate of 31.6 MHz.

Mapping forest functional type in a forest-shrubland ecotone using SPOT imagery and predictive habitat distribution modelling

USGS Publications Warehouse

Assal, Timothy J.; Anderson, Patrick J.; Sibold, Jason

2015-01-01

The availability of land cover data at local scales is an important component in forest management and monitoring efforts. Regional land cover data seldom provide detailed information needed to support local management needs. Here we present a transferable framework to model forest cover by major plant functional type using aerial photos, multi-date Système Pour l’Observation de la Terre (SPOT) imagery, and topographic variables. We developed probability of occurrence models for deciduous broad-leaved forest and needle-leaved evergreen forest using logistic regression in the southern portion of the Wyoming Basin Ecoregion. The model outputs were combined into a synthesis map depicting deciduous and coniferous forest cover type. We evaluated the models and synthesis map using a field-validated, independent data source. Results showed strong relationships between forest cover and model variables, and the synthesis map was accurate with an overall correct classification rate of 0.87 and Cohen’s kappa value of 0.81. The results suggest our method adequately captures the functional type, size, and distribution pattern of forest cover in a spatially heterogeneous landscape.

Functional Polymers and Sequential Copolymers by Phase Transfer Catalysis. Synthesis of Thermotropic Side-Chain Liquid Crystalline Polymers Containing a Poly(2,6-Dimethyl-1,4-Phenylene Oxide) Main Chain.

DTIC Science & Technology

1986-10-01

bromovalerate (Aldrich, 99%), 5-bromovaleronitrile (Aldrich, 95%), and 11-bromoundecanoic acid (Aldrich, 99%) were used without further purification. 4...atic proton’s). 71 Cm, 4 aromatic X~tons). C. Synthesis of 4- 4-oxybipheny1 butyrnc acid , 4-(4-inethoxy 4’-oxy- I hen 1 butyrnc acid , 5-(4-oxybipheny1...valeric acid , 5-(4-inethoxy-4-oxy- bi heny1 valeric acid . 11- 4-ox bipheny1 undecanoic acid and 11- 4-inethox -4 -ox biphenylundecanoic acid . The

Synthesis, solubilization, and surface functionalization of highly fluorescent quantum dots for cellular targeting through a small molecule

NASA Astrophysics Data System (ADS)

Galloway, Justin F.

To achieve long-term fluorescence imaging with quantum dots (QDs), a CdSe core/shell must first be synthesized. The synthesis of bright CdSe QDs is not trivial and as a consequence, the role of surfactant in nucleation and growth was investigated. It was found that the type of surfactant used, either phosphonic or fatty acid, played a pivotal role in the size of the CdSe core. The study of surfactant on CdSe synthesis, ultimately led to an electrical passivation method that utilized a short-chained phosphonic acid and highly reactive organometallic precursors to achieve high quantum yield (QY) as has been previously described. The synthesis of QDs using organometallic precursors and a phosphonic acid for passivation resulted in 4 out of 9 batches of QDs achieving QYs greater than 50% and 8 out of 9 batches with QYs greater than 35%. The synthesis of CdSe QDs was done in organic solutions rendering the surface of the particle hydrophobic. To perform cell-targeting experiments, QDs must be transferred to water. The transfer of QDs to water was successfully accomplished by using single acyl chain lipids. A systematic study of different lipid combinations and coatings demonstrated that 20-40 mol% single acyl chained lipids were able to transfer QDs to water resulting in monodispersed, stable QDs without adversely affecting the QY. The advantage to water solubilization using single acyl chain lipids is that the QD have a hydrodynamic radius less than 15 nm, QYs that can exceed 50% and additional surface functionalization can be down using the reactive sites incorporated into the lipid bilayer. QDs that are bright and stable in water were studied for the purpose of targeting G protein-coupled Receptors (GPCR). GPCRs are transmembrane receptors that internalize extracellular cues, and thus mediate signal transduction. The cyclic Adenosine Monophosphate Receptor 1 of the model organism Dictyostelium disodium was the receptor of interest. The Halo protein, a genetically modified dehalogenase, was added to the N-terminus of the cAR1 receptor without resulting in a phenotype. The Halo protein fused to cAR1 was then shown to bind an organic fluorophore by the cleavage of a chloroalkane bond. Though QDs functionalized with a chloroalkane were able to bind free Halo protein, no specific binding to the Halo protein fused to cAR1 was observed.

A synthetic biology approach to engineer a functional reversal of the β-oxidation cycle.

PubMed

Clomburg, James M; Vick, Jacob E; Blankschien, Matthew D; Rodríguez-Moyá, María; Gonzalez, Ramon

2012-11-16

While we have recently constructed a functional reversal of the β-oxidation cycle as a platform for the production of fuels and chemicals by engineering global regulators and eliminating native fermentative pathways, the system-level approach used makes it difficult to determine which of the many deregulated enzymes are responsible for product synthesis. This, in turn, limits efforts to fine-tune the synthesis of specific products and prevents the transfer of the engineered pathway to other organisms. In the work reported here, we overcome the aforementioned limitations by using a synthetic biology approach to construct and functionally characterize a reversal of the β-oxidation cycle. This was achieved through the in vitro kinetic characterization of each functional unit of the core and termination pathways, followed by their in vivo assembly and functional characterization. With this approach, the four functional units of the core pathway, thiolase, 3-hydroxyacyl-CoA dehydrogenase, enoyl-CoA hydratase/3-hydroxyacyl-CoA dehydratase, and acyl-CoA dehydrogenase/trans-enoyl-CoA reductase, were purified and kinetically characterized in vitro. When these four functional units were assembled in vivo in combination with thioesterases as the termination pathway, the synthesis of a variety of 4-C carboxylic acids from a one-turn functional reversal of the β-oxidation cycle was realized. The individual expression and modular construction of these well-defined core components exerted the majority of control over product formation, with only highly selective termination pathways resulting in shifts in product formation. Further control over product synthesis was demonstrated by overexpressing a long-chain thiolase that enables the operation of multiple turns of the reversal of the β-oxidation cycle and hence the synthesis of longer-chain carboxylic acids. The well-defined and self-contained nature of each functional unit makes the engineered reversal of the β-oxidation cycle "chassis neutral" and hence transferrable to the host of choice for efficient fuel or chemical production.

Aspects and Some Results on Passivity and Positivity of Dynamic Systems

NASA Astrophysics Data System (ADS)

De la Sen, M.

2017-12-01

This paper is devoted to discuss certain aspects of passivity results in dynamic systems and the characterization of the regenerative systems counterparts. In particular, the various concepts of passivity as standard passivity, strict input passivity, strict output passivity and very strict passivity (i.e. joint strict input and output passivity) are given and related to the existence of a storage function and a dissipation function. Later on, the obtained results are related to external positivity of systems and positivity or strict positivity of the transfer matrices and transfer functions in the time-invariant case. On the other hand, it is discussed how to achieve or how eventually to increase the passivity effects via linear feedback by the synthesis of the appropriate feed-forward or feedback controllers or, simply, by adding a positive parallel direct input-output matrix interconnection gain.

Printing Peptide arrays with a complementary metal oxide semiconductor chip.

PubMed

Loeffler, Felix F; Cheng, Yun-Chien; Muenster, Bastian; Striffler, Jakob; Liu, Fanny C; Ralf Bischoff, F; Doersam, Edgar; Breitling, Frank; Nesterov-Mueller, Alexander

2013-01-01

: In this chapter, we discuss the state-of-the-art peptide array technologies, comparing the spot technique, lithographical methods, and microelectronic chip-based approaches. Based on this analysis, we describe a novel peptide array synthesis method with a microelectronic chip printer. By means of a complementary metal oxide semiconductor chip, charged bioparticles can be patterned on its surface. The bioparticles serve as vehicles to transfer molecule monomers to specific synthesis spots. Our chip offers 16,384 pixel electrodes on its surface with a spot-to-spot pitch of 100 μm. By switching the voltage of each pixel between 0 and 100 V separately, it is possible to generate arbitrary particle patterns for combinatorial molecule synthesis. Afterwards, the patterned chip surface serves as a printing head to transfer the particle pattern from its surface to a synthesis substrate. We conducted a series of proof-of-principle experiments to synthesize high-density peptide arrays. Our solid phase synthesis approach is based on the 9-fluorenylmethoxycarbonyl protection group strategy. After melting the particles, embedded monomers diffuse to the surface and participate in the coupling reaction to the surface. The method demonstrated herein can be easily extended to the synthesis of more complicated artificial molecules by using bioparticles with artificial molecular building blocks. The possibility of synthesizing artificial peptides was also shown in an experiment in which we patterned biotin particles in a high-density array format. These results open the road to the development of peptide-based functional modules for diverse applications in biotechnology.

Ion transport in pigmentation.

PubMed

Bellono, Nicholas W; Oancea, Elena V

2014-12-01

Skin melanocytes and ocular pigment cells contain specialized organelles called melanosomes, which are responsible for the synthesis of melanin, the major pigment in mammals. Defects in the complex mechanisms involved in melanin synthesis and regulation result in vision and pigmentation deficits, impaired development of the visual system, and increased susceptibility to skin and eye cancers. Ion transport across cellular membranes is critical for many biological processes, including pigmentation, but the molecular mechanisms by which it regulates melanin synthesis, storage, and transfer are not understood. In this review we first discuss ion channels and transporters that function at the plasma membrane of melanocytes; in the second part we consider ion transport across the membrane of intracellular organelles, with emphasis on melanosomes. We discuss recently characterized lysosomal and endosomal ion channels and transporters associated with pigmentation phenotypes. We then review the evidence for melanosomal channels and transporters critical for pigmentation, discussing potential molecular mechanisms mediating their function. The studies investigating ion transport in pigmentation physiology open new avenues for future research and could reveal novel molecular mechanisms underlying melanogenesis.

Ion transport in pigmentation

PubMed Central

Bellono, Nicholas W.; Oancea, Elena V.

2014-01-01

Skin melanocytes and ocular pigment cells contain specialized organelles called melanosomes, which are responsible for the synthesis of melanin, the major pigment in mammals. Defects in the complex mechanisms involved in melanin synthesis and regulation result in vision and pigmentation deficits, impaired development of the visual system,, and increased susceptibility to skin and eye cancers. Ion transport across cellular membranes is critical for many biological processes, including pigmentation, but the molecular mechanisms by which it regulates melanin synthesis, storage, and transfer are not understood. In this review we first discuss ion channels and transporters that function at the plasma membrane of melanocytes; in the second part we consider ion transport across the membrane of intracellular organelles, with emphasis on melanosomes. We discuss recently characterized lysosomal and endosomal ion channels and transporters associated with pigmentation phenotypes. We then review the evidence for melanosomal channels and transporters critical for pigmentation, discussing potential molecular mechanisms mediating their function. The studies investigating ion transport in pigmentation physiology open new avenues for future research and could reveal novel molecular mechanisms underlying melanogenesis. PMID:25034214

Redox regulation of mitochondrial function with emphasis on cysteine oxidation reactions☆

PubMed Central

Mailloux, Ryan J.; Jin, Xiaolei; Willmore, William G.

2013-01-01

Mitochondria have a myriad of essential functions including metabolism and apoptosis. These chief functions are reliant on electron transfer reactions and the production of ATP and reactive oxygen species (ROS). The production of ATP and ROS are intimately linked to the electron transport chain (ETC). Electrons from nutrients are passed through the ETC via a series of acceptor and donor molecules to the terminal electron acceptor molecular oxygen (O2) which ultimately drives the synthesis of ATP. Electron transfer through the respiratory chain and nutrient oxidation also produces ROS. At high enough concentrations ROS can activate mitochondrial apoptotic machinery which ultimately leads to cell death. However, if maintained at low enough concentrations ROS can serve as important signaling molecules. Various regulatory mechanisms converge upon mitochondria to modulate ATP synthesis and ROS production. Given that mitochondrial function depends on redox reactions, it is important to consider how redox signals modulate mitochondrial processes. Here, we provide the first comprehensive review on how redox signals mediated through cysteine oxidation, namely S-oxidation (sulfenylation, sulfinylation), S-glutathionylation, and S-nitrosylation, regulate key mitochondrial functions including nutrient oxidation, oxidative phosphorylation, ROS production, mitochondrial permeability transition (MPT), apoptosis, and mitochondrial fission and fusion. We also consider the chemistry behind these reactions and how they are modulated in mitochondria. In addition, we also discuss emerging knowledge on disorders and disease states that are associated with deregulated redox signaling in mitochondria and how mitochondria-targeted medicines can be utilized to restore mitochondrial redox signaling. PMID:24455476

Redox regulation of mitochondrial function with emphasis on cysteine oxidation reactions.

PubMed

Mailloux, Ryan J; Jin, Xiaolei; Willmore, William G

2014-01-01

Mitochondria have a myriad of essential functions including metabolism and apoptosis. These chief functions are reliant on electron transfer reactions and the production of ATP and reactive oxygen species (ROS). The production of ATP and ROS are intimately linked to the electron transport chain (ETC). Electrons from nutrients are passed through the ETC via a series of acceptor and donor molecules to the terminal electron acceptor molecular oxygen (O2) which ultimately drives the synthesis of ATP. Electron transfer through the respiratory chain and nutrient oxidation also produces ROS. At high enough concentrations ROS can activate mitochondrial apoptotic machinery which ultimately leads to cell death. However, if maintained at low enough concentrations ROS can serve as important signaling molecules. Various regulatory mechanisms converge upon mitochondria to modulate ATP synthesis and ROS production. Given that mitochondrial function depends on redox reactions, it is important to consider how redox signals modulate mitochondrial processes. Here, we provide the first comprehensive review on how redox signals mediated through cysteine oxidation, namely S-oxidation (sulfenylation, sulfinylation), S-glutathionylation, and S-nitrosylation, regulate key mitochondrial functions including nutrient oxidation, oxidative phosphorylation, ROS production, mitochondrial permeability transition (MPT), apoptosis, and mitochondrial fission and fusion. We also consider the chemistry behind these reactions and how they are modulated in mitochondria. In addition, we also discuss emerging knowledge on disorders and disease states that are associated with deregulated redox signaling in mitochondria and how mitochondria-targeted medicines can be utilized to restore mitochondrial redox signaling.

Band Alignment and Charge Transfer in Complex Oxide Interfaces

NASA Astrophysics Data System (ADS)

Zhong, Zhicheng; Hansmann, Philipp

2017-01-01

The synthesis of transition metal heterostructures is currently one of the most vivid fields in the design of novel functional materials. In this paper, we propose a simple scheme to predict band alignment and charge transfer in complex oxide interfaces. For semiconductor heterostructures, band-alignment rules like the well-known Anderson or Schottky-Mott rule are based on comparison of the work function or electron affinity of the bulk components. This scheme breaks down for oxides because of the invalidity of a single work-function approximation as recently shown in [Phys. Rev. B 93, 235116 (2016), 10.1103/PhysRevB.93.235116; Adv. Funct. Mater. 26, 5471 (2016), 10.1002/adfm.201600243]. Here, we propose a new scheme that is built on a continuity condition of valence states originating in the compounds' shared network of oxygen. It allows for the prediction of sign and relative amplitude of the intrinsic charge transfer, taking as input only information about the bulk properties of the components. We support our claims by numerical density functional theory simulations as well as (where available) experimental evidence. Specific applications include (i) controlled doping of SrTiO3 layers with the use of 4 d and 5 d transition metal oxides and (ii) the control of magnetic ordering in manganites through tuned charge transfer.

Development of a poly(dimethylacrylamide) based matrix material for solid phase high density peptide array synthesis employing a laser based material transfer

NASA Astrophysics Data System (ADS)

Ridder, Barbara; Foertsch, Tobias C.; Welle, Alexander; Mattes, Daniela S.; von Bojnicic-Kninski, Clemens M.; Loeffler, Felix F.; Nesterov-Mueller, Alexander; Meier, Michael A. R.; Breitling, Frank

2016-12-01

Poly(dimethylacrylamide) (PDMA) based matrix materials were developed for laser-based in situ solid phase peptide synthesis to produce high density arrays. In this specific array synthesis approach, amino acid derivatives are embedded into a matrix material, serving as a ;solid; solvent material at room temperature. Then, a laser pulse transfers this mixture to the target position on a synthesis slide, where the peptide array is synthesized. Upon heating above the glass transition temperature of the matrix material, it softens, allowing diffusion of the amino acid derivatives to the synthesis surface and serving as a solvent for peptide bond formation. Here, we synthesized PDMA six-arm star polymers, offering the desired matrix material properties, using atom transfer radical polymerization. With the synthesized polymers as matrix material, we structured and synthesized arrays with combinatorial laser transfer. With densities of up to 20,000 peptide spots per cm2, the resolution could be increased compared to the commercially available standard matrix material. Time-of-Flight Secondary Ion Mass Spectrometry experiments revealed the penetration behavior of an amino acid derivative into the prepared acceptor synthesis surface and the effectiveness of the washing protocols.

[Folic acid in physiology and pathology].

PubMed

Czeczot, Hanna

2008-08-13

This paper presents current knowledge of the biological functions of folic acid, the effects of its deficiency in the organism, as well as the possibilities of its therapeutic use. Folic acid (folate, B9) is a vitamin of special importance in normal cellular functions. Tetrahydrofolate (TH4-folate) is the biologically active form of folic acid. The main role of folic acid in biochemistry is the single-carbon transfer reaction (e.g. transfer of a methyl, methylene, or formyl group). Folic acid is involved in the transformation of certain amino acids as well as in the synthesis of purines and dTMP (2'-deoxythymidine-5'-phosphate) needed for the synthesis of nucleic acid (DNA), required by all rapidly growing cells. In humans, folate deficiency results in serious pathologies, the most important of which are neural tube defects, megablastic anemia, acceleration of the arteriosclerotic process, changes in the central nervous system, and the development of certain types of cancer. To increase the intake of folic acid, preventive actions include dietary education, the main objectives of which are to increase the intake of natural folate in the daily diet, add folic acid to selected dietary products (e.g. fl our, pasta, rice), and encourage supplementation with folic acid-containing pharmaceuticals.

Switchable Synthesis of 4,5-Functionalized 1,2,3-Thiadiazoles and 1,2,3-Triazoles from 2-Cyanothioacetamides under Diazo Group Transfer Conditions.

PubMed

Filimonov, Valeriy O; Dianova, Lidia N; Galata, Kristina A; Beryozkina, Tetyana V; Novikov, Mikhail S; Berseneva, Vera S; Eltsov, Oleg S; Lebedev, Albert T; Slepukhin, Pavel A; Bakulev, Vasiliy A

2017-04-21

High yield solvent-base-controlled, transition metal-free synthesis of 4,5-functionalized 1,2,3-thiadiazoles and 1,2,3-triazoles from 2-cyanothioacetamides and sulfonyl azides is described. Under diazo transfer conditions in the presence of a base in an aprotic solvent 2-cyanothioacetamides operating as C-C-S building blocks produce 5-amino-4-cyano-1,2,3-thiadiazoles exclusively. The use of alkoxide/alcohol system completely switches the reaction course due to the change of one of the reaction centers in the 2-cyanothioacetamide (C-C-N building block) resulting in the formation of 5-sulfonamido-1,2,3-triazole-4-carbothioamide sodium salts as the only products. The latter serve as good precursors for 5-amino-1,2,3-thiadiazole-4-carboximidamides, the products of Cornforth-type rearrangement occurring in neutral protic medium or under acid conditions. According to DFT calculations (B3LYP/6-311+G(d,p)) the rearrangement proceeds via intermediate formation of a diazo compound, and can be catalyzed by acids via the protonation of oxygen atom of the sulfonamide group.

End-group-functionalized poly(N,N-diethylacrylamide) via free-radical chain transfer polymerization: Influence of sulfur oxidation and cyclodextrin on self-organization and cloud points in water

PubMed Central

Reinelt, Sebastian; Steinke, Daniel

2014-01-01

Summary In this work we report the synthesis of thermo-, oxidation- and cyclodextrin- (CD) responsive end-group-functionalized polymers, based on N,N-diethylacrylamide (DEAAm). In a classical free-radical chain transfer polymerization, using thiol-functionalized 4-alkylphenols, namely 3-(4-(1,1-dimethylethan-1-yl)phenoxy)propane-1-thiol and 3-(4-(2,4,4-trimethylpentan-2-yl)phenoxy)propane-1-thiol, poly(N,N-diethylacrylamide) (PDEAAm) with well-defined hydrophobic end-groups is obtained. These end-group-functionalized polymers show different cloud point values, depending on the degree of polymerization and the presence of randomly methylated β-cyclodextrin (RAMEB-CD). Additionally, the influence of the oxidation of the incorporated thioether linkages on the cloud point is investigated. The resulting hydrophilic sulfoxides show higher cloud point values for the lower critical solution temperature (LCST). A high degree of functionalization is supported by 1H NMR-, SEC-, FTIR- and MALDI–TOF measurements. PMID:24778720

Engineering biotin prototrophic Corynebacterium glutamicum strains for amino acid, diamine and carotenoid production.

PubMed

Peters-Wendisch, P; Götker, S; Heider, S A E; Komati Reddy, G; Nguyen, A Q; Stansen, K C; Wendisch, V F

2014-12-20

The Gram-positive Corynebacterium glutamicum is auxotrophic for biotin. Besides the biotin uptake system BioYMN and the transcriptional regulator BioQ, this bacterium possesses functional enzymes for the last three reactions of biotin synthesis starting from pimeloyl-CoA. Heterologous expression of bioF from the Gram-negative Escherichia coli enabled biotin synthesis from pimelic acid added to the medium, but expression of bioF together with bioC and bioH from E. coli did not entail biotin prototrophy. Heterologous expression of bioWAFDBI from Bacillus subtilis encoding another biotin synthesis pathway in C. glutamicum allowed for growth in biotin-depleted media. Stable growth of the recombinant was observed without biotin addition for eight transfers to biotin-depleted medium while the empty vector control stopped growth after the first transfer. Expression of bioWAFDBI from B. subtilis in C. glutamicum strains overproducing the amino acids l-lysine and l-arginine, the diamine putrescine, and the carotenoid lycopene, respectively, enabled formation of these products under biotin-depleted conditions. Thus, biotin-prototrophic growth and production by recombinant C. glutamicum were achieved. Copyright © 2014 Elsevier B.V. All rights reserved.

A reliable algorithm for optimal control synthesis

NASA Technical Reports Server (NTRS)

Vansteenwyk, Brett; Ly, Uy-Loi

1992-01-01

In recent years, powerful design tools for linear time-invariant multivariable control systems have been developed based on direct parameter optimization. In this report, an algorithm for reliable optimal control synthesis using parameter optimization is presented. Specifically, a robust numerical algorithm is developed for the evaluation of the H(sup 2)-like cost functional and its gradients with respect to the controller design parameters. The method is specifically designed to handle defective degenerate systems and is based on the well-known Pade series approximation of the matrix exponential. Numerical test problems in control synthesis for simple mechanical systems and for a flexible structure with densely packed modes illustrate positively the reliability of this method when compared to a method based on diagonalization. Several types of cost functions have been considered: a cost function for robust control consisting of a linear combination of quadratic objectives for deterministic and random disturbances, and one representing an upper bound on the quadratic objective for worst case initial conditions. Finally, a framework for multivariable control synthesis has been developed combining the concept of closed-loop transfer recovery with numerical parameter optimization. The procedure enables designers to synthesize not only observer-based controllers but also controllers of arbitrary order and structure. Numerical design solutions rely heavily on the robust algorithm due to the high order of the synthesis model and the presence of near-overlapping modes. The design approach is successfully applied to the design of a high-bandwidth control system for a rotorcraft.

Electrografting of diazonium-functionalized polyoxometalates: synthesis, immobilisation and electron-transfer characterisation from glassy carbon.

PubMed

Rinfray, Corentin; Izzet, Guillaume; Pinson, Jean; Gam Derouich, Sarra; Ganem, Jean-Jacques; Combellas, Catherine; Kanoufi, Frédéric; Proust, Anna

2013-10-04

Polyoxometalates (POMs) are attractive candidates for the rational design of multi-level charge-storage materials because they display reversible multi-step reduction processes in a narrow range of potentials. The functionalization of POMs allows for their integration in hybrid complementary metal oxide semiconductor (CMOS)/molecular devices, provided that fine control of their immobilisation on various substrates can be achieved. Owing to the wide applicability of the diazonium route to surface modification, a functionalized Keggin-type POM [PW11 O39 {Ge(p-C6 H4 -CC-C6 H4 -${{\\rm N}{{+\\hfill \\atop 2\\hfill}}}$)}](3-) bearing a pending diazonium group was prepared and subsequently covalently anchored onto a glassy carbon electrode. Electron transfer with the immobilised POM was thoroughly investigated and compared to that of the free POM in solution. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Growth factor transgenes interactively regulate articular chondrocytes.

PubMed

Shi, Shuiliang; Mercer, Scott; Eckert, George J; Trippel, Stephen B

2013-04-01

Adult articular chondrocytes lack an effective repair response to correct damage from injury or osteoarthritis. Polypeptide growth factors that stimulate articular chondrocyte proliferation and cartilage matrix synthesis may augment this response. Gene transfer is a promising approach to delivering such factors. Multiple growth factor genes regulate these cell functions, but multiple growth factor gene transfer remains unexplored. We tested the hypothesis that multiple growth factor gene transfer selectively modulates articular chondrocyte proliferation and matrix synthesis. We tested the hypothesis by delivering combinations of the transgenes encoding insulin-like growth factor I (IGF-I), fibroblast growth factor-2 (FGF-2), transforming growth factor beta1 (TGF-β1), bone morphogenetic protein-2 (BMP-2), and bone morphogenetic protien-7 (BMP-7) to articular chondrocytes and measured changes in the production of DNA, glycosaminoglycan, and collagen. The transgenes differentially regulated all these chondrocyte activities. In concert, the transgenes interacted to generate widely divergent responses from the cells. These interactions ranged from inhibitory to synergistic. The transgene pair encoding IGF-I and FGF-2 maximized cell proliferation. The three-transgene group encoding IGF-I, BMP-2, and BMP-7 maximized matrix production and also optimized the balance between cell proliferation and matrix production. These data demonstrate an approach to articular chondrocyte regulation that may be tailored to stimulate specific cell functions, and suggest that certain growth factor gene combinations have potential value for cell-based articular cartilage repair. Copyright © 2012 Wiley Periodicals, Inc.

Genetics Home Reference: TRNT1 deficiency

MedlinePlus

... in the production (synthesis) of other proteins. During protein synthesis, a molecule called transfer RNA (tRNA) helps assemble ... thought to be less able to participate in protein synthesis. Researchers suspect that protein synthesis in cellular structures ...

NESSY: NLTE spectral synthesis code for solar and stellar atmospheres

NASA Astrophysics Data System (ADS)

Tagirov, R. V.; Shapiro, A. I.; Schmutz, W.

2017-07-01

Context. Physics-based models of solar and stellar magnetically-driven variability are based on the calculation of synthetic spectra for various surface magnetic features as well as quiet regions, which are a function of their position on the solar or stellar disc. Such calculations are performed with radiative transfer codes tailored for modeling broad spectral intervals. Aims: We aim to present the NLTE Spectral SYnthesis code (NESSY), which can be used for modeling of the entire (UV-visible-IR and radio) spectra of solar and stellar magnetic features and quiet regions. Methods: NESSY is a further development of the COde for Solar Irradiance (COSI), in which we have implemented an accelerated Λ-iteration (ALI) scheme for co-moving frame (CMF) line radiation transfer based on a new estimate of the local approximate Λ-operator. Results: We show that the new version of the code performs substantially faster than the previous one and yields a reliable calculation of the entire solar spectrum. This calculation is in a good agreement with the available observations.

Interactions between late acting proteins required for peptidoglycan synthesis during sporulation

PubMed Central

Fay, Allison; Meyer, Pablo; Dworkin, Jonathan

2010-01-01

The requirement of peptidoglycan synthesis for growth complicates the analysis of interactions between proteins involved in this pathway. In particular, the later steps that involve membrane-linked substrates have proven largely recalcitrant to in vivo analysis. Here we have taken advantage of the peptidoglycan synthesis that occurs during sporulation in Bacillus subtilis to examine the interactions between SpoVE, a non-essential, sporulation-specific homolog of the well-conserved and essential SEDS proteins, and SpoVD, a non-essential class B penicillin binding protein (PBP). We found that localization of SpoVD is dependent on SpoVE and that SpoVD protects SpoVE from in vivo proteolysis. Co-immunoprecipitations and Fluorescence Resonance Energy Transfer experiments indicated that SpoVE and SpoVD interact and co-affinity purification in E. coli demonstrated that this interaction is direct. Finally, we generated a functional protein consisting of a SpoVE-SpoVD fusion and found that a loss-of-function point mutation in either part of the fusion resulted in a loss of function of the entire fusion that was not complemented by a wild type protein. Thus, SpoVE has a direct and functional interaction with SpoVD and this conclusion will facilitate understanding the essential function SpoVE and related SEDS proteins such as FtsW and RodA play in bacterial growth and division. PMID:20417640

Template Dimerization Promotes an Acceptor Invasion-Induced Transfer Mechanism during Human Immunodeficiency Virus Type 1 Minus-Strand Synthesis

PubMed Central

Balakrishnan, Mini; Roques, Bernard P.; Fay, Philip J.; Bambara, Robert A.

2003-01-01

The biochemical mechanism of template switching by human immunodeficiency virus type 1 (HIV-1) reverse transcriptase and the role of template dimerization were examined. Homologous donor-acceptor template pairs derived from the HIV-1 untranslated leader region and containing the wild-type and mutant dimerization initiation sequences (DIS) were used to examine the efficiency and distribution of transfers. Inhibiting donor-acceptor interaction was sufficient to reduce transfers in DIS-containing template pairs, indicating that template dimerization, and not the mere presence of the DIS, promotes efficient transfers. Additionally, we show evidence that the overall transfer process spans an extended region of the template and proceeds through a two-step mechanism. Transfer is initiated through an RNase H-facilitated acceptor invasion step, while synthesis continues on the donor template. The invasion then propagates towards the primer terminus by branch migration. Transfer is completed with the translocation of the primer terminus at a site distant from the invasion point. In our system, most invasions initiated before synthesis reached the DIS. However, transfer of the primer terminus predominantly occurred after synthesis through the DIS. The two steps were separated by 60 to 80 nucleotides. Sequence markers revealed the position of primer terminus switch, whereas DNA oligomers designed to block acceptor-cDNA interactions defined sites of invasion. Within the region of homology, certain positions on the template were inherently more favorable for invasion than others. In templates with DIS, the proximity of the acceptor facilitates invasion, thereby enhancing transfer efficiency. Nucleocapsid protein enhanced the overall efficiency of transfers but did not alter the mechanism. PMID:12663778

Transglycosylation properties of maltodextrin glucosidase (MalZ) from Escherichia coli and its application for synthesis of a nigerose-containing oligosaccharide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Kyung-Mo; Shim, Jae-Hoon; Park, Jong-Tae

2010-06-18

The transglycosylation reaction of maltodextrin glucosidase (MalZ) cloned and purified from Escherichia coli K12 was characterized and applied to the synthesis of branched oligosaccharides. Purified MalZ preferentially catalyzed the hydrolysis of maltodextrin, {gamma}-cyclodextrin (CD), and cycloamylose (CA). In addition, when the enzyme was incubated with 5% maltotriose (G3), a series of transfer products were produced. The resulting major transfer products, annotated as T1, T2, and T3, were purified and their structures were determined by TLC, MALDI-TOF/MS, {sup 13}C NMR, and enzymatic analysis. T1 was identified as a novel compound, maltosyl {alpha}-1,3-maltose, whereas T2 and T3 were determined to be isopanosemore » and maltosyl-{alpha}-1,6-maltose, respectively. These results indicated that MalZ transferred sugar moiety mainly to C-3 or C-6-OH of glucose of the acceptor molecule. To obtain highly concentrated transfer products, the enzyme was reacted with 10% liquefied cornstarch, and then glucose and maltose were removed by immobilized yeast. The T1 content of the resulting reaction mixture reached 9.0%. The mixture of T1 containing a nigerose moiety can have an immunopotentiating effect on the human body and may be a potential functional sugar stuff.« less

Enantioselective Total Synthesis of Natural Isoflavans: Asymmetric Transfer Hydrogenation/Deoxygenation of Isoflavanones with Dynamic Kinetic Resolution.

PubMed

Keßberg, Anton; Lübken, Tilo; Metz, Peter

2018-05-02

A concise and highly enantioselective synthesis of structurally diverse isoflavans from a single chromone is described. The key transformation is a single-step conversion of racemic isoflavanones into virtually enantiopure isoflavans by domino asymmetric transfer hydrogenation/deoxygenation with dynamic kinetic resolution.

Ab initio study of energy transfer rates and impact sensitivities of crystalline explosives.

PubMed

Bernstein, Jonathan

2018-02-28

Impact sensitivities of various crystalline explosives were predicted by means of plane wave-density functional theory calculations. Crystal structures and complete vibrational spectra of TATB, PETN, FOX7, TEX, 14DNI, and β-HMX molecular crystals were calculated. A correlation between the phonon-vibron coupling (which is proportionally related to the energy transfer rate between the phonon manifold and the intramolecular vibrational modes) and impact sensitivities of secondary explosives was found. We propose a method, based on ab initio calculations, for the evaluation of impact sensitivities, which consequently can assist in screening candidates for chemical synthesis of high energetic materials.

Ab initio study of energy transfer rates and impact sensitivities of crystalline explosives

NASA Astrophysics Data System (ADS)

Bernstein, Jonathan

2018-02-01

Impact sensitivities of various crystalline explosives were predicted by means of plane wave-density functional theory calculations. Crystal structures and complete vibrational spectra of TATB, PETN, FOX7, TEX, 14DNI, and β-HMX molecular crystals were calculated. A correlation between the phonon-vibron coupling (which is proportionally related to the energy transfer rate between the phonon manifold and the intramolecular vibrational modes) and impact sensitivities of secondary explosives was found. We propose a method, based on ab initio calculations, for the evaluation of impact sensitivities, which consequently can assist in screening candidates for chemical synthesis of high energetic materials.

Charge Compensation and Electrostatic Transferability in Three Entropy Stabilized Oxides: Results from Density Functional Theory Calculations

DTIC Science & Technology

2016-09-06

displacements from ideal lattice sites, along with reduction of a few Co and Ni cations. Addition of Li to J14 reduces the lattice constant, consistent...associated with the atoms as well as in displacements of atoms from their ideal lattice sites. II. SYNTHESIS OF THE J141Sc COMPOSITION Berardan et al...Plotted in Figure 6 are the average atom displacements for the three large systems as a function of element type. For J14 (open bars), the dis

Liposome-chaperoned cell-free synthesis for the design of proteoliposomes: Implications for therapeutic delivery.

PubMed

Lu, Mei; Zhao, Xiaoyun; Xing, Haonan; Xun, Zhe; Yang, Tianzhi; Cai, Cuifang; Wang, Dongkai; Ding, Pingtian

2018-04-03

Cell-free (CF) protein synthesis has emerged as a powerful technique platform for efficient protein production in vitro. Liposomes have been widely studied as therapeutic carriers due to their biocompatibility, biodegradability, low toxicity, flexible surface manipulation, easy preparation, and higher cargo encapsulation capability. However, rapid immune clearance, insufficient targeting capacity, and poor cytoplasmic delivery efficiency substantially restrict their clinical application. The incorporation of functional membrane proteins (MPs) or peptides allows the transfer of biological properties to liposomes and imparts them with improved circulation, increased targeting, and efficient intracellular delivery. Liposome-chaperoned CF synthesis enables production of proteoliposomes in one-step reaction, which not only substantially simplifies the production procedure but also keeps protein functionality intact. Building off these observations, proteoliposomes with integrated MPs represent an excellent candidate for therapeutic delivery. In this review, we describe recent advances in CF synthesis with emphasis on detailing key factors for improving CF expression efficiency. Furthermore, we provide insights into strategies for rational design of proteoliposomal nanodelivery systems via CF synthesis. Liposome-chaperoned CF synthesis has emerged as a powerful approach for the design of recombinant proteoliposomes in one-step reaction. The incorporation of bioactive MPs or peptides into liposomes via CF synthesis can facilitate the development of proteoliposomal nanodelivery systems with improved circulation, increased targeting, and enhanced cellular delivery capacity. Moreover, by adapting lessons learned from natural delivery vehicles, novel bio-inspired proteoliposomes with enhanced delivery properties could be produced in CF systems. In this review, we first give an overview of CF synthesis with focus on enhancing protein expression in liposome-chaperoned CF systems. Furthermore, we intend to provide insight into harnessing CF-synthesized proteoliposomes for efficient therapeutic delivery. Copyright © 2018. Published by Elsevier Ltd.

An essential role of the mitochondrial electron transport chain in cell proliferation is to enable aspartate synthesis

PubMed Central

Birsoy, Kıvanç; Wang, Tim; Chen, Walter; Freinkman, Elizaveta; Abu-Remaileh, Monther; Sabatini, David M.

2015-01-01

Summary The mitochondrial electron transport chain (ETC) enables many metabolic processes, but why its inhibition suppresses cell proliferation is unclear. It is also not well understood why pyruvate supplementation allows cells lacking ETC function to proliferate. We used a CRISPR-based genetic screen to identify genes whose loss sensitizes human cells to phenformin, a complex I inhibitor. The screen yielded GOT1, the cytosolic aspartate aminotransferase, loss of which kills cells upon ETC inhibition. GOT1 normally consumes aspartate to transfer electrons into mitochondria, but, upon ETC inhibition, it reverses to generate aspartate in the cytosol, which partially compensates for the loss of mitochondrial aspartate synthesis. Pyruvate stimulates aspartate synthesis in a GOT1-dependent fashion, which is required for pyruvate to rescue proliferation of cells with ETC dysfunction. Aspartate supplementation or overexpression of an aspartate transporter allows cells without ETC activity to proliferate. Thus, enabling aspartate synthesis is an essential role of the ETC in cell proliferation. PMID:26232224

Serine Metabolism Supports the Methionine Cycle and DNA/RNA Methylation through De Novo ATP Synthesis in Cancer Cells

PubMed Central

Maddocks, Oliver D.K.; Labuschagne, Christiaan F.; Adams, Peter D.; Vousden, Karen H.

2016-01-01

Summary Crosstalk between cellular metabolism and the epigenome regulates epigenetic and metabolic homeostasis and normal cell behavior. Changes in cancer cell metabolism can directly impact epigenetic regulation and promote transformation. Here we analyzed the contribution of methionine and serine metabolism to methylation of DNA and RNA. Serine can contribute to this pathway by providing one-carbon units to regenerate methionine from homocysteine. While we observed this contribution under methionine-depleted conditions, unexpectedly, we found that serine supported the methionine cycle in the presence and absence of methionine through de novo ATP synthesis. Serine starvation increased the methionine/S-adenosyl methionine ratio, decreasing the transfer of methyl groups to DNA and RNA. While serine starvation dramatically decreased ATP levels, this was accompanied by lower AMP and did not activate AMPK. This work highlights the difference between ATP turnover and new ATP synthesis and defines a vital function of nucleotide synthesis beyond making nucleic acids. PMID:26774282

Serine Metabolism Supports the Methionine Cycle and DNA/RNA Methylation through De Novo ATP Synthesis in Cancer Cells.

PubMed

Maddocks, Oliver D K; Labuschagne, Christiaan F; Adams, Peter D; Vousden, Karen H

2016-01-21

Crosstalk between cellular metabolism and the epigenome regulates epigenetic and metabolic homeostasis and normal cell behavior. Changes in cancer cell metabolism can directly impact epigenetic regulation and promote transformation. Here we analyzed the contribution of methionine and serine metabolism to methylation of DNA and RNA. Serine can contribute to this pathway by providing one-carbon units to regenerate methionine from homocysteine. While we observed this contribution under methionine-depleted conditions, unexpectedly, we found that serine supported the methionine cycle in the presence and absence of methionine through de novo ATP synthesis. Serine starvation increased the methionine/S-adenosyl methionine ratio, decreasing the transfer of methyl groups to DNA and RNA. While serine starvation dramatically decreased ATP levels, this was accompanied by lower AMP and did not activate AMPK. This work highlights the difference between ATP turnover and new ATP synthesis and defines a vital function of nucleotide synthesis beyond making nucleic acids. Copyright © 2016 The Authors. Published by Elsevier Inc. All rights reserved.

An Essential Role of the Mitochondrial Electron Transport Chain in Cell Proliferation Is to Enable Aspartate Synthesis.

PubMed

Birsoy, Kıvanç; Wang, Tim; Chen, Walter W; Freinkman, Elizaveta; Abu-Remaileh, Monther; Sabatini, David M

2015-07-30

The mitochondrial electron transport chain (ETC) enables many metabolic processes, but why its inhibition suppresses cell proliferation is unclear. It is also not well understood why pyruvate supplementation allows cells lacking ETC function to proliferate. We used a CRISPR-based genetic screen to identify genes whose loss sensitizes human cells to phenformin, a complex I inhibitor. The screen yielded GOT1, the cytosolic aspartate aminotransferase, loss of which kills cells upon ETC inhibition. GOT1 normally consumes aspartate to transfer electrons into mitochondria, but, upon ETC inhibition, it reverses to generate aspartate in the cytosol, which partially compensates for the loss of mitochondrial aspartate synthesis. Pyruvate stimulates aspartate synthesis in a GOT1-dependent fashion, which is required for pyruvate to rescue proliferation of cells with ETC dysfunction. Aspartate supplementation or overexpression of an aspartate transporter allows cells without ETC activity to proliferate. Thus, enabling aspartate synthesis is an essential role of the ETC in cell proliferation. Copyright © 2015 Elsevier Inc. All rights reserved.

The Absence of a Mature Cell Wall Sacculus in Stable Listeria monocytogenes L-Form Cells Is Independent of Peptidoglycan Synthesis.

PubMed

Studer, Patrick; Borisova, Marina; Schneider, Alexander; Ayala, Juan A; Mayer, Christoph; Schuppler, Markus; Loessner, Martin J; Briers, Yves

2016-01-01

L-forms are cell wall-deficient variants of otherwise walled bacteria that maintain the ability to survive and proliferate in absence of the surrounding peptidoglycan sacculus. While transient or unstable L-forms can revert to the walled state and may still rely on residual peptidoglycan synthesis for multiplication, stable L-forms cannot revert to the walled form and are believed to propagate in the complete absence of peptidoglycan. L-forms are increasingly studied as a fundamental biological model system for cell wall synthesis. Here, we show that a stable L-form of the intracellular pathogen Listeria monocytogenes features a surprisingly intact peptidoglycan synthesis pathway including glycosyl transfer, in spite of the accumulation of multiple mutations during prolonged passage in the cell wall-deficient state. Microscopic and biochemical analysis revealed the presence of peptidoglycan precursors and functional glycosyl transferases, resulting in the formation of peptidoglycan polymers but without the synthesis of a mature cell wall sacculus. In conclusion, we found that stable, non-reverting L-forms, which do not require active PG synthesis for proliferation, may still continue to produce aberrant peptidoglycan.

Survey of digital filtering

NASA Technical Reports Server (NTRS)

Nagle, H. T., Jr.

1972-01-01

A three part survey is made of the state-of-the-art in digital filtering. Part one presents background material including sampled data transformations and the discrete Fourier transform. Part two, digital filter theory, gives an in-depth coverage of filter categories, transfer function synthesis, quantization and other nonlinear errors, filter structures and computer aided design. Part three presents hardware mechanization techniques. Implementations by general purpose, mini-, and special-purpose computers are presented.

Synthesis of tris- and tetrakis(pentafluoroethyl)silanes.

PubMed

Steinhauer, Simon; Bader, Julia; Stammler, Hans-Georg; Ignat'ev, Nikolai; Hoge, Berthold

2014-05-12

The synthesis and complete characterization of functional, highly Lewis acidic tris(pentafluoroethyl)silanes as well as tetrakis(perfluoroalkyl)silanes Si(C2F5)4 and Si(C2F5)3 CF3 by direct fluorination is described. The reaction of SiCl4 with LiC2F5 invariably affords (pentafluoroethyl)fluorosilicates. To avoid silicate formation by fluoride transfer from LiC2F5 the Lewis acidity of the silane has to be decreased by electron-donating substituents, such as dialkylamino groups. The easily accessible Si(C2F5)3 NEt2 is a valuable precursor for a series of tris(pentafluoroethyl)silanes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Functional Dynamics within the Human Ribosome Regulate the Rate of Active Protein Synthesis.

PubMed

Ferguson, Angelica; Wang, Leyi; Altman, Roger B; Terry, Daniel S; Juette, Manuel F; Burnett, Benjamin J; Alejo, Jose L; Dass, Randall A; Parks, Matthew M; Vincent, C Theresa; Blanchard, Scott C

2015-11-05

The regulation of protein synthesis contributes to gene expression in both normal physiology and disease, yet kinetic investigations of the human translation mechanism are currently lacking. Using single-molecule fluorescence imaging methods, we have quantified the nature and timing of structural processes in human ribosomes during single-turnover and processive translation reactions. These measurements reveal that functional complexes exhibit dynamic behaviors and thermodynamic stabilities distinct from those observed for bacterial systems. Structurally defined sub-states of pre- and post-translocation complexes were sensitive to specific inhibitors of the eukaryotic ribosome, demonstrating the utility of this platform to probe drug mechanism. The application of three-color single-molecule fluorescence resonance energy transfer (smFRET) methods further revealed a long-distance allosteric coupling between distal tRNA binding sites within ribosomes bearing three tRNAs, which contributed to the rate of processive translation. Copyright © 2015 Elsevier Inc. All rights reserved.

Exosomes released by keratinocytes modulate melanocyte pigmentation

PubMed Central

Cicero, Alessandra Lo; Delevoye, Cédric; Gilles-Marsens, Floriane; Loew, Damarys; Dingli, Florent; Guéré, Christelle; André, Nathalie; Vié, Katell; van Niel, Guillaume; Raposo, Graça

2015-01-01

Cells secrete extracellular vesicles (EVs), exosomes and microvesicles, which transfer proteins, lipids and RNAs to regulate recipient cell functions. Skin pigmentation relies on a tight dialogue between keratinocytes and melanocytes in the epidermis. Here we report that exosomes secreted by keratinocytes enhance melanin synthesis by increasing both the expression and activity of melanosomal proteins. Furthermore, we show that the function of keratinocyte-derived exosomes is phototype-dependent and is modulated by ultraviolet B. In sum, this study uncovers an important physiological function for exosomes in human pigmentation and opens new avenues in our understanding of how pigmentation is regulated by intercellular communication in both healthy and diseased states. PMID:26103923

The prion protein has DNA strand transfer properties similar to retroviral nucleocapsid protein.

PubMed

Gabus, C; Auxilien, S; Péchoux, C; Dormont, D; Swietnicki, W; Morillas, M; Surewicz, W; Nandi, P; Darlix, J L

2001-04-06

The transmissible spongiform encephalopathies are fatal neurodegenerative diseases that are associated with the accumulation of a protease-resistant form of the cellular prion protein (PrP). Although PrP is highly conserved and widely expressed in vertebrates, its function remains a matter of speculation. Indeed PrP null mice develop normally and are healthy. Recent results show that PrP binds to nucleic acids in vitro and is found associated with retroviral particles. Furthermore, in mice the scrapie infectious process appears to be accelerated by MuLV replication. These observations prompted us to further investigate the interaction between PrP and nucleic acids, and compare it with that of the retroviral nucleocapsid protein (NC). As the major nucleic acid-binding protein of the retroviral particle, NC protein is tightly associated with the genomic RNA in the virion nucleocapsid, where it chaperones proviral DNA synthesis by reverse transcriptase. Our results show that the human prion protein (huPrP) functionally resembles NCp7 of HIV-1. Both proteins form large nucleoprotein complexes upon binding to DNA. They accelerate the hybridization of complementary DNA strands and chaperone viral DNA synthesis during the minus and plus DNA strand transfers necessary to generate the long terminal repeats. The DNA-binding and strand transfer properties of huPrP appear to map to the N-terminal fragment comprising residues 23 to 144, whereas the C-terminal domain is inactive. These findings suggest that PrP could be involved in nucleic acid metabolism in vivo. Copyright 2001 Academic Press.

Synthesis and electrochemical studies of charge-transfer complexes of thiazolidine-2,4-dione with σ and π acceptors

NASA Astrophysics Data System (ADS)

Singh, Prashant; Kumar, Pradeep; Katyal, Anju; Kalra, Rashmi; Dass, Sujata K.; Prakash, Satya; Chandra, Ramesh

2010-03-01

In the present work, we report the synthesis and characterization of novel charge-transfer complexes of thiazolidine-2,4-dione (TZD) with sigma acceptor (iodine) and pi acceptors (chloranil, dichlorodicyanoquinone, picric acid and duraquinone). We also evaluated their thermal and electrochemical properties and we conclude that these complexes are frequency dependent. Charge-transfer complex between thiazolidine-2,4-dione and iodine give best conductivity. In conclusion, complex with sigma acceptors are more conducting than with pi acceptors.

SOLID-LIQUID PHASE TRANSFER CATALYZED SYNTHESIS OF CINNAMYL ACETATE-KINETICS AND ANALYSIS OF FACTORS AFFECTING THE REACTION IN A BATCH REACTOR

EPA Science Inventory

The use of solid-liquid phase transfer catalysis has an advantage of carrying out reaction between two immiscible substrates, one in solid phase and the other in liquid phase, with high selectivity and at relatively low temperatures. In this study we investigated the synthesis ci...

EM Propagation & Atmospheric Effects Assessment

DTIC Science & Technology

2008-09-30

The split-step Fourier parabolic equation ( SSPE ) algorithm provides the complex amplitude and phase (group delay) of the continuous wave (CW) signal...the APM is based on the SSPE , we are implementing the more efficient Fourier synthesis technique to determine the transfer function. To this end a...needed in order to sample H(f) via the SSPE , and indeed with the proper parameters chosen, the two pulses can be resolved in the time window shown in

The role of phosphatidylinositol-transfer proteins at membrane contact sites.

PubMed

Selitrennik, Michael; Lev, Sima

2016-04-15

Phosphatidylinositol-transfer proteins (PITPs) have been initially identified as soluble factors that accelerate the monomeric exchange of either phosphatidylinositol (PI) or phosphatidylcholine (PC) between membrane bilayersin vitro They are highly conserved in eukaryotes and have been implicated in different cellular processes, including vesicular trafficking, signal transduction, and lipid metabolism. Recent studies suggest that PITPs function at membrane contact sites (MCSs) to facilitate the transport of PI from its synthesis site at the endoplasmic reticulum (ER) to various membrane compartments. In this review, we describe the underlying mechanism of PITPs targeting to MCSs, discuss their cellular roles and potential mode of action. © 2016 Authors; published by Portland Press Limited.

Research on output feedback control

NASA Technical Reports Server (NTRS)

Calise, A. J.; Kramer, F. S.

1985-01-01

In designing fixed order compensators, an output feedback formulation has been adopted by suitably augmenting the system description to include the compensator states. However, the minimization of the performance index over the range of possible compensator descriptions was impeded due to the nonuniqueness of the compensator transfer function. A controller canonical form of the compensator was chosen to reduce the number of free parameters to its minimal number in the optimization. In the MIMO case, the controller form requires a prespecified set of ascending controllability indices. This constraint on the compensator structure is rather innocuous in relation to the increase in convergence rate of the optimization. Moreover, the controller form is easily relatable to a unique controller transfer function description. This structure of the compensator does not require penalizing the compensator states for a nonzero or coupled solution, a problem that occurs when following a standard output feedback synthesis formulation.

When contemporary aminoacyl-tRNA synthetases invent their cognate amino acid metabolism

PubMed Central

Roy, Hervé; Becker, Hubert Dominique; Reinbolt, Joseph; Kern, Daniel

2003-01-01

Faithful protein synthesis relies on a family of essential enzymes called aminoacyl-tRNA synthetases, assembled in a piecewise fashion. Analysis of the completed archaeal genomes reveals that all archaea that possess asparaginyl-tRNA synthetase (AsnRS) also display a second ORF encoding an AsnRS truncated from its anticodon binding-domain (AsnRS2). We show herein that Pyrococcus abyssi AsnRS2, in contrast to AsnRS, does not sustain asparaginyl-tRNAAsn synthesis but is instead capable of converting aspartic acid into asparagine. Functional analysis and complementation of an Escherichia coli asparagine auxotrophic strain show that AsnRS2 constitutes the archaeal homologue of the bacterial ammonia-dependent asparagine synthetase A (AS-A), therefore named archaeal asparagine synthetase A (AS-AR). Primary sequence- and 3D-based phylogeny shows that an archaeal AspRS ancestor originated AS-AR, which was subsequently transferred into bacteria by lateral gene transfer in which it underwent structural changes producing AS-A. This study provides evidence that a contemporary aminoacyl-tRNA synthetase can be recruited to sustain amino acid metabolism. PMID:12874385

Synthesis of photolabile transcription initiators and preparation of photocleavable functional RNA by transcription.

PubMed

Huang, Faqing; Shi, Yongliang

2012-07-01

Two new photolabile adenosine-containing transcription initiators with terminal thiol and amino functionalities are chemically synthesized. Transcription in the presence of the transcription initiators under the T7 phi2.5 promoter produces 5' thiol- and amino-functionalized RNA conjugated by a photocleavable (PC) linker. Further RNA functionalization with biotin may be achieved through acyl transfer reactions from either biotinyl AMP to the RNA thiol group or biotin NHS to the RNA amino group. Photocleavage of the PC linker displays relatively fast kinetics with a half-life of 4-5 min. The availability of these transcription initiators makes new photolabile RNA accessible for affinity purification of RNA, in vitro selection of functional RNAs, and functional RNA caging. Copyright © 2012 Elsevier Ltd. All rights reserved.

A Working Model of Protein Synthesis Using Lego(TM) Building Blocks.

ERIC Educational Resources Information Center

Templin, Mark A.; Fetters, Marcia K.

2002-01-01

Uses Lego building blocks to improve the effectiveness of teaching about protein synthesis. Provides diagrams and pictures for a 2-3 day student activity. Discusses mRNA, transfer RNA, and a protein synthesis model. (MVL)

Brain glutamine synthesis requires neuronal-born aspartate as amino donor for glial glutamate formation.

PubMed

Pardo, Beatriz; Rodrigues, Tiago B; Contreras, Laura; Garzón, Miguel; Llorente-Folch, Irene; Kobayashi, Keiko; Saheki, Takeyori; Cerdan, Sebastian; Satrústegui, Jorgina

2011-01-01

The glutamate-glutamine cycle faces a drain of glutamate by oxidation, which is balanced by the anaplerotic synthesis of glutamate and glutamine in astrocytes. De novo synthesis of glutamate by astrocytes requires an amino group whose origin is unknown. The deficiency in Aralar/AGC1, the main mitochondrial carrier for aspartate-glutamate expressed in brain, results in a drastic fall in brain glutamine production but a modest decrease in brain glutamate levels, which is not due to decreases in neuronal or synaptosomal glutamate content. In vivo (13)C nuclear magnetic resonance labeling with (13)C(2)acetate or (1-(13)C) glucose showed that the drop in brain glutamine is due to a failure in glial glutamate synthesis. Aralar deficiency induces a decrease in aspartate content, an increase in lactate production, and lactate-to-pyruvate ratio in cultured neurons but not in cultured astrocytes, indicating that Aralar is only functional in neurons. We find that aspartate, but not other amino acids, increases glutamate synthesis in both control and aralar-deficient astrocytes, mainly by serving as amino donor. These findings suggest the existence of a neuron-to-astrocyte aspartate transcellular pathway required for astrocyte glutamate synthesis and subsequent glutamine formation. This pathway may provide a mechanism to transfer neuronal-born redox equivalents to mitochondria in astrocytes.

Synthesis and phase behavior of end-functionalized associating polymers

NASA Astrophysics Data System (ADS)

Wrue, Michelle H.

We have explored polymer blend phase behavior in the presence of multiple hydrogen bonding end-groups. This work details the synthesis of functionalized polymers and their subsequent use in miscibility studies. The synthesis of end-functionalized hydrogen bonding polymers and the investigation of their physical properties and miscibility is presented. Mono-functional and telechelic ureidopyrimidinone (UPy) functionalized polymers were prepared by two main routes: post-polymerization functionalization (of commercially available or synthesized polymers); and polymerization of monomers using a functionalized initiator. UPy-functionalized polymers were prepared with a variety of polymer backbones including poly(ethylene oxide)s; poly(butadiene)s, poly(dimethyl siloxanxe)s; poly(styrene)s and poly(methyl methacrylate)s. The most successful route to polymers with UPy end-groups was atom transfer radical polymerization (ATRP) using a UPy-functionalized initiator, followed by atom transfer radical coupling (ATRC). The incorporation of ureidopyrimidinone end-groups was shown to affect the physical properties of the polymer backbone. Parent polymers that were liquids became viscous liquids or waxy solids upon UPy-functionalization of chain end. UPy-functionalization of a hydroxyl-terminated polybutadiene (HO-PB-OH) resulted in a waxy solid while the HO-PB-OH precursor was a viscous liquid. The thermal properties of functionalized polymers also differed from those of the unfunctionalized parent polymers. Hot-stage optical microscopy revealed that UPy-functionalized PEO displayed a depressed melting point relative to the analogous unfunctionalized precursor. Differential scanning calorimetry was also used to investigate the synthesized UPy-polymers. UPy-functionalized polystyrenes and poly(methyl methacrylate)s showed an increased T g compared to the equivalent homopolymer standards. This increased Tg was determined to be dependent upon the fraction of UPy groups present and chemical cleavage of the end-groups resulted in Tgs near those observed for polymer standards of comparable molecular weight. Aggregation of UPy end-groups in solution was observed using gel permeation chromatography. Aggregation was only observed for telechelic samples of low molecular weight, indicating that the aggregation of end-groups is dependent upon the concentration of the end-groups. The effect of UPy end-groups on blend miscibility was studied in solution using laser light scattering and in the melt state was using laser light scattering, optical microscopy and differential scanning calorimetry. The incorporation of associating groups onto one end of either blend component decreases miscibility relative to unfunctionalized parent blends. Lower miscibility was also observed for blends in which both components were mono-functionalized with associating end-groups. The largest decrease in miscibility was observed for blends containing telechelic UPy-functionalized polymers, which were immiscible across the entire composition range.

Plasmonic properties and enhanced fluorescence of gold and dye-doped silica nanoparticle aggregates

NASA Astrophysics Data System (ADS)

Green, Nathaniel Scott

The development of metal-enhanced fluorescence has prompted a great interest in augmenting the photophysical properties of fluorescent molecules with noble metal nanostructures. Our research efforts, outlined in this dissertation, focus on augmenting properties of fluorophores by conjugation with gold nanostructures. The project goals are split into two separate efforts; the enhancement in brightness of fluorophores and long distance non-radiative energy transfer between fluorophores. We believe that interacting dye-doped silica nanoparticles with gold nanoparticles can facilitate both of these phenomena. Our primary research interest is focused on optimizing brightness, as this goal should open a path to studying the second goal of non-radiative energy transfer. The two major challenges to this are constructing suitable nanomaterials and functionalizing them to promote plasmonically active complexes. The synthesis of dye-doped layered silica nanoparticles allows for control over the discrete location of the dye and a substrate that can be surface functionalized. Controlling the exact location of the dye is important to create a silica spacer, which promotes productive interactions with metal nanostructures. Furthermore, the synthesis of silica nanoparticles allows for various fluorophores to be studied in similar environments (removing solvent and other chemo-sensitive issues). Functionalizing the surface of silica nanoparticles allows control over the degree of silica and gold nanoparticle aggregation in solution. Heteroaggregation in solution is useful for producing well-aggregated clusters of many gold around a single silica nanoparticle. The dye-doped surface functionalized silica nanoparticles can than be mixed efficiently with gold nanomaterials. Aggregating multiple gold nanospheres around a single dye-doped silica nanoparticle can dramatically increase the fluorescent brightness of the sample via metal-enhanced fluorescence due to increase plasmonic scattering. Our aim is to promote heteroaggregation with functionalized silica nanoparticles while minimizing homoaggregation of silica-silica or gold-gold species. Reproducible production of multiple gold nanospheres about a dye-doped silica nanoparticle should lead to dramatic fluorescence brightness enhancements in solution. Gold nanorods can potentially be used to establish radiationless energy transfer between hetero dye-doped silica nanoparticles via gold nanorod plasmon mediated FRET by aggregating two different dye-doped silica nanoparticles preferentially at opposite ends of the nanorod. End-cap binding is accomplished by tuning the strength of gold binding ligands that functionalize the surface of the silica nanoparticles. The gold nanorod can then theoretically serve as a waveguide by employing the longitudinal plasmon as a non-radiative energy transfer agent between the two different fluorophores, giving rise to a new ultrafast signaling paradigm. Heteroaggregation of dye-doped silica nanoparticles and gold nanorods can be potentially employed to as nano waveguides. Construction and aggregation of functionalized silica and gold nano-materials provides an opportunity to advance the field of fluorescence. The synthesis of gold nano-particles allows control over their size and shape, which give rise to useful optical and electronic properties. Silica nanoparticles provide a framework allowing control over a requisite distance for increasing beneficial and deceasing non-radiative dye-metal interactions as well fluorophore protection. Our aim is to take advantage of fine-tuned synthetic control of functionalized nanomaterials to realize the great potential of solution based metal-enhanced fluorescence for future applications.

Synthesis and Luminescence Characteristics of Cr 3+ doped Y 3Al 5O 12 Phosphors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Brenda A.; Dabestani, Reza T.; Lewis, Linda A.

2015-10-01

Luminescence performance of yttrium aluminum garnet (Y 3Al 5O 12) phosphors as a function of Cr 3+ concentration has been investigated via two different wet-chemical synthesis techniques, direct- (DP) and hydrothermal-precipitation (HP). Using either of these methods, the red-emitting phosphor [Y 3Al 5-xCr xO 12 (YAG: Cr 3+)] showed similar photoluminescence (PL) intensities once the dopant concentration was optimized. Specifically, the YAG: Cr 3+ PL emission intensity reached a maximum at Cr3+ concentrations of x = 0.02 (0.4 at.%) and x = 0.13 (2.6 at.%) for DP and HP processed samples, respectively. The results indicated the strong influence of themore » processing method on the optimized YAG: Cr 3+ performance, where a more effective energy transfer rate between a pair of Cr3+ activators at low concentration levels was observed by using the DP synthesis technique. Development of a highly efficient phosphor, using a facile synthesis approach, could significantly benefit consumer and industrial applications by improving the operational efficiency of a wide range of practical devices.« less

Functional characteristics of spirilloxanthin and keto-bearing Analogues in light-harvesting LH2 complexes from Rhodobacter sphaeroides with a genetically modified carotenoid synthesis pathway.

PubMed

Niedzwiedzki, Dariusz M; Dilbeck, Preston L; Tang, Qun; Mothersole, David J; Martin, Elizabeth C; Bocian, David F; Holten, Dewey; Hunter, C Neil

2015-01-01

Light-harvesting 2 (LH2) complexes from a genetically modified strain of the purple photosynthetic bacterium Rhodobacter (Rba.) sphaeroides were studied using static and ultrafast optical methods and resonance Raman spectroscopy. Carotenoid synthesis in the Rba. sphaeroides strain was engineered to redirect carotenoid production away from spheroidene into the spirilloxanthin synthesis pathway. The strain assembles LH2 antennas with substantial amounts of spirilloxanthin (total double-bond conjugation length N=13) if grown anaerobically and of keto-bearing long-chain analogs [2-ketoanhydrorhodovibrin (N=13), 2-ketospirilloxanthin (N=14) and 2,2'-diketospirilloxanthin (N=15)] if grown semi-aerobically (with ratios that depend on growth conditions). We present the photophysical, electronic, and vibrational properties of these carotenoids, both isolated in organic media and assembled within LH2 complexes. Measurements of excited-state energy transfer to the array of excitonically coupled bacteriochlorophyll a molecules (B850) show that the mean lifetime of the first singlet excited state (S1) of the long-chain (N≥13) carotenoids does not change appreciably between organic media and the protein environment. In each case, the S1 state appears to lie lower in energy than that of B850. The energy-transfer yield is ~0.4 in LH2 (from the strain grown aerobically or semi-aerobically), which is less than half that achieved for LH2 that contains short-chain (N≤11) analogues. Collectively, the results suggest that the S1 excited state of the long-chain (N≥13) carotenoids participates little if at all in carotenoid-to-BChl a energy transfer, which occurs predominantly via the carotenoid S2 excited state in these antennas. Copyright © 2015 Elsevier B.V. All rights reserved.

Frataxin Accelerates [2Fe-2S] Cluster Formation on the Human Fe–S Assembly Complex

PubMed Central

Fox, Nicholas G.; Das, Deepika; Chakrabarti, Mrinmoy; Lindahl, Paul A.; Barondeau, David P.

2015-01-01

Iron–sulfur (Fe–S) clusters function as protein cofactors for a wide variety of critical cellular reactions. In human mitochondria, a core Fe–S assembly complex [called SDUF and composed of NFS1, ISD11, ISCU2, and frataxin (FXN) proteins] synthesizes Fe–S clusters from iron, cysteine sulfur, and reducing equivalents and then transfers these intact clusters to target proteins. In vitro assays have relied on reducing the complexity of this complicated Fe–S assembly process by using surrogate electron donor molecules and monitoring simplified reactions. Recent studies have concluded that FXN promotes the synthesis of [4Fe-4S] clusters on the mammalian Fe–S assembly complex. Here the kinetics of Fe–S synthesis reactions were determined using different electron donation systems and by monitoring the products with circular dichroism and absorbance spectroscopies. We discovered that common surrogate electron donor molecules intercepted Fe–S cluster intermediates and formed high-molecular weight species (HMWS). The HMWS are associated with iron, sulfide, and thiol-containing proteins and have properties of a heterogeneous solubilized mineral with spectroscopic properties remarkably reminiscent of those of [4Fe-4S] clusters. In contrast, reactions using physiological reagents revealed that FXN accelerates the formation of [2Fe-2S] clusters rather than [4Fe-4S] clusters as previously reported. In the preceding paper [Fox, N. G., et al. (2015) Biochemistry 54, DOI: 10.1021/bi5014485], [2Fe-2S] intermediates on the SDUF complex were shown to readily transfer to uncomplexed ISCU2 or apo acceptor proteins, depending on the reaction conditions. Our results indicate that FXN accelerates a rate-limiting sulfur transfer step in the synthesis of [2Fe-2S] clusters on the human Fe–S assembly complex. PMID:26016518

Frataxin Accelerates [2Fe-2S] Cluster Formation on the Human Fe-S Assembly Complex.

PubMed

Fox, Nicholas G; Das, Deepika; Chakrabarti, Mrinmoy; Lindahl, Paul A; Barondeau, David P

2015-06-30

Iron-sulfur (Fe-S) clusters function as protein cofactors for a wide variety of critical cellular reactions. In human mitochondria, a core Fe-S assembly complex [called SDUF and composed of NFS1, ISD11, ISCU2, and frataxin (FXN) proteins] synthesizes Fe-S clusters from iron, cysteine sulfur, and reducing equivalents and then transfers these intact clusters to target proteins. In vitro assays have relied on reducing the complexity of this complicated Fe-S assembly process by using surrogate electron donor molecules and monitoring simplified reactions. Recent studies have concluded that FXN promotes the synthesis of [4Fe-4S] clusters on the mammalian Fe-S assembly complex. Here the kinetics of Fe-S synthesis reactions were determined using different electron donation systems and by monitoring the products with circular dichroism and absorbance spectroscopies. We discovered that common surrogate electron donor molecules intercepted Fe-S cluster intermediates and formed high-molecular weight species (HMWS). The HMWS are associated with iron, sulfide, and thiol-containing proteins and have properties of a heterogeneous solubilized mineral with spectroscopic properties remarkably reminiscent of those of [4Fe-4S] clusters. In contrast, reactions using physiological reagents revealed that FXN accelerates the formation of [2Fe-2S] clusters rather than [4Fe-4S] clusters as previously reported. In the preceding paper [Fox, N. G., et al. (2015) Biochemistry 54, DOI: 10.1021/bi5014485], [2Fe-2S] intermediates on the SDUF complex were shown to readily transfer to uncomplexed ISCU2 or apo acceptor proteins, depending on the reaction conditions. Our results indicate that FXN accelerates a rate-limiting sulfur transfer step in the synthesis of [2Fe-2S] clusters on the human Fe-S assembly complex.

Chemical and charge transfer studies on interfaces of a conjugated polymer and ITO

NASA Astrophysics Data System (ADS)

David, Tanya M. S.; Arasho, Wondwosson; Smith, O'Neil; Hong, Kunlun; Bonner, Carl; Sun, Sam-Shajing

2017-08-01

Conjugated oligomers and polymers are very attractive for potential future plastic electronic and opto-electronic device applications such as plastic photo detectors and solar cells, thermoelectric devices, field effect transistors, and light emitting diodes. Understanding and optimizing charge transport between an active polymer layer and conductive substrate is critical to the optimization of polymer based electronic and opto-electronic devices. This study focused on the design, synthesis, self-assembly, and electron transfers and transports of a phosphonic acid end-functionalized polyphenylenevinylene (PPV) that was covalently attached and self-assembled onto an Indium Tin Oxide (ITO) substrate. This study demonstrated how atomic force microscopy (AFM) can be an effective characterization technique in conjunction with conventional electron transfer methods, including cyclic voltammetry (CV), towards determining electron transfer rates in polymer and polymer/conductor interface systems. This study found that the electron transfer rates of covalently attached and self-assembled films were much faster than the spin coated films. The knowledge from this study can be very useful for designing potential polymer based electronic and opto-electronic thin film devices.

Transfer RNA Post-Transcriptional Processing, Turnover, and Subcellular Dynamics in the Yeast Saccharomyces cerevisiae

PubMed Central

Hopper, Anita K.

2013-01-01

Transfer RNAs (tRNAs) are essential for protein synthesis. In eukaryotes, tRNA biosynthesis employs a specialized RNA polymerase that generates initial transcripts that must be subsequently altered via a multitude of post-transcriptional steps before the tRNAs beome mature molecules that function in protein synthesis. Genetic, genomic, biochemical, and cell biological approaches possible in the powerful Saccharomyces cerevisiae system have led to exciting advances in our understandings of tRNA post-transcriptional processing as well as to novel insights into tRNA turnover and tRNA subcellular dynamics. tRNA processing steps include removal of transcribed leader and trailer sequences, addition of CCA to the 3′ mature sequence and, for tRNAHis, addition of a 5′ G. About 20% of yeast tRNAs are encoded by intron-containing genes. The three-step splicing process to remove the introns surprisingly occurs in the cytoplasm in yeast and each of the splicing enzymes appears to moonlight in functions in addition to tRNA splicing. There are 25 different nucleoside modifications that are added post-transcriptionally, creating tRNAs in which ∼15% of the residues are nucleosides other than A, G, U, or C. These modified nucleosides serve numerous important functions including tRNA discrimination, translation fidelity, and tRNA quality control. Mature tRNAs are very stable, but nevertheless yeast cells possess multiple pathways to degrade inappropriately processed or folded tRNAs. Mature tRNAs are also dynamic in cells, moving from the cytoplasm to the nucleus and back again to the cytoplasm; the mechanism and function of this retrograde process is poorly understood. Here, the state of knowledge for tRNA post-transcriptional processing, turnover, and subcellular dynamics is addressed, highlighting the questions that remain. PMID:23633143

Increasing cholesterol synthesis in 7-dehydrosterol reductase (DHCR7) deficient mouse models through gene transfer

PubMed Central

Matabosch, Xavier; Ying, Lee; Serra, Montserrat; Wassif, Christopher A.; Porter, Forbes D.; Shackleton, Cedric; Watson, Gordon

2010-01-01

Smith-Lemli-Opitz syndrome (SLOS) is caused by deficiency in the terminal step of cholesterol biosynthesis: the conversion of 7-dehydrocholesterol (7DHC) to cholesterol (C), catalyzed by 7-dehydrocholesterol reductase (DHCR7). This disorder exhibits several phenotypic traits including dysmorphia and mental retardation with a broad range of severity. There are few proven treatment options. That most commonly used is a high cholesterol diet that seems to enhance the quality of life and improve behavioral characteristics of patients, although these positive effects are controversial. The goal of our study was to investigate the possibility of restoring DHCR7 activity by gene transfer. We constructed an adeno-associated virus (AAV) vector containing the DHCR7 gene. After we infused this vector into affected mice, the introduced DHCR7 gene could be identified in liver, mRNA was expressed and a functional enzyme was produced. Evidence of functionality came from the ability to partially normalize the serum ratio of 7DHC/C in treated animals, apparently by increasing cholesterol production with concomitant decrease in 7DHC precursor. By five weeks after treatment the mean ratio (for 7 animals) had fallen to 0.05 while the ratio for untreated littermate controls had risen to 0.14. This provides proof of principle that gene transfer can ameliorate the genetic defect causing SLOS and provides a new experimental tool for studying the pathogenesis of this disease. If effective in humans, it might also offer a possible alternative to exogenous cholesterol therapy. However, it would not offer a complete cure for the disorder as many of the negative implications of defective synthesis are already established during prenatal development. PMID:20800683

Fundamental studies of energy-and hole/electron- transfer in hydroporphyrin architectures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bocian, David F.

2014-08-20

The long-term objective of the Bocian/Holten/Lindsey research program is to design, synthesize, and characterize tetrapyrrole-based molecular architectures that absorb sunlight, funnel energy, and separate charge with high efficiency and in a manner compatible with current and future solar-energy conversion schemes. The synthetic tetrapyrroles include porphyrins and hydroporphyrins; the latter classes of molecules encompass analogues of the naturally occurring chlorophylls and bacteriochlorophylls (e.g., chlorins, bacteriochlorins, and their derivatives). The attainment of the goals of the research program requires the close interplay of molecular design and synthesis (Lindsey group), static and time-resolved optical spectroscopic measurements (Holten group), and electrochemical, electron paramagnetic resonance,more » and resonance Raman studies, as well as density functional theory calculations (Bocian Group). The proposed research encompasses four interrelated themes: (1) Determination of the rates of ground-state hole/electron transfer between (hydro)porphyrins in multipigment arrays as a function of array size, distance between components, linker type, site of linker connection, and frontier molecular orbital composition. (2) Examination of excited-state energy transfer among hydroporphyrins in multipigment arrrays, including both pairwise and non-adjacent transfer, with a chief aim to identify the relative contributions of through-space (Förster) and through-bond (Dexter) mechanisms of energy transfer, including the roles of site of linker connection and frontier molecular orbital composition. (3) Elucidation of the role of substituents in tuning the spectral and electronic properties of bacteriochlorins, with a primary aim of learning how to shift the long-wavelength absorption band deeper into the near-infrared region. (4) Continued development of the software package PhotochemCAD for spectral manipulations and calculations through the compilation of a database of spectra for naturally occurring and synthetic hydroporphyrins. The availability of such data should augment efforts in the design of light-harvesting systems where spectral coverage in the red and near-infrared regions is desired. Collectively, the proposed studies will provide fundamental insights into molecular properties, interactions, and processes relevant to the design of molecular architectures for solar-energy conversion. The accomplishment of these goals is only possible through a highly synergistic program that encompasses molecular design, synthesis, and characterization.« less

Effect of solar radiation on the functional components of mulberry (Morus alba L.) leaves.

PubMed

Sugiyama, Mari; Katsube, Takuya; Koyama, Akio; Itamura, Hiroyuki

2016-08-01

The functional components of mulberry leaves have attracted the attention of the health food industry, and increasing their concentrations is an industry goal. This study investigated the effects of solar radiation, which may influence the production of flavonol and 1-deoxynojirimycin (DNJ) functional components in mulberry leaves, by comparing a greenhouse (poor solar radiation) and outdoor (rich solar radiation) setting. The level of flavonol in leaves cultivated in the greenhouse was markedly decreased when compared with those cultivated outdoors. In contrast, the DNJ content in greenhouse-cultivated plants was increased only slightly when compared with those cultivated outdoors. Interestingly, the flavonol content was markedly increased in the upper leaves of mulberry trees that were transferred from a greenhouse to the outdoors compared with those cultivated only in the outdoors. Solar radiation conditions influence the synthesis of flavonol and DNJ, the functional components of mulberry leaves. Under high solar radiation, the flavonol level becomes very high but the DNJ level becomes slightly lower, suggesting that the impact of solar radiation is great on flavonol but small on DNJ synthesis. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Characterization of the transacylase activity of rat liver 60-kDa lysophospholipase-transacylase. Acyl transfer from the sn-2 to the sn-1 position.

PubMed

Sugimoto, H; Yamashita, S

1999-05-18

Rat liver 60-kDa lysophospholipase-transacylase catalyzes not only the hydrolysis of 1-acyl-sn-glycero-3-phosphocholine, but also the transfer of its acyl chain to a second molecule of 1-acyl-sn-glycero-3-phosphocholine to form phosphatidylcholine (H. Sugimoto, S. Yamashita, J. Biol. Chem. 269 (1994) 6252-6258). Here we report the detailed characterization of the transacylase activity of the enzyme. The enzyme mediated three types of acyl transfer between donor and acceptor lipids, transferring acyl residues from: (1) the sn-1 to -1(3); (2) sn-1 to -2; and (3) sn-2 to -1 positions. In the sn-1 to -1(3) transfer, the sn-1 acyl residue of 1-acyl-sn-glycero-3-phosphocholine was transferred to the sn-1(3) positions of glycerol and 2-acyl-sn-glycerol, producing 1(3)-acyl-sn-glycerol and 1,2-diacyl-sn-glycerol, respectively. In the sn-1 to -2 transfer, the sn-1 acyl residue of 1-acyl-sn-glycero-3-phosphocholine was transferred to not only the sn-2 positions of 1-acyl-sn-glycero-3-phosphocholine, but also 1-acyl-sn-glycero-3-phosphoethanolamine, producing phosphatidylcholine and phosphatidylethanolamine, respectively. 1-Acyl-sn-glycero-3-phospho-myo-inositol and 1-acyl-sn-glycero-3-phosphoserine were much less effectively transacylated by the enzyme. In the sn-2 to -1 transfer, the sn-2 acyl residue of 2-acyl-sn-glycero-3-phosphocholine was transferred to the sn-1 position of 2-acyl-sn-glycero-3-phosphocholine and 2-acyl-sn-glycero-3-phosphoethanolamine, producing phosphatidylcholine and phosphatidylethanolamine, respectively. Consistently, the enzyme hydrolyzed the sn-2 acyl residue from 2-acyl-sn-glycero-3-phosphocholine. By the sn-2 to -1 transfer activity, arachidonic acid was transferred from the sn-2 position of donor lipids to the sn-1 position of acceptor lipids, thus producing 1-arachidonoyl phosphatidylcholine. When 2-arachidonoyl-sn-glycero-3-phosphocholine was used as the sole substrate, diarachidonoyl phosphatidylcholine was synthesized at a rate of 0.23 micromol/min/mg protein. Thus, 60-kDa lysophospholipase-transacylase may play a role in the synthesis of 1-arachidonoyl phosphatidylcholine needed for important cell functions, such as anandamide synthesis.

Mitochondrial energy-dissipating systems (alternative oxidase, uncoupling proteins, and external NADH dehydrogenase) are involved in development of frost-resistance of winter wheat seedlings.

PubMed

Grabelnych, O I; Borovik, O A; Tauson, E L; Pobezhimova, T P; Katyshev, A I; Pavlovskaya, N S; Koroleva, N A; Lyubushkina, I V; Bashmakov, V Yu; Popov, V N; Borovskii, G B; Voinikov, V K

2014-06-01

Gene expression, protein synthesis, and activities of alternative oxidase (AOX), uncoupling proteins (UCP), adenine nucleotide translocator (ANT), and non-coupled NAD(P)H dehydrogenases (NDex, NDPex, and NDin) were studied in shoots of etiolated winter wheat (Triticum aestivum L.) seedlings after exposure to hardening low positive (2°C for 7 days) and freezing (-2°C for 2 days) temperatures. The cold hardening efficiently increased frost-resistance of the seedlings and decreased the generation of reactive oxygen species (ROS) during further cold shock. Functioning of mitochondrial energy-dissipating systems can represent a mechanism responsible for the decrease in ROS under these conditions. These systems are different in their response to the action of the hardening low positive and freezing temperatures. The functioning of the first system causes induction of AOX and UCP synthesis associated with an increase in electron transfer via AOX in the mitochondrial respiratory chain and also with an increase in the sensitivity of mitochondrial non-phosphorylating respiration to linoleic and palmitic acids. The increase in electron transfer via AOX upon exposure of seedlings to hardening freezing temperature is associated with retention of a high activity of NDex. It seems that NDex but not the NDPex and NDin can play an important role in maintaining the functional state of mitochondria in heterotrophic tissues of plants under the influence of freezing temperatures. The involvement of the mitochondrial energy-dissipating systems and their possible physiological role in the adaptation of winter crops to cold and frost are discussed.

Analyses of advanced rice anther transcriptomes reveal global tapetum secretory functions and potential proteins for lipid exine formation.

PubMed

Huang, Ming-Der; Wei, Fu-Jin; Wu, Cheng-Cheih; Hsing, Yue-Ie Caroline; Huang, Anthony H C

2009-02-01

The anthers in flowers perform important functions in sexual reproduction. Several recent studies used microarrays to study anther transcriptomes to explore genes controlling anther development. To analyze the secretion and other functions of the tapetum, we produced transcriptomes of anthers of rice (Oryza sativa subsp. japonica) at six progressive developmental stages and pollen with sequencing-by-synthesis technology. The transcriptomes included at least 18,000 unique transcripts, about 25% of which had antisense transcripts. In silico anther-minus-pollen subtraction produced transcripts largely unique to the tapetum; these transcripts include all the reported tapetum-specific transcripts of orthologs in other species. The differential developmental profiles of the transcripts and their antisense transcripts signify extensive regulation of gene expression in the anther, especially the tapetum, during development. The transcriptomes were used to dissect two major cell/biochemical functions of the tapetum. First, we categorized and charted the developmental profiles of all transcripts encoding secretory proteins present in the cellular exterior; these transcripts represent about 12% and 30% of the those transcripts having more than 100 and 1,000 transcripts per million, respectively. Second, we successfully selected from hundreds of transcripts several transcripts encoding potential proteins for lipid exine synthesis during early anther development. These proteins include cytochrome P450, acyltransferases, and lipid transfer proteins in our hypothesized mechanism of exine synthesis in and export from the tapetum. Putative functioning of these proteins in exine formation is consistent with proteins and metabolites detected in the anther locule fluid obtained by micropipetting.

Amine functionalized TiO2-carbon nanotube composite: synthesis, characterization and application to glucose biosensing

NASA Astrophysics Data System (ADS)

Tasviri, Mahboubeh; Rafiee-Pour, Hossain-Ali; Ghourchian, Hedayatollah; Gholami, Mohammad Reza

2011-12-01

The synthesis of amine functionalized TiO2-coated multiwalled carbon nanotubes (NH2-TiO2-CNTs) using sol-gel method was investigated. The synthesized nanocomposite was characterized with XRD, FTIR spectroscopy, BET test and SEM imaging. The results demonstrated a unique nanostructure with no destruction of the CNTs' shape. In addition, the presence of amine groups on the composite surface was confirmed by FTIR. This nanocomposite was used for one-step immobilization of glucose oxidase (GOx) to sense glucose. The result of cyclic voltammetry showed a pair of well-defined and quasi-reversible peaks for direct electron transfer of GOx in the absence of glucose. Also, the result of electrochemical impedance spectroscopy indicated that GOx was successfully immobilized on the surface of NH2-TiO2-CNTs. Furthermore, good amperometric response showed that immobilized GOx on the NH2-TiO2-CNTs exhibits exceptional bioelectrocatalytic activity toward glucose oxidation.

In vitro selection of functional nucleic acids

NASA Technical Reports Server (NTRS)

Wilson, D. S.; Szostak, J. W.

1999-01-01

In vitro selection allows rare functional RNA or DNA molecules to be isolated from pools of over 10(15) different sequences. This approach has been used to identify RNA and DNA ligands for numerous small molecules, and recent three-dimensional structure solutions have revealed the basis for ligand recognition in several cases. By selecting high-affinity and -specificity nucleic acid ligands for proteins, promising new therapeutic and diagnostic reagents have been identified. Selection experiments have also been carried out to identify ribozymes that catalyze a variety of chemical transformations, including RNA cleavage, ligation, and synthesis, as well as alkylation and acyl-transfer reactions and N-glycosidic and peptide bond formation. The existence of such RNA enzymes supports the notion that ribozymes could have directed a primitive metabolism before the evolution of protein synthesis. New in vitro protein selection techniques should allow for a direct comparison of the frequency of ligand binding and catalytic structures in pools of random sequence polynucleotides versus polypeptides.

[Sugar Chain Construction of Functional Natural Products Using Plant Glucosyltransferases].

PubMed

Mizukami, Hajime

2015-01-01

Plant secondary product glycosyltransferases belong to family 1 of the glycosyltransferase superfamily and mediate the transfer of a glycosyl residue from activated nucleotide sugars to lipophilic small molecules, thus affecting the solubility, stability and pharmacological activities of the sugar-accepting compounds. The biotechnological application of plant glycosyltransferases in glycoside synthesis has attracted attention because enzymatic glycosylation offers several advantages over chemical methods, including (1) avoiding the use of harsh conditions and toxic catalysts, (2) providing strict control of regio-and stereo-selectivity and (3) high efficiency. This review describes the in vivo and in vitro glycosylation of natural organic compounds using glycosyltransferases, focusing on our investigation of enzymatic synthesis of curcumin glycosides. Our current efforts toward functional characterization of some glycosyltransferases involved in the biosynthesis of iridoids and crocin, as well as in the sugar chain elongation of quercetin glucosides, are described. Finally, I describe the relationship of the structure of sugar chains and the intestinal absorption which was investigated using chemoenzymatically synthesized quercetin glycosides.

Native N-glycopeptide thioester synthesis through N→S acyl transfer

PubMed Central

Premdjee, Bhavesh; Adams, Anna L.; Macmillan, Derek

2011-01-01

Peptide thioesters are important tools for the total synthesis of proteins using native chemical ligation (NCL). Preparation of glycopeptide thioesters, that enable the assembly of homogeneously glycosylated proteins, is complicated by the perceived fragile nature of the sugar moiety. Herein, we demonstrate the compatibility of thioester formation via N→S acyl transfer with native N-glycopeptides and report observations that will aid in their preparation. PMID:21676613

Synthesis, Transfer, and Characterization of Nanoscale 2-Dimensional Materials

DTIC Science & Technology

2015-09-01

deposition systems, leading to reduced operating costs. Transfer has been achieved using polymer-assisted methods , and material quality has been...Introduction and Background 1 2. Materials and Methods 1 3. Results and Discussion 2 3.1 Copper Foil Preparation 2 3.2 Graphene Synthesis and...magnification. a) 10 K, b) 18 K, c) 20 K, and d) 40 K. The red arrows indicate wrinkles in the film

Non-immunogenic, hydrophilic/cationic block copolymers and uses thereof

DOEpatents

Scales, Charles W.; Huang, Faqing; McCormick, Charles L.

2010-05-18

The present invention provides novel non-immunogenic, hydrophilic/cationic block copolymers comprising a neutral-hydrophilic polymer and a cationic polymer, wherein both polymers have well-defined chain-end functionality. A representative example of such a block copolymer comprises poly(N-(2-hydroxypropyl)methacrylamide) (PHPMA) and poly(N-[3-(dimethylamino)propyl]methacrylamide) (PDMAPMA). Also provided is a synthesis method thereof in aqueous media via reversible addition fragmentation chain transfer (RAFT) polymerization. Further provided are uses of these block copolymers as drug delivery vehicles and protection agents.

Experimental dynamic response of a two-dimensional, Mach 2.7, mixed compression inlet

NASA Technical Reports Server (NTRS)

Baumbick, R. J.; Neiner, G. H.; Cole, G. L.

1972-01-01

A test program was conducted on a two-dimensional supersonic inlet. Internal disturbances in diffuser exit mass flow were produced by oscillating overboard bypass doors. Open-loop dynamic responses of shock position, throat exit and diffuser exit static pressures are presented. The steady-state and dynamic coupling between ducts were also obtained. The experimental results from the two-dimensional inlet are compared to results from a similar size axisymmetric inlet and also to a transfer function synthesis program.

Flexible aircraft dynamic modeling for dynamic analysis and control synthesis

NASA Technical Reports Server (NTRS)

Schmidt, David K.

1989-01-01

The linearization and simplification of a nonlinear, literal model for flexible aircraft is highlighted. Areas of model fidelity that are critical if the model is to be used for control system synthesis are developed and several simplification techniques that can deliver the necessary model fidelity are discussed. These techniques include both numerical and analytical approaches. An analytical approach, based on first-order sensitivity theory is shown to lead not only to excellent numerical results, but also to closed-form analytical expressions for key system dynamic properties such as the pole/zero factors of the vehicle transfer-function matrix. The analytical results are expressed in terms of vehicle mass properties, vibrational characteristics, and rigid-body and aeroelastic stability derivatives, thus leading to the underlying causes for critical dynamic characteristics.

Evaluation of substitution monopole models for tire noise sound synthesis

NASA Astrophysics Data System (ADS)

Berckmans, D.; Kindt, P.; Sas, P.; Desmet, W.

2010-01-01

Due to the considerable efforts in engine noise reduction, tire noise has become one of the major sources of passenger car noise nowadays and the demand for accurate prediction models is high. A rolling tire is therefore experimentally characterized by means of the substitution monopole technique, suiting a general sound synthesis approach with a focus on perceived sound quality. The running tire is substituted by a monopole distribution covering the static tire. All monopoles have mutual phase relationships and a well-defined volume velocity distribution which is derived by means of the airborne source quantification technique; i.e. by combining static transfer function measurements with operating indicator pressure measurements close to the rolling tire. Models with varying numbers/locations of monopoles are discussed and the application of different regularization techniques is evaluated.

Simple and Efficient Generation of Aryl Radicals from Aryl Triflates: Synthesis of Aryl Boronates and Aryl Iodides at Room Temperature.

PubMed

Liu, Wenbo; Yang, Xiaobo; Gao, Yang; Li, Chao-Jun

2017-06-28

Despite the wide use of aryl radicals in organic synthesis, current methods to prepare them from aryl halides, carboxylic acids, boronic acids, and diazonium salts suffer from limitations. Aryl triflates, easily obtained from phenols, are promising aryl radical progenitors but remain elusive in this regard. Inspired by the single electron transfer process for aryl halides to access aryl radicals, we developed a simple and efficient protocol to convert aryl triflates to aryl radicals. Our success lies in exploiting sodium iodide as the soft electron donor assisted by light. This strategy enables the scalable synthesis of two types of important organic molecules, i.e., aryl boronates and aryl iodides, in good to high yields, with broad functional group compatibility in a transition-metal-free manner at room temperature. This protocol is anticipated to find potential applications in other aryl-radical-involved reactions by using aryl triflates as aryl radical precursors.

Structural and Mechanistic Insight into the Listeria monocytogenes Two-enzyme Lipoteichoic Acid Synthesis System*

PubMed Central

Campeotto, Ivan; Percy, Matthew G.; MacDonald, James T.; Förster, Andreas; Freemont, Paul S.; Gründling, Angelika

2014-01-01

Lipoteichoic acid (LTA) is an important cell wall component required for proper cell growth in many Gram-positive bacteria. In Listeria monocytogenes, two enzymes are required for the synthesis of this polyglycerolphosphate polymer. The LTA primase LtaPLm initiates LTA synthesis by transferring the first glycerolphosphate (GroP) subunit onto the glycolipid anchor and the LTA synthase LtaSLm extends the polymer by the repeated addition of GroP subunits to the tip of the growing chain. Here, we present the crystal structures of the enzymatic domains of LtaPLm and LtaSLm. Although the enzymes share the same fold, substantial differences in the cavity of the catalytic site and surface charge distribution contribute to enzyme specialization. The eLtaSLm structure was also determined in complex with GroP revealing a second GroP binding site. Mutational analysis confirmed an essential function for this binding site and allowed us to propose a model for the binding of the growing chain. PMID:25128528

Nanoarchitectonics with Porphyrin Functionalized DNA

PubMed Central

2017-01-01

Conspectus DNA is well-known as bearer of the genetic code. Since its structure elucidation nearly seven decades ago by Watson, Crick, Wilkins, and Franklin, much has been learned about its detailed structure, function, and genetic coding. The development of automated solid-phase synthesis, and with it the availability of synthetic DNA with any desired sequence in lengths of up to hundreds of bases in the best case, has contributed much to the advancement of the field of DNA research. In addition, classic organic synthesis has allowed introduction of a very large number of modifications in the DNA in a sequence specific manner, which have initially been targeted at altering the biological function of DNA. However, in recent years DNA has become a very attractive scaffold in supramolecular chemistry, where DNA is taken out of its biological role and serves as both stick and glue molecule to assemble novel functional structures with nanometer precision. The attachment of functionalities to DNA has led to the creation of supramolecular systems with applications in light harvesting, energy and electron transfer, sensing, and catalysis. Functional DNA is clearly having a significant impact in the field of bioinspired nanosystems. Of particular interest is the use of porphyrins in supramolecular chemistry and bionanotechnology, because they are excellent functional groups due to their electronic properties that can be tailored through chemical modifications of the aromatic core or through insertion of almost any metal of the periodic table into the central cavity. The porphyrins can be attached either to the nucleobase, to the phosphate group, or to the ribose moiety. Additionally, noncovalent templating through Watson–Crick base pairing forms an alternative and attractive approach. With this, the combination of two seemingly simple molecules gives rise to a highly complex system with unprecedented possibilities for modulation of function, and with it applications, particularly when combined with other functional groups. Here, an overview is given on the developments of using porphyrin modified DNA for the construction of functional assemblies. Strategies for the synthesis and characterization are presented alongside selected applications where the porphyrin modification has proven to be particularly useful and superior to other modifiers but also has revealed its limitations. We also discuss implications on properties and behavior of the porphyrin–DNA, where similar issues could arise when using other hydrophobic and bulky substituents on DNA. This includes particularly problems regarding synthesis of the building blocks, DNA synthesis, yields, solubility, and intermolecular interactions. PMID:28272871

The flavoprotein Tah18-dependent NO synthesis confers high-temperature stress tolerance on yeast cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nishimura, Akira; Kawahara, Nobuhiro; Takagi, Hiroshi, E-mail: hiro@bs.naist.jp

Highlights: Black-Right-Pointing-Pointer NO is produced from L-arginine in response to elevated temperature in yeast. Black-Right-Pointing-Pointer Tah18 was first identified as the yeast protein involved in NO synthesis. Black-Right-Pointing-Pointer Tah18-dependent NO synthesis confers tolerance to high-temperature on yeast cells. -- Abstract: Nitric oxide (NO) is a ubiquitous signaling molecule involved in the regulation of a large number of cellular functions. In the unicellular eukaryote yeast, NO may be involved in stress response pathways, but its role is poorly understood due to the lack of mammalian NO synthase (NOS) orthologues. Previously, we have proposed the oxidative stress-induced L-arginine synthesis and its physiologicalmore » role under stress conditions in yeast Saccharomyces cerevisiae. Here, our experimental results indicated that increased conversion of L-proline into L-arginine led to NO production in response to elevated temperature. We also showed that the flavoprotein Tah18, which was previously reported to transfer electrons to the Fe-S cluster protein Dre2, was involved in NO synthesis in yeast. Gene knockdown analysis demonstrated that Tah18-dependent NO synthesis confers high-temperature stress tolerance on yeast cells. As it appears that such a unique cell protection mechanism is specific to yeasts and fungi, it represents a promising target for antifungal activity.« less

Photochemical reactions of aromatic compounds and the concept of the photon as a traceless reagent.

PubMed

Hoffmann, Norbert

2012-11-01

Electronic excitation significantly changes the reactivity of chemical compounds. Compared to ground state reactions, photochemical reactions considerably enlarge the application spectrum of a particular functional group in organic synthesis. Multistep syntheses may be simplified and perspectives for target oriented synthesis (TOS) and diversity oriented synthesis (DOS) are developed. New compound families become available or may be obtained more easily. In contrast to common chemical reagents, photons don't generate side products resulting from the transformation of a chemical reagent. Therefore, they are considered as a traceless reagent. Consequently, photochemical reactions play a central role in the methodology of sustainable chemistry. This aspect has been recognized since the beginning of the 20th century. As with many other photochemical transformations, photochemical reactions of aromatic, benzene-like compounds illustrate well the advantages in this context. Photochemical cycloadditions of aromatic compounds have been investigated for a long time. Currently, they are applied in various fields of organic synthesis. They are also studied in supramolecular structures. The phenomena of reactivity and stereoselectivity are investigated. During recent years, photochemical electron transfer mediated reactions are particularly focused. Such transformations have likewise been performed with aromatic compounds. Reactivity and selectivity as well as application to organic synthesis are studied.

Adjustment of interaural time difference in head related transfer functions based on listeners' anthropometry and its effect on sound localization

NASA Astrophysics Data System (ADS)

Suzuki, Yôiti; Watanabe, Kanji; Iwaya, Yukio; Gyoba, Jiro; Takane, Shouichi

2005-04-01

Because the transfer functions governing subjective sound localization (HRTFs) show strong individuality, sound localization systems based on synthesis of HRTFs require suitable HRTFs for individual listeners. However, it is impractical to obtain HRTFs for all listeners based on measurements. Improving sound localization by adjusting non-individualized HRTFs to a specific listener based on that listener's anthropometry might be a practical method. This study first developed a new method to estimate interaural time differences (ITDs) using HRTFs. Then correlations between ITDs and anthropometric parameters were analyzed using the canonical correlation method. Results indicated that parameters relating to head size, and shoulder and ear positions are significant. Consequently, it was attempted to express ITDs based on listener's anthropometric data. In this process, the change of ITDs as a function of azimuth angle was parameterized as a sum of sine functions. Then the parameters were analyzed using multiple regression analysis, in which the anthropometric parameters were used as explanatory variables. The predicted or individualized ITDs were installed in the nonindividualized HRTFs to evaluate sound localization performance. Results showed that individualization of ITDs improved horizontal sound localization.

Synthesis and property of solvatochromic fluorophore based on D-pi-A molecular system: 2-[[3-cyano-4-(N-ethyl-N-(2-hydroxyethyl)amino)styryl]-5,5-dimethylfuran-2(5H)-ylidene]malononitrile dye.

PubMed

Son, Young-A; Gwon, Seon-Yeong; Lee, Sue-Yoen; Kim, Sung-Hoon

2010-01-01

2-[[3-Cyano-4-(N-ethyl-N-(2-hydroxyethyl)amino)styryl]-5,5-dimethylfuran-2(5H)-ylidene]malononitrile styryl dye was prepared by the condensation of 4-[(2-hydroxy-ethyl)-methyl-amino]-benzaldehyde (donor moiety) with 2-cyanomethylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran (acceptor moiety). The corresponding design, synthesis and solvatochromic characteristics of the intramolecular charge-transfer (ICT) dye chromophore were discussed and determined. Optical properties such as absorption and fluorescence emission spectra were monitored in several solvent media with different polarity. In this determination, the prepared dye chromophore showed positive solvatochromism effect and the resulting solvatochromic characteristics were studied with semiempirical calculations. The energy potentials of this dye chromophore such as HOMO and LUMO values were calculated by computational simulation approaches using Material Studio 4.3. Furthermore, the functions as a molecular switching sensor with pH stimulation of alkali-acid addition were determined in DMSO, which was operated by deprotonation/protonation effects based on intramolecular charge-transfer system. Copyright 2009 Elsevier B.V. All rights reserved.

Endoplasmic reticulum mediated signaling in cellular microdomains

PubMed Central

Biwer, Lauren; Isakson, Brant E

2016-01-01

The endoplasmic reticulum (ER) is a prime mediator of cellular signaling due to its functions as an internal cellular store for calcium, as well as a site for synthesis of proteins and lipids. Its peripheral network of sheets and tubules facilitate calcium and lipid signaling, especially in areas of the cell that are more distant to the main cytoplasmic network. Specific membrane proteins shape the peripheral ER architecture and influence the network stability in order to project into restricted spaces. The signaling microdomains are anatomically separate from the cytoplasm as a whole and exhibit localized protein, ion channel and cytoskeletal element expression. Signaling can also occur between the ER and other organelles, such as the Golgi or mitochondria. Lipids made in the ER membrane can be sent to the Golgi via specialized transfer proteins and specific phospholipid synthases are enriched at ER-mitochondria junctions to more efficiently expedite phospholipid transfer. As a hub for protein and lipid synthesis, a store for intracellular calcium [Ca2+]i, and a mediator of cellular stress, the ER is an important cellular organelle. Its ability to organize into tubules and project into restricted spaces allows for discrete and temporal signaling, which is important for cellular physiology and organism homeostasis. PMID:26973141

Uncertainty of Monetary Valued Ecosystem Services – Value Transfer Functions for Global Mapping

PubMed Central

Schmidt, Stefan; Manceur, Ameur M.; Seppelt, Ralf

2016-01-01

Growing demand of resources increases pressure on ecosystem services (ES) and biodiversity. Monetary valuation of ES is frequently seen as a decision-support tool by providing explicit values for unconsidered, non-market goods and services. Here we present global value transfer functions by using a meta-analytic framework for the synthesis of 194 case studies capturing 839 monetary values of ES. For 12 ES the variance of monetary values could be explained with a subset of 93 study- and site-specific variables by utilizing boosted regression trees. This provides the first global quantification of uncertainties and transferability of monetary valuations. Models explain from 18% (water provision) to 44% (food provision) of variance and provide statistically reliable extrapolations for 70% (water provision) to 91% (food provision) of the terrestrial earth surface. Although the application of different valuation methods is a source of uncertainty, we found evidence that assuming homogeneity of ecosystems is a major error in value transfer function models. Food provision is positively correlated with better life domains and variables indicating positive conditions for human well-being. Water provision and recreation service show that weak ownerships affect valuation of other common goods negatively (e.g. non-privately owned forests). Furthermore, we found support for the shifting baseline hypothesis in valuing climate regulation. Ecological conditions and societal vulnerability determine valuation of extreme event prevention. Valuation of habitat services is negatively correlated with indicators characterizing less favorable areas. Our analysis represents a stepping stone to establish a standardized integration of and reporting on uncertainties for reliable and valid benefit transfer as an important component for decision support. PMID:26938447

Shifting Native Chemical Ligation into Reverse through N→S Acyl Transfer

PubMed Central

Macmillan, Derek; Adams, Anna; Premdjee, Bhavesh

2011-01-01

Peptide thioester synthesis by N→S acyl transfer is being intensively explored by many research groups the world over. Reasons for this likely include the often straightforward method of precursor assembly using Fmoc-based chemistry and the fundamentally interesting acyl migration process. In this review we introduce recent advances in this exciting area and discuss, in more detail, our own efforts towards the synthesis of peptide thioesters through N→S acyl transfer in native peptide sequences. We have found that several peptide thioesters can be readily prepared and, what’s more, there appears to be ample opportunity for further development and discovery. PMID:22347724

Digital Transfer Growth of Patterned 2D Metal Chalcogenides by Confined Nanoparticle Evaporation

DOE PAGES

Mahjouri-Samani, Masoud; Tian, Mengkun; Wang, Kai; ...

2014-10-19

Developing methods for the facile synthesis of two-dimensional (2D) metal chalcogenides and other layered materials is crucial for emerging applications in functional devices. Controlling the stoichiometry, number of the layers, crystallite size, growth location, and areal uniformity is challenging in conventional vapor phase synthesis. Here, we demonstrate a new route to control these parameters in the growth of metal chalcogenide (GaSe) and dichalcogenide (MoSe 2) 2D crystals by precisely defining the mass and location of the source materials in a confined transfer growth system. A uniform and precise amount of stoichiometric nanoparticles are first synthesized and deposited onto a substratemore » by pulsed laser deposition (PLD) at room temperature. This source substrate is then covered with a receiver substrate to form a confined vapor transport growth (VTG) system. By simply heating the source substrate in an inert background gas, a natural temperature gradient is formed that evaporates the confined nanoparticles to grow large, crystalline 2D nanosheets on the cooler receiver substrate, the temperature of which is controlled by the background gas pressure. Large monolayer crystalline domains (~ 100 m lateral sizes) of GaSe and MoSe 2 are demonstrated, as well as continuous monolayer films through the deposition of additional precursor materials. This novel PLD-VTG synthesis and processing method offers a unique approach for the controlled growth of large-area, metal chalcogenides with a controlled number of layers in patterned growth locations for optoelectronics and energy related applications.« less

Production of chlorphenesin galactoside by whole cells of β-galactosidase-containing Escherichia coli.

PubMed

Lee, Sang-Eun; Lee, Hyang-Yeol; Jung, Kyung-Hwan

2013-06-28

We investigated the transgalactosylation reaction of chlorphenesin (CPN) using β-galactosidase (β-gal)-containing Escherichia coli (E. coli) cells, in which galactose from lactose was transferred to CPN. The optimal CPN concentration for CPN galactoside (CPN-G) synthesis was observed at 40 mM under the conditions that lactose and β-gal (as E. coli cells) were 400 g/l and 4.8 U/ml, respectively, and the pH and temperature were 7.0 and 40oC, respectively. The time-course profile of CPN-G synthesis under these optimal conditions showed that CPN-G synthesis from 40 mM CPN reached a maximum of about 27 mM at 12 h. This value corresponded to an about 67% conversion of CPN to CPN-G, which was 4.47-5.36-fold higher than values in previous reports. In addition, we demonstrated by thin-layer chromatography to detect the sugar moiety that galactose was mainly transferred from lactose to CPN. Liquid chromatography-mass spectrometry revealed that CPN-G and CPN-GG (CPN galactoside, which accepted two galactose molecules) were definitively identified as the synthesized products using β-gal-containing E. coli cells. In particular, because we did not use purified β-gal, our β-gal-containing E. coli cells might be practical and cost-effective for enzymatically synthesizing CPN-G. It is expected that the use of β-gal-containing E. coli will be extended to galactose derivatization of other drugs to improve their functionality.

Engineering and Applications of fungal laccases for organic synthesis

PubMed Central

Kunamneni, Adinarayana; Camarero, Susana; García-Burgos, Carlos; Plou, Francisco J; Ballesteros, Antonio; Alcalde, Miguel

2008-01-01

Laccases are multi-copper containing oxidases (EC 1.10.3.2), widely distributed in fungi, higher plants and bacteria. Laccase catalyses the oxidation of phenols, polyphenols and anilines by one-electron abstraction, with the concomitant reduction of oxygen to water in a four-electron transfer process. In the presence of small redox mediators, laccase offers a broader repertory of oxidations including non-phenolic substrates. Hence, fungal laccases are considered as ideal green catalysts of great biotechnological impact due to their few requirements (they only require air, and they produce water as the only by-product) and their broad substrate specificity, including direct bioelectrocatalysis. Thus, laccases and/or laccase-mediator systems find potential applications in bioremediation, paper pulp bleaching, finishing of textiles, bio-fuel cells and more. Significantly, laccases can be used in organic synthesis, as they can perform exquisite transformations ranging from the oxidation of functional groups to the heteromolecular coupling for production of new antibiotics derivatives, or the catalysis of key steps in the synthesis of complex natural products. In this review, the application of fungal laccases and their engineering by rational design and directed evolution for organic synthesis purposes are discussed. PMID:19019256

A Hypothesis for Examining Skeletal Muscle Biopsy-Derived Sarcolemmal nNOSμ as Surrogate for Enteric nNOSα Function

PubMed Central

Chaudhury, Arun

2015-01-01

The pathophysiology of gastrointestinal motility disorders is controversial and largely unresolved. This provokes empiric approaches to patient management of these so-called functional gastrointestinal disorders. Preliminary evidence demonstrates that defects in neuronal nitric oxide synthase (nNOS) expression and function, the enzyme that synthesizes nitric oxide (NO), the key inhibitory neurotransmitter mediating mechano-electrical smooth muscle relaxation, is the major pathophysiological basis for sluggishness of oro-aboral transit of luminal contents. This opinion is an ansatz of the potential of skeletal muscle biopsy and examining sarcolemmal nNOSμ to provide complementary insights regarding nNOSα expression, localization, and function within enteric nerve terminals, the site of stimulated de novo NO synthesis. The main basis of this thesis is twofold: (a) the molecular similarity of the structures of nNOS α and μ, similar mechanisms of localizations to “active zones” of nitrergic synthesis, and same mechanisms of electron transfers during NO synthesis and (b) pragmatic difficulty to routinely obtain full-thickness biopsies of gastrointestinal tract, even in patients presenting with the most recalcitrant manifestations of stasis and delayed transit of luminal contents. This opinion attempts to provoke dialog whether this approach is feasible as a surrogate to predict catalytic potential of nNOSα and defects in nitrergic neurotransmission. This discussion makes an assumption that similar molecular mechanisms of nNOS defects shall be operant in both the enteric nerve terminals and the skeletal muscles. These overlaps of skeletal and gastrointestinal dysfunction are largely unknown, thus meriting that the thesis be validated in future by proof-of-principle experiments. PMID:26284245

Synthesis and characterization of Nd3+: Yb3+ co-doped near infrared sensitive fluorapatite nanoparticles as a bioimaging probe

NASA Astrophysics Data System (ADS)

Karthi, S.; Kumar, G. A.; Sardar, D. K.; Santhosh, C.; Girija, E. K.

2018-03-01

Trivalent Nd and Yb co-doped rod shaped hexagonal phase fluorapatite (FAP) nanoparticles of length and width about 32 and 13 nm, respectively were prepared by hydrothermal method and investigated the ability for 980 nm emission via Nd3+ → Yb3+ energy transfer with the objective of utilizing them in biomedical imaging. Nd3+ → Yb3+ energy transfer in FAP was studied as a function of both Nd3+ and Yb3+ concentrations and found that when Yb3+ concentration was 10 mol% the FAP phase has partially turned in to YbPO4 phase. The Yb3+ emission intensity at 980 nm significantly increased up to 5 mol% Yb3+ doping and then reduced drastically for further increase in its concentration. Nd3+ →Yb3+ energy transfer rates were evaluated from the decay curves and found that a transfer rate of 71% for 2 mol% Nd3+ co-doped with 5 mol% Yb3+. The cytocompatibility test with fibroblast like cells using MTT assay revealed that the nanoparticles are compatible with the cells.

Graphene wrapped multiwalled carbon nanotubes dispersed nanofluids for heat transfer applications

NASA Astrophysics Data System (ADS)

Jyothirmayee Aravind, S. S.; Ramaprabhu, S.

2012-12-01

A two step method is employed for the preparation of graphene wrapped multiwalled carbon nanotubes (MWNT) dispersed nanofluids. Graphene wrapped MWNT composite is prepared by simple chemical vapor deposition technique and further purified prior to the synthesis of nanofluids. The functionalization of MWNT with the poly electrolyte, graphene drives out the need for surfactants or long term harsh chemical treatments as in the case of pristine carbon materials based nanofluids. The enhancement in thermal transport properties of surfactant free graphene wrapped MWNT composite in de-ionized (DI) water and ethylene glycol (EG) base fluids than that of pristine carbon nanomaterial based nanofluids indicates the potential usage of the hybrid composite based nanofluids in heat transfer applications. An enhancement in thermal conductivity of 11.3% and 13.7% has been attained with 0.04% volume fraction of hybrid composite based DI water and EG nanofluids at 25 °C. The nanocomposite possesses extreme stability in a variety of aqueous solvents without any surfactant. Electrical conductivity of the nanofluids analyzed as a function of volume fraction of nanoparticles and temperature shows a positive effect. Further, the analysis of forced convective heat transfer coefficients of the nanofluids flowing through a stain less steel tube shows significant enhancement in heat transfer, attributed to good aspect ratio of graphene wrapped MWNT and synergistic effect of high thermally conducting graphene and MWNT.

Occupationally-Transferable Skills and Characteristics: Review of Literature and Research. Information Series No. 105.

ERIC Educational Resources Information Center

Sjogren, Douglas

In this synthesis of research and literature on the nature of occupationally-transferable skills, the author identifies skills that seem to be highly transferable in the sense of being general to a number of occupations. He then speculates about characteristics of skills that are generalizable or transferable and discusses some implications for…

Intrinsically Radioactive [64Cu]CuInS/ZnS Quantum Dots for PET and Optical Imaging: Improved Radiochemical Stability and Controllable Cerenkov Luminescence

PubMed Central

2015-01-01

Functionalized quantum dots (QDs) have been widely explored for multimodality bioimaging and proven to be versatile agents. Attaching positron-emitting radioisotopes onto QDs not only endows their positron emission tomography (PET) functionality, but also results in self-illuminating QDs, with no need for an external light source, by Cerenkov resonance energy transfer (CRET). Traditional chelation methods have been used to incorporate the radionuclide, but these methods are compromised by the potential for loss of radionuclide due to cleavage of the linker between particle and chelator, decomplexation of the metal, and possible altered pharmacokinetics of nanomaterials. Herein, we described a straightforward synthesis of intrinsically radioactive [64Cu]CuInS/ZnS QDs by directly incorporating 64Cu into CuInS/ZnS nanostructure with 64CuCl2 as synthesis precursor. The [64Cu]CuInS/ZnS QDs demonstrated excellent radiochemical stability with less than 3% free 64Cu detected even after exposure to serum containing EDTA (5 mM) for 24 h. PEGylation can be achieved in situ during synthesis, and the PEGylated radioactive QDs showed high tumor uptake (10.8% ID/g) in a U87MG mouse xenograft model. CRET efficiency was studied as a function of concentration and 64Cu radioactivity concentration. These [64Cu]CuInS/ZnS QDs were successfully applied as an efficient PET/self-illuminating luminescence in vivo imaging agents. PMID:25549258

Intrinsically radioactive [64Cu]CuInS/ZnS quantum dots for PET and optical imaging: improved radiochemical stability and controllable Cerenkov luminescence.

PubMed

Guo, Weisheng; Sun, Xiaolian; Jacobson, Orit; Yan, Xuefeng; Min, Kyunghyun; Srivatsan, Avinash; Niu, Gang; Kiesewetter, Dale O; Chang, Jin; Chen, Xiaoyuan

2015-01-27

Functionalized quantum dots (QDs) have been widely explored for multimodality bioimaging and proven to be versatile agents. Attaching positron-emitting radioisotopes onto QDs not only endows their positron emission tomography (PET) functionality, but also results in self-illuminating QDs, with no need for an external light source, by Cerenkov resonance energy transfer (CRET). Traditional chelation methods have been used to incorporate the radionuclide, but these methods are compromised by the potential for loss of radionuclide due to cleavage of the linker between particle and chelator, decomplexation of the metal, and possible altered pharmacokinetics of nanomaterials. Herein, we described a straightforward synthesis of intrinsically radioactive [(64)Cu]CuInS/ZnS QDs by directly incorporating (64)Cu into CuInS/ZnS nanostructure with (64)CuCl2 as synthesis precursor. The [(64)Cu]CuInS/ZnS QDs demonstrated excellent radiochemical stability with less than 3% free (64)Cu detected even after exposure to serum containing EDTA (5 mM) for 24 h. PEGylation can be achieved in situ during synthesis, and the PEGylated radioactive QDs showed high tumor uptake (10.8% ID/g) in a U87MG mouse xenograft model. CRET efficiency was studied as a function of concentration and (64)Cu radioactivity concentration. These [(64)Cu]CuInS/ZnS QDs were successfully applied as an efficient PET/self-illuminating luminescence in vivo imaging agents.

Synthesis and operation of an FFT-decoupled fixed-order reversed-field pinch plasma control system based on identification data

NASA Astrophysics Data System (ADS)

Olofsson, K. Erik J.; Brunsell, Per R.; Witrant, Emmanuel; Drake, James R.

2010-10-01

Recent developments and applications of system identification methods for the reversed-field pinch (RFP) machine EXTRAP T2R have yielded plasma response parameters for decoupled dynamics. These data sets are fundamental for a real-time implementable fast Fourier transform (FFT) decoupled discrete-time fixed-order strongly stabilizing synthesis as described in this work. Robustness is assessed over the data set by bootstrap calculation of the sensitivity transfer function worst-case H_{\\infty} -gain distribution. Output tracking and magnetohydrodynamic mode m = 1 tracking are considered in the same framework simply as two distinct weighted traces of a performance channel output-covariance matrix as derived from the closed-loop discrete-time Lyapunov equation. The behaviour of the resulting multivariable controller is investigated with dedicated T2R experiments.

Synthesis of Novel Thiazole Based Carbaldehyde as Potential Sensor for Fluoride Anion and their Spectroscopic Properties.

PubMed

Tayade, Rajratna P; Sekar, Nagaiyan

2017-05-01

A novel thiazole based carbaldehyde bearing benzimidazole fluorophore as the receptor unit for F - anion was prepared by multi steps synthesis. Density functional theory was used to understand the structural and electronic properties the receptor. The anion sensing activities of receptor 4 were studied for various anions in acetonitrile solvent. The receptor showed fluorescence enhancement in the presence of fluoride anion due to intramolecular charge transfer (ICT) mechanism. No significant changes were observed upon addition of less basic anions such as OAc - , Cl - , Br - , I - , HSO 4 - . After the interaction of fluoride anion with the receptor 4 leads to an 88 nm red shift in emission maxima. [TBA]OH and 1 H NMR titration experiments indicated that deprotonation of N-H in the benzimidazole due to interaction with fluoride anions.

[Gene deletion and functional analysis of the heptyl glycosyltransferase (waaF) gene in Vibrio parahemolyticus O-antigen cluster].

PubMed

Zhao, Feng; Meng, Songsong; Zhou, Deqing

2016-02-04

To construct heptyl glycosyltransferase gene II (waaF) gene deletion mutant of Vibrio parahaemolyticus, and explore the function of the waaF gene in Vibrio parahaemolyticus. The waaF gene deletion mutant was constructed by chitin-based transformation technology using clinical isolates, and then the growth rate, morphology and serotypes were identified. The different sources (O3, O5 and O10) waaF gene complementations were constructed through E. coli S17λpir strains conjugative transferring with Vibrio parahaemolyticus, and the function of the waaF gene was further verified by serotypes. The waaF gene deletion mutant strain was successfully constructed and it grew normally. The growth rate and morphology of mutant were similar with the wild type strains (WT), but the mutant could not occurred agglutination reaction with O antisera. The O3 and O5 sources waaF gene complementations occurred agglutination reaction with O antisera, but the O10 sources waaF gene complementations was not. The waaF gene was related with O-antigen synthesis and it was the key gene of O-antigen synthesis pathway in Vibrio parahaemolyticus. The function of different sources waaF gene were not the same.

Synthesis and Characterization of Polyfunctional Polyhedral Silsesquioxane Cages

NASA Astrophysics Data System (ADS)

Sulaiman, Santy

Recent studies on octameric polyhedral silsesquioxanes, (RSiO1.5 )8, indicate that the silsesquioxane cage is not just a passive component but appears to be involved in electron delocalization with conjugated organic tethers in the excited state. This dissertation presents the synthesis and characterization of (RSiO1.5)8 molecules with unique photophysical properties that provide support for the existence of conjugation that involves the (RSiO1.5)8 cage. The dissertation first discusses the elaboration of octavinylsilsesquioxane via cross-metathesis to form styrenyl-functionalized octasilsesquioxane molecules. Subsequent Heck coupling reactions of p-bromostyrenyl derivative provides vinylstilbene-functionalized octasilsesquioxane. The amino derivative, NH2VinylStilbeneOS, show highly red-shifted emission spectrum (100 nm from the simple organic analog p-vinylstilbene) and high two-photon absorption (TPA) cross-section value (100 GM/moiety), indicating charge-transfer processes involving the silsesquioxane cage as the electron acceptor. The unique photophysical properties of polyfunctional luminescent cubic silsesquioxanes synthesized from ortho-8-, (2,5)-16-, and 24-brominated octaphenylsilsesquioxane (OPS) via Heck coupling show how the steric interactions of the organic tethers at the silsesquioxane cage corner affect conjugation with the silsesquioxane cage. Furthermore, the high TPA cross-section (10 GM/moiety) and photoluminescence quantum yield (20%) of OPS functionalized with 24 acetoxystyrenyl groups suggest that the existence excited states in these molecules with similar energies and decay rates: normal radiative pi- pi* transition and charge transfer involving the silsesquioxane cage. The fluoride ion-catalyzed rearrangement reactions of cage and polymeric silsesquioxanes provide a convenient route to a mixture of deca- and dodecameric silsesquioxane molecules in high yields, giving us the opportunity to investigate the effect of silsesquioxane cage geometry on their photophysical properties. The ability to recycle polymeric silsesquioxane resins, byproducts from cubic silsesquioxane syntheses, into useful cage silsesquioxane molecules adds another advantage. Lastly, we present the synthesis of octa(aminophenyl)silsesquioxane-based epoxy resins with coefficient of thermal expansion (CTE) as low as 25°C/ppm without ceramic fillers. The CTEs of these resins can be tailored over an order of magnitude by choosing epoxy crosslinking agents having different flexibilities.

Temperature-Dependent Function of the Glutamine Phosphoribosylpyrophosphate Amidotransferase Ammonia Channel and Coupling with Glycinamide Ribonucleotide Synthetase in a Hyperthermophile†

PubMed Central

Bera, Aloke Kumar; Chen, Sihong; Smith, Janet L.; Zalkin, Howard

2000-01-01

Genes encoding glutamine phosphoribosylpyrophosphate amidotransferase (GPAT) and glycinamide ribonucleotide synthetase (GARS) from Aquifex aeolicus were expressed in Escherichia coli, and the enzymes were purified to near homogeneity. Both enzymes were maximally active at a temperature of at least 90°C, with half-lives of 65 min for GPAT and 60 h for GARS at 80°C. GPAT activity is known to depend upon channeling of NH3 from a site in an N-terminal glutaminase domain to a distal phosphoribosylpyrophosphate site in a C-terminal domain where synthesis of phosphoribosylamine (PRA) takes place. The efficiency of channeling of NH3 for synthesis of PRA was found to increase from 34% at 37°C to a maximum of 84% at 80°C. The mechanism for transfer of PRA to GARS is not established, but diffusion between enzymes as a free intermediate appears unlikely based on a calculated PRA half-life of approximately 0.6 s at 90°C. Evidence was obtained for coupling between GPAT and GARS for PRA transfer. The coupling was temperature dependent, exhibiting a transition between 37 and 50°C, and remained relatively constant up to 90°C. The calculated PRA chemical half-life, however, decreased by a factor of 20 over this temperature range. These results provide evidence that coupling involves direct PRA transfer through GPAT-GARS interaction rather than free diffusion. PMID:10850988

Temperature-dependent function of the glutamine phosphoribosylpyrophosphate amidotransferase ammonia channel and coupling with glycinamide ribonucleotide synthetase in a hyperthermophile.

PubMed

Bera, A K; Chen, S; Smith, J L; Zalkin, H

2000-07-01

Genes encoding glutamine phosphoribosylpyrophosphate amidotransferase (GPAT) and glycinamide ribonucleotide synthetase (GARS) from Aquifex aeolicus were expressed in Escherichia coli, and the enzymes were purified to near homogeneity. Both enzymes were maximally active at a temperature of at least 90 degrees C, with half-lives of 65 min for GPAT and 60 h for GARS at 80 degrees C. GPAT activity is known to depend upon channeling of NH(3) from a site in an N-terminal glutaminase domain to a distal phosphoribosylpyrophosphate site in a C-terminal domain where synthesis of phosphoribosylamine (PRA) takes place. The efficiency of channeling of NH(3) for synthesis of PRA was found to increase from 34% at 37 degrees C to a maximum of 84% at 80 degrees C. The mechanism for transfer of PRA to GARS is not established, but diffusion between enzymes as a free intermediate appears unlikely based on a calculated PRA half-life of approximately 0.6 s at 90 degrees C. Evidence was obtained for coupling between GPAT and GARS for PRA transfer. The coupling was temperature dependent, exhibiting a transition between 37 and 50 degrees C, and remained relatively constant up to 90 degrees C. The calculated PRA chemical half-life, however, decreased by a factor of 20 over this temperature range. These results provide evidence that coupling involves direct PRA transfer through GPAT-GARS interaction rather than free diffusion.

Biogenesis and functions of mammalian iron-sulfur proteins in the regulation of iron homeostasis and pivotal metabolic pathways.

PubMed

Rouault, Tracey A; Maio, Nunziata

2017-08-04

Fe-S cofactors are composed of iron and inorganic sulfur in various stoichiometries. A complex assembly pathway conducts their initial synthesis and subsequent binding to recipient proteins. In this minireview, we discuss how discovery of the role of the mammalian cytosolic aconitase, known as iron regulatory protein 1 (IRP1), led to the characterization of the function of its Fe-S cluster in sensing and regulating cellular iron homeostasis. Moreover, we present an overview of recent studies that have provided insights into the mechanism of Fe-S cluster transfer to recipient Fe-S proteins. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

Pentacene appended to a TEMPO stable free radical: the effect of magnetic exchange coupling on photoexcited pentacene.

PubMed

Chernick, Erin T; Casillas, Rubén; Zirzlmeier, Johannes; Gardner, Daniel M; Gruber, Marco; Kropp, Henning; Meyer, Karsten; Wasielewski, Michael R; Guldi, Dirk M; Tykwinski, Rik R

2015-01-21

Understanding the fundamental spin dynamics of photoexcited pentacene derivatives is important in order to maximize their potential for optoelectronic applications. Herein, we report on the synthesis of two pentacene derivatives that are functionalized with the [(2,2,6,6-tetramethylpiperidin-1-yl)oxy] (TEMPO) stable free radical. The presence of TEMPO does not quench the pentacene singlet excited state, but does quench the photoexcited triplet excited state as a function of TEMPO-to-pentacene distance. Time-resolved electron paramagnetic resonance experiments confirm that triplet quenching is accompanied by electron spin polarization transfer from the pentacene excited state to the TEMPO doublet state in the weak coupling regime.

Synthesis, structural, spectroscopic and optical studies of charge transfer complex salts.

PubMed

Manikandan, Maruthappan; Mahalingam, Thaiyan; Hayakawa, Yasuhiro; Ravi, Ganesan

2013-01-15

New charge transfer molecular complex adducts of picric acid (C6H3N3O7) with triethylamine (C6H15N) and dimethylformamide (HCON(CH3)2) were synthesized successfully for the first time. Chemical composition and stoichiometry of the synthesized complex salts were verified by CHN elemental analysis. Solubility of the complex salts have been determined by gravimetric method and single crystals of two new salts were grown by low temperature solution growth technique. Crystal system, crystalline nature and cell parameters of the grown crystals were determined by single crystal X-ray diffraction (SXRD) and powder X-ray diffraction (PXRD) analyses. The formations of the charge-transfer complex, functional groups and the modes of vibrations have been confirmed by Fourier transform infrared (FTIR) spectroscopy. In order to know the linear and nonlinear optical suitability for device fabrication, UV-Vis (UV) spectral analysis and relative second harmonic generation (SHG) efficiency test were performed for the grown crystals. Copyright © 2012 Elsevier B.V. All rights reserved.

Synthesis of surface-anchored DNA-polymer bioconjugates using reversible addition-fragmentation chain transfer polymerization.

PubMed

He, Peng; He, Lin

2009-07-13

We report here an approach to grafting DNA-polymer bioconjugates on a planar solid support using reversible addition-fragmentation chain transfer (RAFT) polymerization. In particular, a trithiocarbonate compound as the RAFT chain transfer agent (CTA) is attached to the distal point of a surface-immobilized oligonucleotide. Initiation of RAFT polymerization leads to controlled growth of polymers atop DNA molecules on the surface. Growth kinetics of poly(monomethoxy-capped oligo(ethylene glycol) methacrylate) atop DNA molecules is investigated by monitoring the change of polymer film thickness as a function of reaction time. The reaction conditions, including the polymerization temperature, the initiator concentration, the CTA surface density, and the selection of monomers, are varied to examine their impacts on the grafting efficiency of DNA-polymer conjugates. Comparing to polymer growth atop small molecules, the experimental results suggest that DNA molecules significantly accelerate polymer growth, which is speculated as a result of the presence of highly charged DNA backbones and purine/pyrimidine moieties surrounding the reaction sites.

Tandem catalysis of ring-closing metathesis/atom transfer radical reactions with homobimetallic ruthenium–arene complexes

PubMed Central

Borguet, Yannick; Sauvage, Xavier; Zaragoza, Guillermo; Demonceau, Albert

2010-01-01

Summary The tandem catalysis of ring-closing metathesis/atom transfer radical reactions was investigated with the homobimetallic ruthenium–indenylidene complex [(p-cymene)Ru(μ-Cl)3RuCl(3-phenyl-1-indenylidene)(PCy3)] (1) to generate active species in situ. The two catalytic processes were first carried out independently in a case study before the whole sequence was optimized and applied to the synthesis of several polyhalogenated bicyclic γ-lactams and lactones from α,ω-diene substrates bearing trihaloacetamide or trichloroacetate functionalities. The individual steps were carefully monitored by 1H and 31P NMR spectroscopies in order to understand the intimate details of the catalytic cycles. Polyhalogenated substrates and the ethylene released upon metathesis induced the clean transformation of catalyst precursor 1 into the Ru(II)–Ru(III) mixed-valence compound [(p-cymene)Ru(μ-Cl)3RuCl2(PCy3)], which was found to be an efficient promoter for atom transfer radical reactions under the adopted experimental conditions. PMID:21160564

Synthesis, structural, spectroscopic and optical studies of charge transfer complex salts

NASA Astrophysics Data System (ADS)

Manikandan, Maruthappan; Mahalingam, Thaiyan; Hayakawa, Yasuhiro; Ravi, Ganesan

2013-01-01

New charge transfer molecular complex adducts of picric acid (C6H3N3O7) with triethylamine (C6H15N) and dimethylformamide (HCON(CH3)2) were synthesized successfully for the first time. Chemical composition and stoichiometry of the synthesized complex salts were verified by CHN elemental analysis. Solubility of the complex salts have been determined by gravimetric method and single crystals of two new salts were grown by low temperature solution growth technique. Crystal system, crystalline nature and cell parameters of the grown crystals were determined by single crystal X-ray diffraction (SXRD) and powder X-ray diffraction (PXRD) analyses. The formations of the charge-transfer complex, functional groups and the modes of vibrations have been confirmed by Fourier transform infrared (FTIR) spectroscopy. In order to know the linear and nonlinear optical suitability for device fabrication, UV-Vis (UV) spectral analysis and relative second harmonic generation (SHG) efficiency test were performed for the grown crystals.

A facile, bio-based, novel approach for synthesis of covalently functionalized graphene nanoplatelet nano-coolants toward improved thermo-physical and heat transfer properties.

PubMed

Sadri, Rad; Hosseini, Maryam; Kazi, S N; Bagheri, Samira; Abdelrazek, Ali H; Ahmadi, Goodarz; Zubir, Nashrul; Ahmad, Roslina; Abidin, N I Z

2018-01-01

In this study, we synthesized covalently functionalized graphene nanoplatelet (GNP) aqueous suspensions that are highly stable and environmentally friendly for use as coolants in heat transfer systems. We evaluated the heat transfer and hydrodynamic properties of these nano-coolants flowing through a horizontal stainless steel tube subjected to a uniform heat flux at its outer surface. The GNPs functionalized with clove buds using the one-pot technique. We characterized the clove-treated GNPs (CGNPs) using X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). We then dispersed the CGNPs in distilled water at three particle concentrations (0.025, 0.075 and 0.1wt%) in order to prepare the CGNP-water nanofluids (nano-coolants). We used ultraviolet-visible (UV-vis) spectroscopy to examine the stability and solubility of the CGNPs in the distilled water. There is significant enhancement in thermo-physical properties of CGNPs nanofluids relative those for distilled water. We validated our experimental set-up by comparing the friction factor and Nusselt number for distilled water obtained from experiments with those determined from empirical correlations, indeed, our experimental set-up is reliable and produces results with reasonable accuracy. We conducted heat transfer experiments for the CGNP-water nano-coolants flowing through the horizontal heated tube in fully developed turbulent condition. Our results are indeed promising since there is a significant enhancement in the Nusselt number and convective heat transfer coefficient for the CGNP-water nanofluids, with only a negligible increase in the friction factor and pumping power. More importantly, we found that there is a significant increase in the performance index, which is a positive indicator that our nanofluids have potential to substitute conventional coolants in heat transfer systems because of their overall thermal performance and energy savings benefits. Copyright © 2017 Elsevier Inc. All rights reserved.

Functionalizing the γ-Position of α-Diazo-β-ketoesters.

PubMed

Nguyen, Thu Q; Alqurafi, Maha; Edwards, Cash; Nguyen, Pauline; Kim, Jean; Casco, Samuel; Bennet, Maricka; Chiang, Christopher; Lohry, Maureen; Cox, Melina; Meshram, Byron; Le, Duyen; Kim, Eugene; Smriti, Snigdha; Oelschlaeger, Peter; Buynak, John D

2016-06-27

Although α-diazo-β-ketoesters are synthetically versatile intermediates, methodology for introducing this functionality into complex molecules is still limited, most frequently involving a carboxylic acid precursor, which is then activated and transformed into a β-ketoester, with the diazo group being subsequently added with a diazo transfer reagent. While introducing this highly functional moiety in a convergent one step process would be ideal, such an objective is limited by the relatively few studies which address functionalization of the α-diazo-β-ketoester at the γ-position. In the present investigation, we evaluate strategies, both new and established, for functionalizing α-diazo-β-ketoesters, particularly with regard to generating compounds prospectively useful in the synthesis of C1-substituted carbapenems. We report the first δ-aldehydo-α-diazo-β-ketoester as well as a method for its oxidation to the corresponding methyl ester, and the formation of a new substituted pyrazole under basic conditions.

Electron-deficient triarylborane block copolymers: synthesis by controlled free radical polymerization and application in the detection of fluoride ions.

PubMed

Cheng, Fei; Bonder, Edward M; Jäkle, Frieder

2013-11-20

Luminescent triarylborane homo and block copolymers with well-defined chain architectures were synthesized via reversible addition-fragmentation chain transfer polymerization of a vinyl-functionalized borane monomer. The Lewis acid properties of the polymers were exploited in the luminescent detection of fluoride ions. A dual-responsive fluoride sensor was developed by taking advantage of the reversible self-assembly of a PNIPAM-based amphiphilic block copolymer. Anion detection in aqueous solution was realized by introducing positively charged pyridinium moieties along the polymer chain.

Synthesis, crystal structure and redox properties of dihydropyrazole-bridged ferrocene-based derivatives

NASA Astrophysics Data System (ADS)

Li, Heng-Dong; Ma, Zai-He; Yang, Kun; Xie, Li-Li; Yuan, Yao-Feng

2012-09-01

Dihydropyrazole-bridged ferrocene-based derivatives were prepared by corresponding chalcones with hydrazine hydrate, then acylation with 3-(ethoxycarbonyl)propionyl chloride directly in high yields and purity. All of these compounds were characterized by MS, IR, 1H NMR, 13C NMR and elemental analysis. The relationship between the structure and redox properties was investigated based on the results of single crystal X-ray structure determinations and cyclic voltammetry. The mechanism of the electron transfer for representative compound 4b was verified by density functional theory (DFT) calculations.

Synthesis of Iowa research to address rural safety : [tech transfer summary].

DOT National Transportation Integrated Search

2014-10-01

Information about roadway departures, rural intersections, and : rural speed management countermeasures relevant to Iowa was : summarized on webpages (www.ctre.iastate.edu/research-synthesis/) : to allow agencies to more effectively target specific t...

Expanding the Enzyme Universe: Accessing Non-Natural Reactions by Mechanism-Guided Directed Evolution

PubMed Central

Renata, Hans; Wang, Z. Jane

2015-01-01

High selectivities and exquisite control over reaction outcomes entice chemists to use biocatalysts in organic synthesis. However, many useful reactions are not accessible because they are not in nature’s known repertoire. We will use this review to outline an evolutionary approach to engineering enzymes to catalyze reactions not found in nature. We begin with examples of how nature has discovered new catalytic functions and how such evolutionary progressions have been recapitulated in the laboratory starting from extant enzymes. We then examine non-native enzyme activities that have been discovered and exploited for chemical synthesis, emphasizing reactions that do not have natural counterparts. The new functions have mechanistic parallels to the native reaction mechanisms that often manifest as catalytic promiscuity and the ability to convert from one function to the other with minimal mutation. We present examples of how non-natural activities have been improved by directed evolution, mimicking the process used by nature to create new catalysts. Examples of new enzyme functions include epoxide opening reactions with non-natural nucleophiles catalyzed by a laboratory-evolved halohydrin dehalogenase, cyclopropanation and other carbene transfer reactions catalyzed by cytochrome P450 variants, and non-natural modes of cyclization by a modified terpene synthase. Lastly, we describe discoveries of non-native catalytic functions that may provide future opportunities for expanding the enzyme universe. PMID:25649694

Synthesis, characterization, and nonlinear optical properties of graphene oxide functionalized with tetra-amino porphyrin

NASA Astrophysics Data System (ADS)

Yamuna, R.; Ramakrishnan, S.; Dhara, Keerthy; Devi, R.; Kothurkar, Nikhil K.; Kirubha, E.; Palanisamy, P. K.

2013-01-01

The synthesis of a porphyrin-graphene oxide hybrid (GO-TAP) was carried out by covalently functionalizing graphene oxide (GO) with 5,10,15,20 mesotetra (4-aminophenyl) porphyrin (TAP) through an amide linkage. The GO-TAP hybrid has been characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and UV-visible spectroscopy. The peak intensity of the Soret band of the material was suppressed compared to neat TAP. This indicates a strong interaction between the electronic energy level of TAP and GO in the GO-TAP hybrid. The functionalization of GO with TAP significantly improved its solubility and dispersion stability in organic solvents. Scanning electron micrographs reveal that the hybrid was found to be similar to the unmodified GO but slightly more wrinkled. Transmission electron micrographs also demonstrate that GO sheet in the hybrid is more wrinkled with some dark spot due to functionalization. Atomic force microscopy results also reveal that the TAP functionalization increases the thickness of GO sheet to 2.0-3.0 nm from 1.2 to 1.8 nm. We observed improved nonlinear optical and optical limiting properties for the hybrid compared to both graphene oxide and porphyrin. GO-TAP shows fluorescence quenching compared with porphyrin, indicating excellent electron and/or energy transfer to GO from TAP. Thermogravimetric analysis confirms that the GO-TAP hybrid has outstanding thermal stability.

Piezoelectric Templates - New Views on Biomineralization and Biomimetics.

PubMed

Stitz, Nina; Eiben, Sabine; Atanasova, Petia; Domingo, Neus; Leineweber, Andreas; Burghard, Zaklina; Bill, Joachim

2016-05-23

Biomineralization in general is based on electrostatic interactions and molecular recognition of organic and inorganic phases. These principles of biomineralization have also been utilized and transferred to bio-inspired synthesis of functional materials during the past decades. Proteins involved in both, biomineralization and bio-inspired processes, are often piezoelectric due to their dipolar character hinting to the impact of a template's piezoelectricity on mineralization processes. However, the piezoelectric contribution on the mineralization process and especially the interaction of organic and inorganic phases is hardly considered so far. We herein report the successful use of the intrinsic piezoelectric properties of tobacco mosaic virus (TMV) to synthesize piezoelectric ZnO. Such films show a two-fold increase of the piezoelectric coefficient up to 7.2 pm V(-1) compared to films synthesized on non-piezoelectric templates. By utilizing the intrinsic piezoelectricity of a biotemplate, we thus established a novel synthesis pathway towards functional materials, which sheds light on the whole field of biomimetics. The obtained results are of even broader and general interest since they are providing a new, more comprehensive insight into the mechanisms involved into biomineralization in living nature.

Piezoelectric Templates - New Views on Biomineralization and Biomimetics

NASA Astrophysics Data System (ADS)

Stitz, Nina; Eiben, Sabine; Atanasova, Petia; Domingo, Neus; Leineweber, Andreas; Burghard, Zaklina; Bill, Joachim

2016-05-01

Biomineralization in general is based on electrostatic interactions and molecular recognition of organic and inorganic phases. These principles of biomineralization have also been utilized and transferred to bio-inspired synthesis of functional materials during the past decades. Proteins involved in both, biomineralization and bio-inspired processes, are often piezoelectric due to their dipolar character hinting to the impact of a template’s piezoelectricity on mineralization processes. However, the piezoelectric contribution on the mineralization process and especially the interaction of organic and inorganic phases is hardly considered so far. We herein report the successful use of the intrinsic piezoelectric properties of tobacco mosaic virus (TMV) to synthesize piezoelectric ZnO. Such films show a two-fold increase of the piezoelectric coefficient up to 7.2 pm V-1 compared to films synthesized on non-piezoelectric templates. By utilizing the intrinsic piezoelectricity of a biotemplate, we thus established a novel synthesis pathway towards functional materials, which sheds light on the whole field of biomimetics. The obtained results are of even broader and general interest since they are providing a new, more comprehensive insight into the mechanisms involved into biomineralization in living nature.

One-step synthesis of boronic acid functionalized gold nanoclusters for photoluminescence sensing of dopamine

NASA Astrophysics Data System (ADS)

Chen, Huide; Liu, Chunxiu; Xia, Yunsheng

2017-03-01

This study is the first to report one-step synthesis of boronic acid functionalized gold nanoclusters (AuNCs) using mixed ligands of 4-mercaptophenylboronic acid (MPBA) and glutathione. Furthermore, the emission color of the products can be fancily tuned from green to near-infrared by simply changing the proportion of the two stabilizers. In basic media, dopamine (DA) molecules themselves polymerize each other and form polydopamine with large amounts of cis-diol groups, which then react with boronic acid groups on the AuNC’s surface based on the formation of boronate esters. As a result, the photoluminescence of the AuNCs is well quenched by the electron transfer effect. Accordingly, DA molecules are assayed from 0.5 to 9 μM, and the detection limit is as low as 0.1 μM. The as-prepared AuNCs exhibit high selectivity; the existing biomolecules including various amino acids, ascorbic acid, uric acid, glucose, etc, do not interfere with the assay. The proposed method is successfully applied to the assay of DA in human serum, indicating its practical potential.

Gold Decorated Graphene for Rapid Dye Reduction and Efficient Electro Catalytic Oxidation of Ethanol

NASA Astrophysics Data System (ADS)

Siddhardha, R. S.; Kumar v, Lakshman; Kaniyoor, A.; Podila, R.; Kumar, V. S.; Venkataramaniah, K.; Ramaprabhu, S.; Rao, A.; Ramamurthy, S. S.; Clemson University Team; Sri Sathya Sai Institute of Higher Learning Team; IITMadras Team

2013-03-01

A well known disadvantage in fabrication of metal-graphene composite is the use of surfactants that strongly adsorb on the surface and reduce the performance of the catalyst. Here, we demonstrate a novel one pot synthesis of gold nanoparticles (AuNPs) by laser ablation of gold strip and simultaneous decoration of these on functionalized graphene derivatives. Not only the impregnation of AuNPs was linker free, but also the synthesis by itself was surfactant free. This resulted in in-situ decoration of pristine AuNPs on functionalized graphene derivatives. These materials were well characterized and tested for catalytic applications pertaining to dye reduction and electrooxidation. The catalytic reduction rates are 1.4 x 102 and 9.4x102 times faster for Rhodamine B and Methylene Blue dyes respectively, compared to earlier reports. The enhanced rate involves synergistic interplay of electronic relay between AuNPs and the dye, also charge transfer between the graphene system and dye. In addition, the onset potential for ethanol oxidation was found to be more negative ~ 100 mV, an indication of its promising application in direct ethanol fuel cells.

Copper cluster size effect in methanol synthesis from CO 2

DOE PAGES

Yang, Bing; Liu, Cong; Halder, Avik; ...

2017-05-08

Here, size-selected Cu n catalysts ( n = 3, 4, 20) were synthesized on Al 2O 3 thin films using mass-selected cluster deposition. A systematic study of size and support effects was carried out for CO 2 hydrogenation at atmospheric pressure using a combination of in situ grazing incidence X-ray absorption spectroscopy, catalytic activity measurement, and first-principles calculations. The catalytic activity for methanol synthesis is found to strongly vary as a function of the cluster size; the Cu 4/Al 2O 3 catalyst shows the highest turnover rate for CH 3OH production. With only one atom less than Cu 4, Cumore » 3 showed less than 50% activity. Density functional theory calculations predict that the activities of the gas-phase Cu clusters increase as the cluster size decreases; however, the stronger charge transfer interaction with Al 2O 3 support for Cu 3 than for Cu 4 leads to remarkably reduced binding strength between the adsorbed intermediates and supported Cu 3, which subsequently results in a less favorable energetic pathway to transform carbon dioxide to methanol.« less

Microparticle-mediated transfer of the viral receptors CAR and CD46, and the CFTR channel in a CHO cell model confers new functions to target cells.

PubMed

Gonzalez, Gaëlle; Vituret, Cyrielle; Di Pietro, Attilio; Chanson, Marc; Boulanger, Pierre; Hong, Saw-See

2012-01-01

Cell microparticles (MPs) released in the extracellular milieu can embark plasma membrane and intracellular components which are specific of their cellular origin, and transfer them to target cells. The MP-mediated, cell-to-cell transfer of three human membrane glycoproteins of different degrees of complexity was investigated in the present study, using a CHO cell model system. We first tested the delivery of CAR and CD46, two monospanins which act as adenovirus receptors, to target CHO cells. CHO cells lack CAR and CD46, high affinity receptors for human adenovirus serotype 5 (HAdV5), and serotype 35 (HAdV35), respectively. We found that MPs derived from CHO cells (MP-donor cells) constitutively expressing CAR (MP-CAR) or CD46 (MP-CD46) were able to transfer CAR and CD46 to target CHO cells, and conferred selective permissiveness to HAdV5 and HAdV35. In addition, target CHO cells incubated with MP-CD46 acquired the CD46-associated function in complement regulation. We also explored the MP-mediated delivery of a dodecaspanin membrane glycoprotein, the CFTR to target CHO cells. CFTR functions as a chloride channel in human cells and is implicated in the genetic disease cystic fibrosis. Target CHO cells incubated with MPs produced by CHO cells constitutively expressing GFP-tagged CFTR (MP-GFP-CFTR) were found to gain a new cellular function, the chloride channel activity associated to CFTR. Time-course analysis of the appearance of GFP-CFTR in target cells suggested that MPs could achieve the delivery of CFTR to target cells via two mechanisms: the transfer of mature, membrane-inserted CFTR glycoprotein, and the transfer of CFTR-encoding mRNA. These results confirmed that cell-derived MPs represent a new class of promising therapeutic vehicles for the delivery of bioactive macromolecules, proteins or mRNAs, the latter exerting the desired therapeutic effect in target cells via de novo synthesis of their encoded proteins.

Effect of bed characters on the direct synthesis of dimethyldichlorosilane in fluidized bed reactor.

PubMed

Zhang, Pan; Duan, Ji H; Chen, Guang H; Wang, Wei W

2015-03-06

This paper presents the numerical investigation of the effects of the general bed characteristics such as superficial gas velocities, bed temperature, bed heights and particle size, on the direct synthesis in a 3D fluidized bed reactor. A 3D model for the gas flow, heat transfer, and mass transfer was coupled to the direct synthesis reaction mechanism verified in the literature. The model was verified by comparing the simulated reaction rate and dimethyldichlorosilane (M2) selectivity with the experimental data in the open literature and real production data. Computed results indicate that superficial gas velocities, bed temperature, bed heights, and particle size have vital effect on the reaction rates and/or M2 selectivity.

Effect of Bed Characters on the Direct Synthesis of Dimethyldichlorosilane in Fluidized Bed Reactor

PubMed Central

Zhang, Pan; Duan, Ji H.; Chen, Guang H.; Wang, Wei W.

2015-01-01

This paper presents the numerical investigation of the effects of the general bed characteristics such as superficial gas velocities, bed temperature, bed heights and particle size, on the direct synthesis in a 3D fluidized bed reactor. A 3D model for the gas flow, heat transfer, and mass transfer was coupled to the direct synthesis reaction mechanism verified in the literature. The model was verified by comparing the simulated reaction rate and dimethyldichlorosilane (M2) selectivity with the experimental data in the open literature and real production data. Computed results indicate that superficial gas velocities, bed temperature, bed heights, and particle size have vital effect on the reaction rates and/or M2 selectivity. PMID:25742729

What do magnetic resonance-based measurements of Pi→ATP flux tell us about skeletal muscle metabolism?

PubMed

Kemp, Graham J; Brindle, Kevin M

2012-08-01

Magnetic resonance spectroscopy (MRS) methods offer a potentially valuable window into cellular metabolism. Measurement of flux between inorganic phosphate (Pi) and ATP using (31)P MRS magnetization transfer has been used in resting muscle to assess what is claimed to be mitochondrial ATP synthesis and has been particularly popular in the study of insulin effects and insulin resistance. However, the measured Pi→ATP flux in resting skeletal muscle is far higher than the true rate of oxidative ATP synthesis, being dominated by a glycolytically mediated Pi↔ATP exchange reaction that is unrelated to mitochondrial function. Furthermore, even if measured accurately, the ATP production rate in resting muscle has no simple relationship to mitochondrial capacity as measured either ex vivo or in vivo. We summarize the published measurements of Pi→ATP flux, concentrating on work relevant to diabetes and insulin, relate it to current understanding of the physiology of mitochondrial ATP synthesis and glycolytic Pi↔ATP exchange, and discuss some possible implications of recently reported correlations between Pi→ATP flux and other physiological measures.

Synthesis, Characterization and Reactivity of a Hexane-Soluble Silver Salt

ERIC Educational Resources Information Center

Stockland, Robert A. Jr.; Wilson, Brian D.; Goodman, Caton C.; Giese, Barret J.; Shrimp, Frederick L., II

2007-01-01

The connectivity of a hexane-soluble silver salt is established by using NMR spectroscopy to describe the synthesis, characterization and reactivity of the salt. The results found hexane-soluble silver to be an effective transfer agent.

Synthesis and characterization of a potential prebiotic trisaccharide from cheese whey permeate and sucrose by Leuconostoc mesenteroides dextransucrase.

PubMed

Díez-Municio, Marina; Montilla, Antonia; Jimeno, M Luisa; Corzo, Nieves; Olano, Agustín; Moreno, F Javier

2012-02-29

The production of new bioactive oligosaccharides is currently garnering much attention for their potential use as functional ingredients. This work addresses the enzymatic synthesis and NMR structural characterization of 2-α-D-glucopyranosyl-lactose derived from sucrose:lactose and sucrose:cheese whey permeate mixtures by using a Leuconostoc mesenteroides B-512F dextransucrase. The effect of synthesis conditions, including concentration of substrates, molar ratio of donor/acceptor, enzyme concentration, reaction time, and temperature, on the formation of transfer products is evaluated. Results indicated that cheese whey permeate is a suitable material for the synthesis of 2-α-D-glucopyranosyl-lactose, giving rise to yields around 50% (in weight respect to the initial amount of lactose) under the optimum reaction conditions. According to its structure, this trisaccharide is an excellent candidate for a new prebiotic ingredient, due to the reported high resistance of α-(1→2) linkages to the digestive enzymes in humans and animals, as well as to its potential selective stimulation of beneficial bacteria in the large intestine mainly attributed to the two linked glucose units located at the reducing end that reflects the disaccharide kojibiose (2-α-D-glucopyranosyl-D-glucose). These findings could contribute to broadening the use of important agricultural raw materials, such as sucrose or cheese whey permeates, as renewable substrates for enzymatic synthesis of oligosaccharides of nutritional interest.

Neuropeptides affecting the transfer of juvenile hormones from males to females during mating in Spodoptera frugiperda.

PubMed

Hassanien, Intisar T E; Grötzner, Manuela; Meyering-Vos, Martina; Hoffmann, Klaus H

2014-07-01

In the polyandric moth, Spodopterafrugiperda, juvenile hormone (JH) is transferred from the male accessory reproductive glands (AG) to the female bursa copulatrix (BC) during copulation (see Hassanien et al., 2014). Here we used the RNA interference technique to study the role of allatoregulating neuropeptides in controlling the synthesis and transfer of JH during mating. Knockdown of S. frugiperda allatostatin C (Spofr-AS type C) in freshly emerged males leads to an accumulation of JH in the AG beyond that in the control and mating results in a higher transport of JH I and JH II into the female BC. Knockdown of S. frugiperda allatotropin 2 (Spofr-AT2) significantly reduces the amount of JH in the AG as well as its transfer into the female BC during copulation. Knockdown of S. frugiperda allatostatin A (Spofr-AS type A) and S. frugiperda allatotropin (Spofr-AT; Hassanien et al., 2014) only slightly affects the accumulation of JH in the AG and its transfer from the male to the female. We conclude that Spofr-AS type C and Spofr-AT2 act as true allatostatin and true allatotropin, respectively, on the synthesis of JH I and JH II in the male AG. Moreover, both peptides seem to control the synthesis of JH III in the corpora allata of adult males and its release into the hemolymph. Copyright © 2014 Elsevier Ltd. All rights reserved.

Transfer of the cytochrome P450-dependent dhurrin pathway from Sorghum bicolor into Nicotiana tabacum chloroplasts for light-driven synthesis

PubMed Central

Gnanasekaran, Thiyagarajan; Karcher, Daniel; Nielsen, Agnieszka Zygadlo; Martens, Helle Juel; Ruf, Stephanie; Kroop, Xenia; Olsen, Carl Erik; Motawie, Mohammed Saddik; Pribil, Mathias; Møller, Birger Lindberg; Bock, Ralph; Jensen, Poul Erik

2016-01-01

Plant chloroplasts are light-driven cell factories that have great potential to act as a chassis for metabolic engineering applications. Using plant chloroplasts, we demonstrate how photosynthetic reducing power can drive a metabolic pathway to synthesise a bio-active natural product. For this purpose, we stably engineered the dhurrin pathway from Sorghum bicolor into the chloroplasts of Nicotiana tabacum (tobacco). Dhurrin is a cyanogenic glucoside and its synthesis from the amino acid tyrosine is catalysed by two membrane-bound cytochrome P450 enzymes (CYP79A1 and CYP71E1) and a soluble glucosyltransferase (UGT85B1), and is dependent on electron transfer from a P450 oxidoreductase. The entire pathway was introduced into the chloroplast by integrating CYP79A1, CYP71E1, and UGT85B1 into a neutral site of the N. tabacum chloroplast genome. The two P450s and the UGT85B1 were functional when expressed in the chloroplasts and converted endogenous tyrosine into dhurrin using electrons derived directly from the photosynthetic electron transport chain, without the need for the presence of an NADPH-dependent P450 oxidoreductase. The dhurrin produced in the engineered plants amounted to 0.1–0.2% of leaf dry weight compared to 6% in sorghum. The results obtained pave the way for plant P450s involved in the synthesis of economically important compounds to be engineered into the thylakoid membrane of chloroplasts, and demonstrate that their full catalytic cycle can be driven directly by photosynthesis-derived electrons. PMID:26969746

Metabolic pathway analysis of Scheffersomyces (Pichia) stipitis: effect of oxygen availability on ethanol synthesis and flux distributions.

PubMed

Unrean, Pornkamol; Nguyen, Nhung H A

2012-06-01

Elementary mode analysis (EMA) identifies all possible metabolic states of the cell metabolic network. Investigation of these states can provide a detailed insight into the underlying metabolism in the cell. In this study, the flux states of Scheffersomyces (Pichia) stipitis metabolism were examined. It was shown that increasing oxygen levels led to a decrease of ethanol synthesis. This trend was confirmed by experimental evaluation of S. stipitis in glucose-xylose fermentation. The oxygen transfer rate for an optimal ethanol production was 1.8 mmol/l/h, which gave the ethanol yield of 0.40 g/g and the ethanol productivity of 0.25 g/l/h. For a better understanding of the cell's regulatory mechanism in response to oxygenation levels, EMA was used to examine metabolic flux patterns under different oxygen levels. Up- and downregulation of enzymes in the network during the change of culturing condition from oxygen limitation to oxygen sufficiency were identified. The results indicated the flexibility of S. stipitis metabolism to cope with oxygen availability. In addition, relevant genetic targets towards improved ethanol-producing strains under all oxygenation levels were identified. These targeted genes limited the metabolic functionality of the cell to function according to the most efficient ethanol synthesis pathways. The presented approach is promising and can contribute to the development of culture optimization and strain engineers for improved lignocellulosic ethanol production by S. stipitis.

Directional Carrier Transfer in Strongly Coupled Binary Nanocrystal Superlattice Films Formed by Assembly and in Situ Ligand Exchange at a Liquid–Air Interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Yaoting; Li, Siming; Gogotsi, Natalie

Two species of monodisperse nanocrystals (NCs) can self-assemble into a variety of complex 2D and 3D periodic structures, or binary NC superlattice (BNSL) films, based on the relative number and size of the NCs. BNSL films offer great promise for both fundamental scientific studies and optoelectronic applications; however, the utility of as-assembled structures has been limited by the insulating ligands that originate from the synthesis of NCs. Here we report the application of an in situ ligand exchange strategy at a liquid–air interface to replace the long synthesis ligands with short ligands while preserving the long-range order of BNSL films.more » This approach is demonstrated for BNSL structures consisting of PbSe NCs of different size combinations and ligands of interest for photovoltaic devices, infrared detectors, and light-emitting diodes. To confirm enhanced coupling introduced by ligand exchange, we show ultrafast (~1 ps) directional carrier transfer across the type-I heterojunction formed by NCs of different sizes within ligand-exchanged BNSL films. In conclusion, this approach shows the potential promise of functional BNSL films, where the local and long-range energy landscape and electronic coupling can be adjusted by tuning NC composition, size, and interparticle spacing.« less

Prefoldin–Nascent Chain Complexes in the Folding of Cytoskeletal Proteins

PubMed Central

Hansen, William J.; Cowan, Nicholas J.; Welch, William J.

1999-01-01

In vitro transcription/translation of actin cDNA and analysis of the translation products by native-PAGE was used to study the maturation pathway of actin. During the course of actin synthesis, several distinct actin-containing species were observed and the composition of each determined by immunological procedures. After synthesis of the first ∼145 amino acids, the nascent ribosome-associated actin chain binds to the recently identified heteromeric chaperone protein, prefoldin (PFD). PFD remains bound to the relatively unfolded actin polypeptide until its posttranslational delivery to cytosolic chaperonin (CCT). We show that α- and β-tubulin follow a similar maturation pathway, but to date find no evidence for an interaction between PFD and several noncytoskeletal proteins. We conclude that PFD functions by selectively targeting nascent actin and tubulin chains pending their transfer to CCT for final folding and/or assembly. PMID:10209023

Solar Synthesis of PbS-SnS2 Superstructure Nanoparticles.

PubMed

Brontvein, Olga; Albu-Yaron, Ana; Levy, Moshe; Feuerman, Daniel; Popovitz-Biro, Ronit; Tenne, Reshef; Enyashin, Andrey; Gordon, Jeffrey M

2015-08-25

We report the synthesis and supporting density-functional-theory computations for a closed-cage, misfit layered-compound superstructure from PbS-SnS2, generated by highly concentrated sunlight from a precursor mixture of Pb, SnS2, and graphite. The unique reactor conditions created in our solar furnace are found to be particularly conducive to the formation of these nanomaterials. Detailed structural and chemical characterization revealed a spontaneous inside-out formation mechanism, with a broad range of nonhollow fullerene-like structures starting at a diameter of ∼20 nm and a wall thickness of ∼5 layers. The computations also reveal a counterintuitive charge transfer pathway from the SnS2 layers to the PbS layers, which indicates that, in contrast to binary-layered compounds where it is principally van der Waals forces that hold the layers together, polar forces appear to be as important in stabilizing superstructures of misfit layered compounds.

An Ultimate Stereocontrol in Asymmetric Synthesis of Optically Pure Fully Aromatic Helicenes.

PubMed

Šámal, Michal; Chercheja, Serghei; Rybáček, Jiří; Vacek Chocholoušová, Jana; Vacek, Jaroslav; Bednárová, Lucie; Šaman, David; Stará, Irena G; Starý, Ivo

2015-07-08

The role of the helicity of small molecules in enantioselective catalysis, molecular recognition, self-assembly, material science, biology, and nanoscience is much less understood than that of point-, axial-, or planar-chiral molecules. To uncover the envisaged potential of helically chiral polyaromatics represented by iconic helicenes, their availability in an optically pure form through asymmetric synthesis is urgently needed. We provide a solution to this problem present since the birth of helicene chemistry in 1956 by developing a general synthetic methodology for the preparation of uniformly enantiopure fully aromatic [5]-, [6]-, and [7]helicenes and their functionalized derivatives. [2 + 2 + 2] Cycloisomerization of chiral triynes combined with asymmetric transformation of the first kind (ultimately controlled by the 1,3-allylic-type strain) is central to this endeavor. The point-to-helical chirality transfer utilizing a traceless chiral auxiliary features a remarkable resistance to diverse structural perturbations.

Progress in multirate digital control system design

NASA Technical Reports Server (NTRS)

Berg, Martin C.; Mason, Gregory S.

1991-01-01

A new methodology for multirate sampled-data control design based on a new generalized control law structure, two new parameter-optimization-based control law synthesis methods, and a new singular-value-based robustness analysis method are described. The control law structure can represent multirate sampled-data control laws of arbitrary structure and dynamic order, with arbitrarily prescribed sampling rates for all sensors and update rates for all processor states and actuators. The two control law synthesis methods employ numerical optimization to determine values for the control law parameters. The robustness analysis method is based on the multivariable Nyquist criterion applied to the loop transfer function for the sampling period equal to the period of repetition of the system's complete sampling/update schedule. The complete methodology is demonstrated by application to the design of a combination yaw damper and modal suppression system for a commercial aircraft.

Chemometric study of Maya Blue from the voltammetry of microparticles approach.

PubMed

Doménech, Antonio; Doménech-Carbó, María Teresa; de Agredos Pascual, María Luisa Vazquez

2007-04-01

The use of the voltammetry of microparticles at paraffin-impregnated graphite electrodes allows for the characterization of different types of Maya Blue (MB) used in wall paintings from different archaeological sites of Campeche and YucatAn (Mexico). Using voltammetric signals for electron-transfer processes involving palygorskite-associated indigo and quinone functionalities generated by scratching the graphite surface, voltammograms provide information on the composition and texture of MB samples. Application of hierarchical cluster analysis and other chemometric methods allows us to characterize samples from different archaeological sites and to distinguish between samples proceeding from different chronological periods. Comparison between microscopic, spectroscopic, and electrochemical examination of genuine MB samples and synthetic specimens indicated that the preparation procedure of the pigment evolved in time via successive steps anticipating modern synthetic procedures, namely, hybrid organic-inorganic synthesis, temperature control of chemical reactivity, and template-like synthesis.

Glycosyltransferases in the Golgi membranes of onion stem

PubMed Central

Powell, Janet T.; Brew, Keith

1974-01-01

Cell fractions consisting largely of Golgi membranes were prepared from the meristematic region of the onion. Several enzyme activities were found to be localized in these fractions: inosine diphosphatase, galactosyltransferases and glucosyltransferases. The fractions catalysed the transfer of [14C]galactose from UDP-galactose to endogenous and cell-sap acceptors, to N-acetylglucosamine and to ovalbumin. In the presence of bovine α-lactalbumin, transfer to glucose (lactose synthesis) was catalysed. [14C]Glucose was transferred from UDP-glucose to endogenous and cell-sap acceptors, to cellobiose and to fructose (sucrose synthesis). All these activities were latent, being potentiated by detergents (Triton X-100 or sodium deoxycholate). The characteristics of some of these enzyme activities are described and their biological significance is discussed. ImagesPLATE 1 PMID:4374190

Expression of Caenorhabditis elegans PCS in the AtPCS1-deficient Arabidopsis thaliana cad1-3 mutant separates the metal tolerance and non-host resistance functions of phytochelatin synthases.

PubMed

Kühnlenz, Tanja; Westphal, Lore; Schmidt, Holger; Scheel, Dierk; Clemens, Stephan

2015-11-01

Phytochelatin synthases (PCS) play key roles in plant metal tolerance. They synthesize small metal-binding peptides, phytochelatins, under conditions of metal excess. Respective mutants are strongly cadmium and arsenic hypersensitive. However, their ubiquitous presence and constitutive expression had long suggested a more general function of PCS besides metal detoxification. Indeed, phytochelatin synthase1 from Arabidopsis thaliana (AtPCS1) was later implicated in non-host resistance. The two different physiological functions may be attributable to the two distinct catalytic activities demonstrated for AtPCS1, that is the dipeptidyl transfer onto an acceptor molecule in phytochelatin synthesis, and the proteolytic deglycylation of glutathione conjugates. In order to test this hypothesis and to possibly separate the two biological roles, we expressed a phylogenetically distant PCS from Caenorhabditis elegans in an AtPCS1 mutant. We confirmed the involvement of AtPCS1 in non-host resistance by showing that plants lacking the functional gene develop a strong cell death phenotype when inoculated with the potato pathogen Phytophthora infestans. Furthermore, we found that the C. elegans gene rescues phytochelatin synthesis and cadmium tolerance, but not the defect in non-host resistance. This strongly suggests that the second enzymatic function of AtPCS1, which remains to be defined in detail, is underlying the plant immunity function. © 2015 John Wiley & Sons Ltd.

Extended Minus-Strand DNA as Template for R-U5-Mediated Second-Strand Transfer in Recombinational Rescue of Primer Binding Site-Modified Retroviral Vectors

PubMed Central

Mikkelsen, Jacob Giehm; Lund, Anders H.; Dybkær, Karen; Duch, Mogens; Pedersen, Finn Skou

1998-01-01

We have previously demonstrated recombinational rescue of primer binding site (PBS)-impaired Akv murine leukemia virus-based vectors involving initial priming on endogenous viral sequences and template switching during cDNA synthesis to obtain PBS complementarity in second-strand transfer of reverse transcription (Mikkelsen et al., J. Virol. 70:1439–1447, 1996). By use of the same forced recombination system, we have now found recombinant proviruses of different structures, suggesting that PBS knockout vectors may be rescued through initial priming on endogenous virus RNA, read-through of the mutated PBS during minus-strand synthesis, and subsequent second-strand transfer mediated by the R-U5 complementarity of the plus strand and the extended minus-strand DNA acceptor template. Mechanisms for R-U5-mediated second-strand transfer and its possible role in retrovirus replication and evolution are discussed. PMID:9499117

Origins of tmRNA: the missing link in the birth of protein synthesis?

PubMed

Macé, Kevin; Gillet, Reynald

2016-09-30

The RNA world hypothesis refers to the early period on earth in which RNA was central in assuring both genetic continuity and catalysis. The end of this era coincided with the development of the genetic code and protein synthesis, symbolized by the apparition of the first non-random messenger RNA (mRNA). Modern transfer-messenger RNA (tmRNA) is a unique hybrid molecule which has the properties of both mRNA and transfer RNA (tRNA). It acts as a key molecule during trans-translation, a major quality control pathway of modern bacterial protein synthesis. tmRNA shares many common characteristics with ancestral RNA. Here, we present a model in which proto-tmRNAs were the first molecules on earth to support non-random protein synthesis, explaining the emergence of early genetic code. In this way, proto-tmRNA could be the missing link between the first mRNA and tRNA molecules and modern ribosome-mediated protein synthesis. © The Author(s) 2016. Published by Oxford University Press on behalf of Nucleic Acids Research.

mTOR-dependent synthesis of Bcl-3 controls the retraction of fibrin clots by activated human platelets

PubMed Central

Weyrich, Andrew S.; Denis, Melvin M.; Schwertz, Hansjorg; Tolley, Neal D.; Foulks, Jason; Spencer, Eliott; Kraiss, Larry W.; Albertine, Kurt H.; McIntyre, Thomas M.

2007-01-01

New activities of human platelets continue to emerge. One unexpected response is new synthesis of proteins from previously transcribed RNAs in response to activating signals. We previously reported that activated human platelets synthesize B-cell lymphoma-3 (Bcl-3) under translational control by mammalian target of rapamycin (mTOR). Characterization of the ontogeny and distribution of the mTOR signaling pathway in CD34+ stem cell–derived megakaryocytes now demonstrates that they transfer this regulatory system to developing proplatelets. We also found that Bcl-3 is required for condensation of fibrin by activated platelets, demonstrating functional significance for mTOR-regulated synthesis of the protein. Inhibition of mTOR by rapamycin blocks clot retraction by human platelets. Platelets from wild-type mice synthesize Bcl-3 in response to activation, as do human platelets, and platelets from mice with targeted deletion of Bcl-3 have defective retraction of fibrin in platelet-fibrin clots mimicking treatment of human platelets with rapamycin. In contrast, overexpression of Bcl-3 in a surrogate cell line enhanced clot retraction. These studies identify new features of post-transcriptional gene regulation and signal-dependant protein synthesis in activated platelets that may contribute to thrombus and wound remodeling and suggest that posttranscriptional pathways are targets for molecular intervention in thrombotic disorders. PMID:17110454

Mechanism of energy conversion and transfer in bioluminescence. Final report. [Sea pansy Renilla reniformis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cormier, M.J.

1979-01-01

Bioluminescence in the sea pansy, Renilla reniformis, a marine anthozoan coelenterate, is a complex process involving the participation of three proteins specific to anthozoan coelenterate-type systems. These are: (1) the luciferin binding protein, (2) the enzyme luciferase, and (3) the green-fluorescent protein. Each of these have been purified and characterized and the structure of luciferin has been confirmed by synthesis. Luciferin binding protein (BP-LH/sub 2/) is a specific substrate binding protein which binds one molecule of coelenterate-type luciferin per molecule of protein and which then releases luciferin in the presence of Ca/sup + +/. Luciferase is the enzyme which catalyzesmore » oxidation (by O/sub 2/) of coelenterate-type luciferin, leading to the production of CO/sub 2/ and enzyme-bound, excited-state oxyluciferin. Oxyluciferin may then emit blue light by a direct de-excitation pathway or may transfer excitation energy to the green-fluorescent protein (GFP). GFP is a non-catalytic accessory protein which accepts excitation energy from oxyluciferin, by radiationless energy transfer, and then emits green bioluminescence. The Renilla bioluminescence system is thus the first radiationless energy transfer system the individual components of which have been purified to homogeneity, characterized, and then reassembled in vitro with restoration of the energy transfer function.« less

Valence and charge-transfer optical properties for some SinCm (m, n ≤ 12) clusters: Comparing TD-DFT, complete-basis-limit EOMCC, and benchmarks from spectroscopy

NASA Astrophysics Data System (ADS)

Lutz, Jesse J.; Duan, Xiaofeng F.; Ranasinghe, Duminda S.; Jin, Yifan; Margraf, Johannes T.; Perera, Ajith; Burggraf, Larry W.; Bartlett, Rodney J.

2018-05-01

Accurate optical characterization of the closo-Si12C12 molecule is important to guide experimental efforts toward the synthesis of nano-wires, cyclic nano-arrays, and related array structures, which are anticipated to be robust and efficient exciton materials for opto-electronic devices. Working toward calibrated methods for the description of closo-Si12C12 oligomers, various electronic structure approaches are evaluated for their ability to reproduce measured optical transitions of the SiC2, Si2Cn (n = 1-3), and Si3Cn (n = 1, 2) clusters reported earlier by Steglich and Maier [Astrophys. J. 801, 119 (2015)]. Complete-basis-limit equation-of-motion coupled-cluster (EOMCC) results are presented and a comparison is made between perturbative and renormalized non-iterative triples corrections. The effect of adding a renormalized correction for quadruples is also tested. Benchmark test sets derived from both measurement and high-level EOMCC calculations are then used to evaluate the performance of a variety of density functionals within the time-dependent density functional theory (TD-DFT) framework. The best-performing functionals are subsequently applied to predict valence TD-DFT excitation energies for the lowest-energy isomers of SinC and Sin-1C7-n (n = 4-6). TD-DFT approaches are then applied to the SinCn (n = 4-12) clusters and unique spectroscopic signatures of closo-Si12C12 are discussed. Finally, various long-range corrected density functionals, including those from the CAM-QTP family, are applied to a charge-transfer excitation in a cyclic (Si4C4)4 oligomer. Approaches for gauging the extent of charge-transfer character are also tested and EOMCC results are used to benchmark functionals and make recommendations.

Analysis of the critical step in catalytic carbodiimide transformation: proton transfer from amines, phosphines, and alkynes to guanidinates, phosphaguanidinates, and propiolamidinates with Li and Al catalysts.

PubMed

Rowley, Christopher N; Ong, Tiow-Gan; Priem, Jessica; Richeson, Darrin S; Woo, Tom K

2008-12-15

While lithium amides supported by tetramethylethylenediamine (TMEDA) are efficient catalysts in the synthesis of substituted guanidines via the guanylation of an amine with carbodiimide, as well as the guanylation of phosphines and conversion of alkynes into propiolamidines, aluminum amides are only efficient catalysts for the guanylation of amides. Density functional theory (DFT) calculations were used to explain this difference in activity. The origin of this behavior is apparent in the critical step where a proton is transferred from the substrate to a metal guanidinate. The activation energies of these steps are modest for amines, phosphines, and alkynes when a lithium catalyst was used, but are prohibitively high for the analogous reactions with phosphines and alkynes for aluminum amide catalysts. Energy decomposition analysis (EDA) indicates that these high activations energies are due to the high energetic cost of the detachment of a chelating guanidinate nitrogen from the aluminum in the proton transfer transition state. Amines are able to adopt an ideal geometry for facile proton transfer to the aluminum guanidinate and concomitant Al-N bond formation, while phosphines and alkynes are not.

Synthesis, spectroscopic, thermal and electrical conductivity studies of three charge transfer complexes formed between 1,3-di[( E)-1-(2-hydroxyphenyl)methylideneamino]-2-propanol Schiff base and different acceptors

NASA Astrophysics Data System (ADS)

Refat, Moamen S.; Ibrahim, Mohamed M.; Moussa, Mohamed A. A.

2012-01-01

Charge-transfer complexes (CTC) resulting from interactions of 1,3-di[( E)-1-(2-hydroxyphenyl) methylideneamino]-2-propanol Schiff base with some acceptors such as iodine (I2), bromine (Br2), and picric acid (PiA) have been isolated in the solid state in a chloroform solvent at room temperature. Based on elemental analysis, UV-Vis, infrared, and 1H NMR spectra, and thermogravimetric analysis (TG/DTG) of the solid CTC, [(Schiff)(I2)] (1), [(Schiff)(Br2)] complexes with a ratio of 1:1 and [(Schiff)(PiA)3] complexes with 1:3 have been prepared. In the picric acid complex, infrared and 1H NMR spectroscopic data indicate that the charge-transfer interaction is associated with a hydrogen bonding, whereas the iodine and bromine complexes were interpreted in terms of the formation of dative ion pairs [Schiff+, I{2/•-}] and [Schiff+, Br{2/•-}], respectively. Kinetic parameters were obtained for each stage of thermal degradation of the CT complexes using Coats-Redfern and Horowitz-Metzger methods. DC electrical properties as a function of temperature of these charge transfer complexes have been studied.

Charge transfer and surface defect healing within ZnO nanoparticle decorated graphene hybrid materials

NASA Astrophysics Data System (ADS)

Pham, Chuyen V.; Repp, Sergej; Thomann, Ralf; Krueger, Michael; Weber, Stefan; Erdem, Emre

2016-05-01

To harness the unique properties of graphene and ZnO nanoparticles (NPs) for novel applications, the development of graphene-ZnO nanoparticle hybrid materials has attracted great attention and is the subject of ongoing research. For this contribution, graphene-oxide-ZnO (GO-ZnO) and thiol-functionalized reduced graphene oxide-ZnO (TrGO-ZnO) nanohybrid materials were prepared by novel self-assembly processes. Based on electron paramagnetic resonance (EPR) and photoluminescence (PL) investigations on bare ZnO NPs, GO-ZnO and TrGO-ZnO hybrid materials, we found that several physical phenomena were occurring when ZnO NPs were hybridized with GO and TrGO. The electrons trapped in Zn vacancy defects (VZn-) within the core of ZnO NPs vanished by transfer to GO and TrGO in the hybrid materials, thus leading to the disappearance of the core signals in the EPR spectra of ZnO NPs. The thiol groups of TrGO and sulfur can effectively ``heal'' the oxygen vacancy (VO+) related surface defects of ZnO NPs while oxygen-containing functionalities have low healing ability at a synthesis temperature of 100 °C. Photoexcited electron transfer from the conduction band of ZnO NPs to graphene leads to photoluminescence (PL) quenching of near band gap emission (NBE) of both GO-ZnO and TrGO-ZnO. Simultaneously, electron transfer from graphene to defect states of ZnO NPs is the origin of enhanced green defect emission from GO-ZnO. This observation is consistent with the energy level diagram model of hybrid materials.To harness the unique properties of graphene and ZnO nanoparticles (NPs) for novel applications, the development of graphene-ZnO nanoparticle hybrid materials has attracted great attention and is the subject of ongoing research. For this contribution, graphene-oxide-ZnO (GO-ZnO) and thiol-functionalized reduced graphene oxide-ZnO (TrGO-ZnO) nanohybrid materials were prepared by novel self-assembly processes. Based on electron paramagnetic resonance (EPR) and photoluminescence (PL) investigations on bare ZnO NPs, GO-ZnO and TrGO-ZnO hybrid materials, we found that several physical phenomena were occurring when ZnO NPs were hybridized with GO and TrGO. The electrons trapped in Zn vacancy defects (VZn-) within the core of ZnO NPs vanished by transfer to GO and TrGO in the hybrid materials, thus leading to the disappearance of the core signals in the EPR spectra of ZnO NPs. The thiol groups of TrGO and sulfur can effectively ``heal'' the oxygen vacancy (VO+) related surface defects of ZnO NPs while oxygen-containing functionalities have low healing ability at a synthesis temperature of 100 °C. Photoexcited electron transfer from the conduction band of ZnO NPs to graphene leads to photoluminescence (PL) quenching of near band gap emission (NBE) of both GO-ZnO and TrGO-ZnO. Simultaneously, electron transfer from graphene to defect states of ZnO NPs is the origin of enhanced green defect emission from GO-ZnO. This observation is consistent with the energy level diagram model of hybrid materials. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr00393a

Speech coding, reconstruction and recognition using acoustics and electromagnetic waves

DOEpatents

Holzrichter, J.F.; Ng, L.C.

1998-03-17

The use of EM radiation in conjunction with simultaneously recorded acoustic speech information enables a complete mathematical coding of acoustic speech. The methods include the forming of a feature vector for each pitch period of voiced speech and the forming of feature vectors for each time frame of unvoiced, as well as for combined voiced and unvoiced speech. The methods include how to deconvolve the speech excitation function from the acoustic speech output to describe the transfer function each time frame. The formation of feature vectors defining all acoustic speech units over well defined time frames can be used for purposes of speech coding, speech compression, speaker identification, language-of-speech identification, speech recognition, speech synthesis, speech translation, speech telephony, and speech teaching. 35 figs.

Speech coding, reconstruction and recognition using acoustics and electromagnetic waves

DOEpatents

Holzrichter, John F.; Ng, Lawrence C.

1998-01-01

The use of EM radiation in conjunction with simultaneously recorded acoustic speech information enables a complete mathematical coding of acoustic speech. The methods include the forming of a feature vector for each pitch period of voiced speech and the forming of feature vectors for each time frame of unvoiced, as well as for combined voiced and unvoiced speech. The methods include how to deconvolve the speech excitation function from the acoustic speech output to describe the transfer function each time frame. The formation of feature vectors defining all acoustic speech units over well defined time frames can be used for purposes of speech coding, speech compression, speaker identification, language-of-speech identification, speech recognition, speech synthesis, speech translation, speech telephony, and speech teaching.

Direct synthesis of vertically aligned ZnO nanowires on FTO substrates using a CVD method and the improvement of photovoltaic performance

PubMed Central

2012-01-01

In this work, we report a direct synthesis of vertically aligned ZnO nanowires on fluorine-doped tin oxide-coated substrates using the chemical vapor deposition (CVD) method. ZnO nanowires with a length of more than 30 μm were synthesized, and dye-sensitized solar cells (DSSCs) based on the as-grown nanowires were fabricated, which showed improvement of the device performance compared to those fabricated using transferred ZnO nanowires. Dependence of the cell performance on nanowire length and annealing temperature was also examined. This synthesis method provided a straightforward, one-step CVD process to grow relatively long ZnO nanowires and avoided subsequent nanowire transfer process, which simplified DSSC fabrication and improved cell performance. PMID:22673046

Hypothesis: Co-transfer of genuine embryos and implantation-promoting compounds via artificial containers improve endometrium receptivity.

PubMed

Celik, Onder; Acet, Mustafa; Celik, Sudenaz; Sahin, Levent; Koc, Onder; Celik, Nilufer

2017-06-01

As with other organs endometrial functions are altered with the advancing age. Age related decrease in reproductive functions leads to decline in the number of oocytes retrieved and the synthesis of endometrial receptivity molecules. Despite the significant improvement in assisted reproductive technologies we do not have so many options to enhance endometrial receptivity. Due to lack of drugs having endometrium receptivity enhancement properties, oocyte donation seems to be the only solution for women with implantation failure. The euploid oocytes come from young and healthy donors may overcome age associated endometrial receptivity defect. Nevertheless, many reasons restrict us from using oocyte donation in women with implantation failure. We, therefore, hypothesized that by mimicking a young blastocyst's effect on endometrium, the transfer of genuine embryos and implantation-promoting compounds together might be the new treatment option for infertile women with recurrent implantation failure. Artificial beads, MI or GV oocytes, and empty zona can be used as a container for intrauterine replacement of implantation-promoting compounds. Copyright © 2017 Elsevier Ltd. All rights reserved.

A Structural Model for a Self-Assembled Nanotube Provides Insight into Its Exciton Dynamics

PubMed Central

2016-01-01

The design and synthesis of functional self-assembled nanostructures is frequently an empirical process fraught with critical knowledge gaps about atomic-level structure in these noncovalent systems. Here, we report a structural model for a semiconductor nanotube formed via the self-assembly of naphthalenediimide-lysine (NDI-Lys) building blocks determined using experimental 13C–13C and 13C–15N distance restraints from solid-state nuclear magnetic resonance supplemented by electron microscopy and X-ray powder diffraction data. The structural model reveals a two-dimensional-crystal-like architecture of stacked monolayer rings each containing ∼50 NDI-Lys molecules, with significant π-stacking interactions occurring both within the confines of the ring and along the long axis of the tube. Excited-state delocalization and energy transfer are simulated for the nanotube based on time-dependent density functional theory and an incoherent hopping model. Remarkably, these calculations reveal efficient energy migration from the excitonic bright state, which is in agreement with the rapid energy transfer within NDI-Lys nanotubes observed previously using fluorescence spectroscopy. PMID:26120375

Synthesis of feedback systems with large plant ignorance for prescribed time domain tolerances

NASA Technical Reports Server (NTRS)

Horowitz, I. M.; Sidi, M.

1971-01-01

There is given a minimum-phase plant transfer function, with prescribed bounds on its parameter values. The plant is imbedded in a two-degree-of freedom feedback system, which is to be designed such that the system time response to a deterministic input lies within specified boundaries. Subject to the above, the design should be such as to minimize the effect of sensor noise at the input to the plant. This report presents a design procedure for this purpose, based on frequency response concepts. The time-domain tolerances are translated into equivalent frequency response tolerances. The latter lead to bounds on the loop transmission function in the form of continuous curves on the Nichols chart. The properties of the loop transmission function which satisfy these bounds with minimum effect of sensor noise, are derived.

Photon up-conversion production in Tb{sup 3+}–Yb{sup 3+} co-doped CaF{sub 2} phosphors prepared by combustion synthesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rakov, Nikifor, E-mail: nikifor.gomez@univasf.edu.br; Guimarães, Renato B.; Maciel, Glauco S., E-mail: glauco@if.uff.br

2016-02-15

Graphical abstract: Up-conversion luminescence from Tb{sup 3+} obtained by energy transfer from Yb{sup 3+} pairs in CaF{sub 2} powder prepared by combustion synthesis. - Highlights: • Calcium fluoride (CaF{sub 2}) powders were prepared by combustion synthesis. • Rare-earth ions doped in this material were found in interstitial sites. • Cooperative up-conversion was observed in Tb{sup 3+}:Yb{sup 3+}:CaF{sub 2} powder. • Energy transfer between Tb{sup 3+} and pairs of Yb{sup 3+} was analyzed using rate equations. - Abstract: Calcium fluoride (CaF{sub 2}) crystalline powders were successfully prepared by the combustion synthesis method. The powder material containing luminescent rare-earth ions, more specificallymore » terbium (Tb{sup 3+}) and ytterbium (Yb{sup 3+}), was studied by X-ray diffraction, scanning electronic microscopy and optical spectroscopy. These ions are allocated in charge compensated interstitial positions of tetragonal (C{sub 4v}) and trigonal (C{sub 3v}) symmetry sites of the cubic (O{sub h}) CaF{sub 2} lattice. Up-conversion (UC) luminescence in Tb{sup 3+} was achieved using a low power diode laser operating at 975 nm. Tb{sup 3+} is insensitive to near-infrared radiation but UC can be achieved via energy transfer from pairs of Yb{sup 3+} ions to Tb{sup 3+} ions. The UC luminescence dynamics of Tb{sup 3+} was used to study the energy transfer mechanism.« less

Formation of stable and functional HIV-1 nucleoprotein complexes in vitro.

PubMed

Tanchou, V; Gabus, C; Rogemond, V; Darlix, J L

1995-10-06

HIV genomic RNA resides within the nucleocapsid, in the interior of the virus, which serves to protect the RNA against nuclease degradation and to promote its reverse transcription. To investigate the role of nucleocapsid protein (NCp7) in the stability and replication of genomic RNA within the nucleocapsid, we used NCp7, reverse transcriptase (RT) and RNAs representing the 5' and 3' regions of the genome to reconstitute functional HIV-1 nucleocapsids. The nucleoprotein complexes generated in vitro were found to be stable, which, according to biochemical and genetic data, probably results from the tight binding of NCp7 molecules to the RNA and strong NCp7/NCp7 interactions. The nucleoprotein complexes efficiently protected viral RNA against RNase degradation and, at the same time, promoted viral DNA synthesis by RT. DNA strand transfer from the 5' to the 3' RNA template was very efficient in nucleoprotein complexes formed in the presence of both RNAs, but not when the RNAs were in separate complexes. These results indicate that the in vitro reconstituted HIV-1 nucleoprotein complexes function like virion nucleocapsids and thus provide a way to study at the molecular level this viral substructure and the synthesis of proviral DNA, and to search for new anti-HIV agents.

Alcohols as alkylating agents in heteroarene C-H functionalization

NASA Astrophysics Data System (ADS)

Jin, Jian; MacMillan, David W. C.

2015-09-01

Redox processes and radical intermediates are found in many biochemical processes, including deoxyribonucleotide synthesis and oxidative DNA damage. One of the core principles underlying DNA biosynthesis is the radical-mediated elimination of H2O to deoxygenate ribonucleotides, an example of `spin-centre shift', during which an alcohol C-O bond is cleaved, resulting in a carbon-centred radical intermediate. Although spin-centre shift is a well-understood biochemical process, it is underused by the synthetic organic chemistry community. We wondered whether it would be possible to take advantage of this naturally occurring process to accomplish mild, non-traditional alkylation reactions using alcohols as radical precursors. Because conventional radical-based alkylation methods require the use of stoichiometric oxidants, increased temperatures or peroxides, a mild protocol using simple and abundant alkylating agents would have considerable use in the synthesis of diversely functionalized pharmacophores. Here we describe the development of a dual catalytic alkylation of heteroarenes, using alcohols as mild alkylating reagents. This method represents the first, to our knowledge, broadly applicable use of unactivated alcohols as latent alkylating reagents, achieved via the successful merger of photoredox and hydrogen atom transfer catalysis. The value of this multi-catalytic protocol has been demonstrated through the late-stage functionalization of the medicinal agents, fasudil and milrinone.

Alcohols as alkylating agents in heteroarene C-H functionalization.

PubMed

Jin, Jian; MacMillan, David W C

2015-09-03

Redox processes and radical intermediates are found in many biochemical processes, including deoxyribonucleotide synthesis and oxidative DNA damage. One of the core principles underlying DNA biosynthesis is the radical-mediated elimination of H2O to deoxygenate ribonucleotides, an example of 'spin-centre shift', during which an alcohol C-O bond is cleaved, resulting in a carbon-centred radical intermediate. Although spin-centre shift is a well-understood biochemical process, it is underused by the synthetic organic chemistry community. We wondered whether it would be possible to take advantage of this naturally occurring process to accomplish mild, non-traditional alkylation reactions using alcohols as radical precursors. Because conventional radical-based alkylation methods require the use of stoichiometric oxidants, increased temperatures or peroxides, a mild protocol using simple and abundant alkylating agents would have considerable use in the synthesis of diversely functionalized pharmacophores. Here we describe the development of a dual catalytic alkylation of heteroarenes, using alcohols as mild alkylating reagents. This method represents the first, to our knowledge, broadly applicable use of unactivated alcohols as latent alkylating reagents, achieved via the successful merger of photoredox and hydrogen atom transfer catalysis. The value of this multi-catalytic protocol has been demonstrated through the late-stage functionalization of the medicinal agents, fasudil and milrinone.

Synthesis of Single-walled Carbon Nanotubes Coated with Thiol-reactive Gel via Emulsion Polymerization.

PubMed

Nagai, Yukiko; Tsutsumi, Yusuke; Nakashima, Naotoshi; Fujigaya, Tsuyohiko

2018-06-15

Single-walled carbon nanotubes (SWNTs) have unique near-infrared absorption and photoemission properties that are attractive for in vivo biological applications such as photothermal cancer treatment and bioimaging. Therefore, a smart functionalization strategy for SWNTs to create biocompatible surfaces and introduce various ligands to target active cancer cells without losing the unique optical properties of the SWNTs is strongly desired. This paper reports the de-sign and synthesis of a SWNT/gel hybrid containing maleimide groups, which react with various thiol compounds through Michael addition reactions. In this hybrid, the method called carbon nanotube micelle polymerization was used to non-covalently modify the surface of SWNTs with a cross-linked polymer gel layer. This method can form an extremely stable gel layer on SWNTs; such stability is essential for in vivo biological applications. The monomer used to form the gel layer contained a maleimide group, which was protected with furan in endo-form. The resulting hybrid was treated in water to induce deprotection via retro Diels-Alder reaction and then functionalized with thiol com-pounds through Michael addition. The functionalization of the hybrid was explored using a thiol-containing fluores-cent dye as a model thiol and the formation of the SWNT-dye conjugate was confirmed by energy transfer from the dye to SWNTs. Our strategy offers a promising SWNT-based platform for biological functionalization for cancer targeting, imaging, and treatment.

Synthesis of Novel μ-Star Copolymers with Poly(N-Octyl Benzamide) and Poly(ε-Caprolactone) Miktoarms through Chain-Growth Condensation Polymerization, Styrenics-Assisted Atom Transfer Radical Coupling, and Ring-Opening Polymerization.

PubMed

Huang, Chih-Feng; Aimi, Junko; Lai, Kuan-Yu

2017-02-01

Star copolymers are known to phase separate on the nanoscale, providing useful self-assembled morphologies. In this study, the authors investigate synthesis and assembly behavior of miktoarm star (μ-star) copolymers. The authors employ a new strategy for the synthesis of unprecedented μ-star copolymers presenting poly(N-octyl benzamide) (PBA) and poly(ε-caprolactone) (PCL) arms: a combination of chain-growth condensation polymerization, styrenics-assisted atom transfer radical coupling, and ring-opening polymerization. Gel permeation chromatography, mass-analyzed laser desorption/ionization mass spectrometry, and 1 H NMR spectroscopy reveal the successful synthesis of a well-defined (PBA 11 ) 2 -(PCL 15 ) 4 μ-star copolymer (M n ,NMR ≈ 12 620; Đ = 1.22). Preliminary examination of the PBA 2 PCL 4 μ-star copolymer reveals assembled nanofibers having a uniform diameter of ≈20 nm. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Investigation of Optimal Discrete Approximations for Real Time Flight Simulations

NASA Technical Reports Server (NTRS)

Parrish, E. A.; Mcvey, E. S.; Cook, G.; Henderson, K. C.

1976-01-01

The results are presented of an investigation of discrete approximations for real time flight simulation. Major topics discussed include: (1) consideration of the particular problem of approximation of continuous autopilots by digital autopilots; (2) use of Bode plots and synthesis of transfer functions by asymptotic fits in a warped frequency domain; (3) an investigation of the various substitution formulas, including the effects of nonlinearities; (4) use of pade approximation to the solution of the matrix exponential arising from the discrete state equations; and (5) an analytical integration of the state equation using interpolated input.

Synthesis of collagenase-sensitive polyureas for ligament tissue engineering.

PubMed

Benhardt, Hugh; Sears, Nick; Touchet, Tyler; Cosgriff-Hernandez, Elizabeth

2011-08-11

Recently, poly(ester urethanes) were investigated for use as ligament grafts due to their exceptional mechanical properties and highly tunable structure; however, these grafts are susceptible to hydrolytic degradation that occurs independent of tissue regeneration. To address this limitation, polyureas containing collagen-derived peptides were synthesized which enable cellular release of proteases to dictate degradation rate. It is hypothesized that this cell-responsive design will facilitate load transfer from the biodegradable scaffold to neotissue at a rate that promotes proper tissue orientation and function while maintaining construct integrity. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct role for the RNA polymerase domain of T7 primase in primer delivery

PubMed Central

Zhu, Bin; Lee, Seung-Joo; Richardson, Charles C.

2010-01-01

Gene 4 protein (gp4) encoded by bacteriophage T7 contains a C-terminal helicase and an N-terminal primase domain. After synthesis of tetraribonucleotides, gp4 must transfer them to the polymerase for use as primers to initiate DNA synthesis. In vivo gp4 exists in two molecular weight forms, a 56-kDa form and the full-length 63-kDa form. The 56-kDa gp4 lacks the N-terminal Cys4 zinc-binding motif important in the recognition of primase sites in DNA. The 56-kDa gp4 is defective in primer synthesis but delivers a wider range of primers to initiate DNA synthesis compared to the 63-kDa gp4. Suppressors exist that enable the 56-kDa gp4 to support the growth of T7 phage lacking gene 4 (T7Δ4). We have identified 56-kDa DNA primases defective in primer delivery by screening for their ability to support growth of T7Δ4 phage in the presence of this suppressor. Trp69 is critical for primer delivery. Replacement of Trp69 with lysine in either the 56- or 63-kDa gp4 results in defective primer delivery with other functions unaffected. DNA primase harboring lysine at position 69 fails to stabilize the primer on DNA. Thus, a primase subdomain not directly involved in primer synthesis is involved in primer delivery. The stabilization of the primer by DNA primase is necessary for DNA polymerase to initiate synthesis. PMID:20439755

Evolution of Saxitoxin Synthesis in Cyanobacteria and Dinoflagellates

PubMed Central

Hackett, Jeremiah D.; Wisecaver, Jennifer H.; Brosnahan, Michael L.; Kulis, David M.; Anderson, Donald M.; Bhattacharya, Debashish; Plumley, F. Gerald; Erdner, Deana L.

2013-01-01

Dinoflagellates produce a variety of toxic secondary metabolites that have a significant impact on marine ecosystems and fisheries. Saxitoxin (STX), the cause of paralytic shellfish poisoning, is produced by three marine dinoflagellate genera and is also made by some freshwater cyanobacteria. Genes involved in STX synthesis have been identified in cyanobacteria but are yet to be reported in the massive genomes of dinoflagellates. We have assembled comprehensive transcriptome data sets for several STX-producing dinoflagellates and a related non-toxic species and have identified 265 putative homologs of 13 cyanobacterial STX synthesis genes, including all of the genes directly involved in toxin synthesis. Putative homologs of four proteins group closely in phylogenies with cyanobacteria and are likely the functional homologs of sxtA, sxtG, and sxtB in dinoflagellates. However, the phylogenies do not support the transfer of these genes directly between toxic cyanobacteria and dinoflagellates. SxtA is split into two proteins in the dinoflagellates corresponding to the N-terminal portion containing the methyltransferase and acyl carrier protein domains and a C-terminal portion with the aminotransferase domain. Homologs of sxtB and N-terminal sxtA are present in non-toxic strains, suggesting their functions may not be limited to saxitoxin production. Only homologs of the C-terminus of sxtA and sxtG were found exclusively in toxic strains. A more thorough survey of STX+ dinoflagellates will be needed to determine if these two genes may be specific to SXT production in dinoflagellates. The A. tamarense transcriptome does not contain homologs for the remaining STX genes. Nevertheless, we identified candidate genes with similar predicted biochemical activities that account for the missing functions. These results suggest that the STX synthesis pathway was likely assembled independently in the distantly related cyanobacteria and dinoflagellates, although using some evolutionarily related proteins. The biological role of STX is not well understood in either cyanobacteria or dinoflagellates. However, STX production in these two ecologically distinct groups of organisms suggests that this toxin confers a benefit to producers that we do not yet fully understand. PMID:22628533

Evolution of saxitoxin synthesis in cyanobacteria and dinoflagellates.

PubMed

Hackett, Jeremiah D; Wisecaver, Jennifer H; Brosnahan, Michael L; Kulis, David M; Anderson, Donald M; Bhattacharya, Debashish; Plumley, F Gerald; Erdner, Deana L

2013-01-01

Dinoflagellates produce a variety of toxic secondary metabolites that have a significant impact on marine ecosystems and fisheries. Saxitoxin (STX), the cause of paralytic shellfish poisoning, is produced by three marine dinoflagellate genera and is also made by some freshwater cyanobacteria. Genes involved in STX synthesis have been identified in cyanobacteria but are yet to be reported in the massive genomes of dinoflagellates. We have assembled comprehensive transcriptome data sets for several STX-producing dinoflagellates and a related non-toxic species and have identified 265 putative homologs of 13 cyanobacterial STX synthesis genes, including all of the genes directly involved in toxin synthesis. Putative homologs of four proteins group closely in phylogenies with cyanobacteria and are likely the functional homologs of sxtA, sxtG, and sxtB in dinoflagellates. However, the phylogenies do not support the transfer of these genes directly between toxic cyanobacteria and dinoflagellates. SxtA is split into two proteins in the dinoflagellates corresponding to the N-terminal portion containing the methyltransferase and acyl carrier protein domains and a C-terminal portion with the aminotransferase domain. Homologs of sxtB and N-terminal sxtA are present in non-toxic strains, suggesting their functions may not be limited to saxitoxin production. Only homologs of the C-terminus of sxtA and sxtG were found exclusively in toxic strains. A more thorough survey of STX+ dinoflagellates will be needed to determine if these two genes may be specific to SXT production in dinoflagellates. The A. tamarense transcriptome does not contain homologs for the remaining STX genes. Nevertheless, we identified candidate genes with similar predicted biochemical activities that account for the missing functions. These results suggest that the STX synthesis pathway was likely assembled independently in the distantly related cyanobacteria and dinoflagellates, although using some evolutionarily related proteins. The biological role of STX is not well understood in either cyanobacteria or dinoflagellates. However, STX production in these two ecologically distinct groups of organisms suggests that this toxin confers a benefit to producers that we do not yet fully understand.

A One-Step Route to CO2 -Based Block Copolymers by Simultaneous ROCOP of CO2 /Epoxides and RAFT Polymerization of Vinyl Monomers.

PubMed

Wang, Yong; Zhao, Yajun; Ye, Yunsheng; Peng, Haiyan; Zhou, Xingping; Xie, Xiaolin; Wang, Xianhong; Wang, Fosong

2018-03-26

The one-step synthesis of well-defined CO 2 -based diblock copolymers was achieved by simultaneous ring-opening copolymerization (ROCOP) of CO 2 /epoxides and RAFT polymerization of vinyl monomers using a trithiocarbonate compound bearing a carboxylic group (TTC-COOH) as the bifunctional chain transfer agent (CTA). The double chain-transfer effect allows for independent and precise control over the molecular weight of the two blocks and ensures narrow polydispersities of the resultant block copolymers (1.09-1.14). Notably, an unusual axial group exchange reaction between the aluminum porphyrin catalyst and TTC-COOH impedes the formation of homopolycarbonates. By taking advantage of the RAFT technique, it is able to meet the stringent demand for functionality control to well expand the application scopes of CO 2 -based polycarbonates. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrodehalogenation of alkyl iodides with base-mediated hydrogenation and catalytic transfer hydrogenation: application to the asymmetric synthesis of N-protected α-methylamines.

PubMed

Mandal, Pijus K; Birtwistle, J Sanderson; McMurray, John S

2014-09-05

We report a very mild synthesis of N-protected α-methylamines from the corresponding amino acids. Carboxyl groups of amino acids are reduced to iodomethyl groups via hydroxymethyl intermediates. Reductive deiodination to methyl groups is achieved by hydrogenation or catalytic transfer hydrogenation under alkaline conditions. Basic hydrodehalogenation is selective for the iodomethyl group over hydrogenolysis-labile protecting groups, such as benzyloxycarbonyl, benzyl ester, benzyl ether, and 9-fluorenyloxymethyl, thus allowing the conversion of virtually any protected amino acid into the corresponding N-protected α-methylamine.

Hydrodehalogenation of Alkyl Iodides with Base-Mediated Hydrogenation and Catalytic Transfer Hydrogenation: Application to the Asymmetric Synthesis of N-Protected α-Methylamines

PubMed Central

2015-01-01

We report a very mild synthesis of N-protected α-methylamines from the corresponding amino acids. Carboxyl groups of amino acids are reduced to iodomethyl groups via hydroxymethyl intermediates. Reductive deiodination to methyl groups is achieved by hydrogenation or catalytic transfer hydrogenation under alkaline conditions. Basic hydrodehalogenation is selective for the iodomethyl group over hydrogenolysis-labile protecting groups, such as benzyloxycarbonyl, benzyl ester, benzyl ether, and 9-fluorenyloxymethyl, thus allowing the conversion of virtually any protected amino acid into the corresponding N-protected α-methylamine. PMID:25116734

Synthesis of Available Research and Databases on the Migrant Education Program. Volume II: the Migrant Student Record Transfer System.

ERIC Educational Resources Information Center

Eckels, Elaine; Vorek, Robert

The Migrant Student Record Transfer System (MSRTS) is a nationwide computer-based communications network originally designed to transfer the health and educational records of migrant workers' children. This report assesses MSRTS data from September 1984 through June 1986 to determine the potential utility of such data for national studies of the…

University Knowledge/Technology Transfer and Public Decision-Making: Review, Synthesis, and Alternative Models. Rural Development Series No. 11.

ERIC Educational Resources Information Center

Sollie, Carlton R.; Howell, Frank M.

Issues and problems associated with university involvement in public sector activities and the knowledge transfer process are examined. After a brief statement of the state-of-the-art in knowledge transfer, attention is directed to one of the basic issues presented in the literature: the appropriateness and inappropriateness of university…

Extended cooperative control synthesis

NASA Technical Reports Server (NTRS)

Davidson, John B.; Schmidt, David K.

1994-01-01

This paper reports on research for extending the Cooperative Control Synthesis methodology to include a more accurate modeling of the pilot's controller dynamics. Cooperative Control Synthesis (CCS) is a methodology that addresses the problem of how to design control laws for piloted, high-order, multivariate systems and/or non-conventional dynamic configurations in the absence of flying qualities specifications. This is accomplished by emphasizing the parallel structure inherent in any pilot-controlled, augmented vehicle. The original CCS methodology is extended to include the Modified Optimal Control Model (MOCM), which is based upon the optimal control model of the human operator developed by Kleinman, Baron, and Levison in 1970. This model provides a modeling of the pilot's compensation dynamics that is more accurate than the simplified pilot dynamic representation currently in the CCS methodology. Inclusion of the MOCM into the CCS also enables the modeling of pilot-observation perception thresholds and pilot-observation attention allocation affects. This Extended Cooperative Control Synthesis (ECCS) allows for the direct calculation of pilot and system open- and closed-loop transfer functions in pole/zero form and is readily implemented in current software capable of analysis and design for dynamic systems. Example results based upon synthesizing an augmentation control law for an acceleration command system in a compensatory tracking task using the ECCS are compared with a similar synthesis performed by using the original CCS methodology. The ECCS is shown to provide augmentation control laws that yield more favorable, predicted closed-loop flying qualities and tracking performance than those synthesized using the original CCS methodology.

Vtc5, a Novel Subunit of the Vacuolar Transporter Chaperone Complex, Regulates Polyphosphate Synthesis and Phosphate Homeostasis in Yeast*

PubMed Central

Desfougères, Yann; Gerasimaitė, R̄uta; Jessen, Henning Jacob

2016-01-01

SPX domains control phosphate homeostasis in eukaryotes. Ten genes in yeast encode SPX-containing proteins, among which YDR089W is the only one of unknown function. Here, we show that YDR089W encodes a novel subunit of the vacuole transporter chaperone (VTC) complex that produces inorganic polyphosphate (polyP). The polyP synthesis transfers inorganic phosphate (Pi) from the cytosol into the acidocalcisome- and lysosome-related vacuoles of yeast, where it can be released again. It was therefore proposed for buffer changes in cytosolic Pi concentration (Thomas, M. R., and O'Shea, E. K. (2005) Proc. Natl. Acad. Sci. U.S.A. 102, 9565–9570). Vtc5 physically interacts with the VTC complex and accelerates the accumulation of polyP synthesized by it. Deletion of VTC5 reduces polyP accumulation in vivo and in vitro. Its overexpression hyperactivates polyP production and triggers the phosphate starvation response via the PHO pathway. Because this Vtc5-induced starvation response can be reverted by shutting down polyP synthesis genetically or pharmacologically, we propose that polyP synthesis rather than Vtc5 itself is a regulator of the PHO pathway. Our observations suggest that polyP synthesis not only serves to establish a buffer for transient drops in cytosolic Pi levels but that it can actively decrease or increase the steady state of cytosolic Pi. PMID:27587415

Optical aperture synthesis: limitations and interest for the earth observation

NASA Astrophysics Data System (ADS)

Brouard, Laurent; Safa, Frederic; Crombez, Vincent; Laubier, David

2017-11-01

For very large telescope diameters, typically above 4 meters, monolithic telescopes can hardly be envisaged for space applications. Optical aperture synthesis can be envisaged in the future for improving the image resolution from high altitude orbits by co-phasing several individual telescopes of smaller size and reconstituting an aperture of large surface. The telescopes can be deployed on a single spacecraft or distributed on several spacecrafts in free flying formation. Several future projects are based on optical aperture synthesis for science or earth observation. This paper specifically discusses the limitations and interest of aperture synthesis technique for Earth observation from high altitude orbits, in particular geostationary orbit. Classical Fizeau and Michelson configurations are recalled, and system design aspects are investigated: synthesis of the Modulation Transfer Function (MTF), integration time and imaging procedure are first discussed then co-phasing strategies and instrument metrology are developed. The discussion is supported by specific designs made at EADS Astrium. As example, a telescope design is presented with a surface of only 6.6 m2 for the primary mirror for an external diameter of 10.6 m allowing a theoretical resolution of 1.2 m from geostationary orbit with a surface lower than 10% of the overall surface. The impact is that the integration time is increasing leading to stringent satellite attitude requirements. Image simulation results are presented. The practical implementation of the concept is evaluated in terms of system impacts in particular spacecraft attitude control, spacecraft operations and imaging capability limitations.

Lipid transfer proteins in the assembly of apoB-containing lipoproteins.

PubMed

Sirwi, Alaa; Hussain, M Mahmood

2018-04-12

A better understanding of intracellular lipoprotein assembly may help identify proteins with important roles in lipid disorders. ApoB-containing lipoproteins are macromolecular lipid and protein micelles that act as specialized transport vehicles for hydrophobic lipids. They are assembled predominantly in enterocytes and hepatocytes to transport dietary and endogenous fat, respectively, to different tissues. Assembly occurs in the endoplasmic reticulum and is dependent on lipid re-synthesis in the endoplasmic reticulum and on a chaperone, namely microsomal triglyceride transfer protein. Precursors for lipid synthesis are obtained from extracellular sources and from cytoplasmic lipid droplets. Microsomal triglyceride transfer protein is the major and essential lipid transfer protein that transfers phospholipids and triacylglycerols to nascent apoB for the assembly of lipoproteins. Assembly is aided by cell death-inducing DFF45-like effector B and by phospholipid transfer protein, which may facilitate additional deposition of triacylglycerols and phospholipids, respectively, to apoB. Here, we summarize the current understanding of the different steps in the assembly of apoB-containing lipoproteins and discuss the role of lipid transfer proteins in these steps to help identify new clinical targets for lipid-associated disorders, such as heart disease. Published under license by The American Society for Biochemistry and Molecular Biology, Inc.

Method for forming synthesis gas using a plasma-catalyzed fuel reformer

DOEpatents

Hartvigsen, Joseph J; Elangovan, S; Czernichowski, Piotr; Hollist, Michele

2015-04-28

A method of forming a synthesis gas utilizing a reformer is disclosed. The method utilizes a reformer that includes a plasma zone to receive a pre-heated mixture of reactants and ionize the reactants by applying an electrical potential thereto. A first thermally conductive surface surrounds the plasma zone and is configured to transfer heat from an external heat source into the plasma zone. The reformer further includes a reaction zone to chemically transform the ionized reactants into synthesis gas comprising hydrogen and carbon monoxide. A second thermally conductive surface surrounds the reaction zone and is configured to transfer heat from the external heat source into the reaction zone. The first thermally conductive surface and second thermally conductive surface are both directly exposed to the external heat source. A corresponding apparatus and system are also disclosed herein.

Oxidation levels differentially impact melanocytes: low versus high concentration of hydrogen peroxide promotes melanin synthesis and melanosome transfer.

PubMed

Tang, Luyan; Li, Jian; Lin, Xiao; Wu, Wenyu; Kang, Kefei; Fu, Wenwen

2012-01-01

UVB light can generate potentially harmful hydrogen peroxide (H(2)O(2)) in vivo, but it can also promote the beneficial proliferation and migration of melanocytes. The successful use of UVB monotherapy for treatment of vitiligo suggests that H(2)O(2) may have a biphasic effect on melanin synthesis and melanosome transfer. To study the beneficial role of H(2)O(2) on melanogenesis and melanosome transport in living melanocytes and keratinocytes. A co-culture system model was constructed using the primary human melanocytes and keratinocytes. The MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assay was used to determine cell proliferation, NaOH was used to determine the melanin content, and real-time PCR was used to determine tyrosinase expression. Western blot was used to determine Rab-27A and protease-activated receptor 2 (PAR-2) expression. This study demonstrated that tyrosinase was activated by low concentrations of H(2)O(2) (≤0.3 mM); however, this activity was downregulated by high concentrations of H(2)O(2) (>0.3 mM). Activation of high levels of melanin synthesis was induced when cells were treated with low concentrations of H(2)O(2) (0.3 mM). Further observation using an in vitro co-culture system of fluorescein (carboxyfluorescein diacetate succinimidyl ester, CFDA-SE)-labeled melanocytes and keratinocytes indicated that melanosome transfer occurred in normal human epidermal melanocytes. Fluorescence microscopy revealed increased melanosome transfer into keratinocytes treated with 0.3 mM H(2)O(2) in the co-culture compared to the control. Examination of melanosomes in the keratinocytes by flow cytometry confirmed these results. Furthermore, treatment with H(2)O(2) (0.3 mM) upregulated the expression of Rab-27A and PAR-2, significant proteins involved in melanosome transfer, according to Western blot. These results confirmed that low concentration levels of H(2)O(2) play a major role in the regulation of human pigmentation by increasing melanin synthesis and melanosome transfer. Copyright © 2012 S. Karger AG, Basel.

Thiophene-based covalent organic frameworks

PubMed Central

Bertrand, Guillaume H. V.; Michaelis, Vladimir K.; Ong, Ta-Chung; Griffin, Robert G.; Dincă, Mircea

2013-01-01

We report the synthesis and characterization of covalent organic frameworks (COFs) incorporating thiophene-based building blocks. We show that these are amenable to reticular synthesis, and that bent ditopic monomers, such as 2,5-thiophenediboronic acid, are defect-prone building blocks that are susceptible to synthetic variations during COF synthesis. The synthesis and characterization of an unusual charge transfer complex between thieno[3,2-b]thiophene-2,5-diboronic acid and tetracyanoquinodimethane enabled by the unique COF architecture is also presented. Together, these results delineate important synthetic advances toward the implementation of COFs in electronic devices. PMID:23479656

Pollination in Nicotiana alata stimulates synthesis and transfer to the stigmatic surface of NaStEP, a vacuolar Kunitz proteinase inhibitor homologue.

PubMed

Busot, Grethel Yanet; McClure, Bruce; Ibarra-Sánchez, Claudia Patricia; Jiménez-Durán, Karina; Vázquez-Santana, Sonia; Cruz-García, Felipe

2008-01-01

After landing on a wet stigma, pollen grains hydrate and germination generally occurs. However, there is no certainty of the pollen tube growth through the style to reach the ovary. The pistil is a gatekeeper that evolved in many species to recognize and reject the self-pollen, avoiding endogamy and encouraging cross-pollination. However, recognition is a complex process, and specific factors are needed. Here the isolation and characterization of a stigma-specific protein from N. alata, NaStEP (N. alata Stigma Expressed Protein), that is homologous to Kunitz-type proteinase inhibitors, are reported. Activity gel assays showed that NaStEP is not a functional serine proteinase inhibitor. Immunohistochemical and protein blot analyses revealed that NaStEP is detectable in stigmas of self-incompatible (SI) species N. alata, N. forgetiana, and N. bonariensis, but not in self-compatible (SC) species N. tabacum, N. plumbaginifolia, N. benthamiana, N. longiflora, and N. glauca. NaStEP contains the vacuolar targeting sequence NPIVL, and immunocytochemistry experiments showed vacuolar localization in unpollinated stigmas. After self-pollination or pollination with pollen from the SC species N. tabacum or N. plumbaginifolia, NaStEP was also found in the stigmatic exudate. The synthesis and presence in the stigmatic exudate of this protein was strongly induced in N. alata following incompatible pollination with N. tabacum pollen. The transfer of NaStEP to the stigmatic exudate was accompanied by perforation of the stigmatic cell wall, which appeared to release the vacuolar contents to the apoplastic space. The increase in NaStEP synthesis after pollination and its presence in the stigmatic exudates suggest that this protein may play a role in the early pollen-stigma interactions that regulate pollen tube growth in Nicotiana.

Transfer of the cytochrome P450-dependent dhurrin pathway from Sorghum bicolor into Nicotiana tabacum chloroplasts for light-driven synthesis.

PubMed

Gnanasekaran, Thiyagarajan; Karcher, Daniel; Nielsen, Agnieszka Zygadlo; Martens, Helle Juel; Ruf, Stephanie; Kroop, Xenia; Olsen, Carl Erik; Motawie, Mohammed Saddik; Pribil, Mathias; Møller, Birger Lindberg; Bock, Ralph; Jensen, Poul Erik

2016-04-01

Plant chloroplasts are light-driven cell factories that have great potential to act as a chassis for metabolic engineering applications. Using plant chloroplasts, we demonstrate how photosynthetic reducing power can drive a metabolic pathway to synthesise a bio-active natural product. For this purpose, we stably engineered the dhurrin pathway from Sorghum bicolor into the chloroplasts of Nicotiana tabacum (tobacco). Dhurrin is a cyanogenic glucoside and its synthesis from the amino acid tyrosine is catalysed by two membrane-bound cytochrome P450 enzymes (CYP79A1 and CYP71E1) and a soluble glucosyltransferase (UGT85B1), and is dependent on electron transfer from a P450 oxidoreductase. The entire pathway was introduced into the chloroplast by integrating CYP79A1, CYP71E1, and UGT85B1 into a neutral site of the N. tabacum chloroplast genome. The two P450s and the UGT85B1 were functional when expressed in the chloroplasts and converted endogenous tyrosine into dhurrin using electrons derived directly from the photosynthetic electron transport chain, without the need for the presence of an NADPH-dependent P450 oxidoreductase. The dhurrin produced in the engineered plants amounted to 0.1-0.2% of leaf dry weight compared to 6% in sorghum. The results obtained pave the way for plant P450s involved in the synthesis of economically important compounds to be engineered into the thylakoid membrane of chloroplasts, and demonstrate that their full catalytic cycle can be driven directly by photosynthesis-derived electrons. © The Author 2016. Published by Oxford University Press on behalf of the Society for Experimental Biology.

Coupling between d-3-phosphoglycerate dehydrogenase and d-2-hydroxyglutarate dehydrogenase drives bacterial l-serine synthesis

PubMed Central

Zhang, Wen; Zhang, Manman; Gao, Chao; Zhang, Yipeng; Ge, Yongsheng; Guo, Shiting; Guo, Xiaoting; Zhou, Zikang; Liu, Qiuyuan; Zhang, Yingxin; Ma, Cuiqing; Tao, Fei; Xu, Ping

2017-01-01

l-Serine biosynthesis, a crucial metabolic process in most domains of life, is initiated by d-3-phosphoglycerate (d-3-PG) dehydrogenation, a thermodynamically unfavorable reaction catalyzed by d-3-PG dehydrogenase (SerA). d-2-Hydroxyglutarate (d-2-HG) is traditionally viewed as an abnormal metabolite associated with cancer and neurometabolic disorders. Here, we reveal that bacterial anabolism and catabolism of d-2-HG are involved in l-serine biosynthesis in Pseudomonas stutzeri A1501 and Pseudomonas aeruginosa PAO1. SerA catalyzes the stereospecific reduction of 2-ketoglutarate (2-KG) to d-2-HG, responsible for the major production of d-2-HG in vivo. SerA combines the energetically favorable reaction of d-2-HG production to overcome the thermodynamic barrier of d-3-PG dehydrogenation. We identified a bacterial d-2-HG dehydrogenase (D2HGDH), a flavin adenine dinucleotide (FAD)-dependent enzyme, that converts d-2-HG back to 2-KG. Electron transfer flavoprotein (ETF) and ETF-ubiquinone oxidoreductase (ETFQO) are also essential in d-2-HG metabolism through their capacity to transfer electrons from D2HGDH. Furthermore, while the mutant with D2HGDH deletion displayed decreased growth, the defect was rescued by adding l-serine, suggesting that the D2HGDH is functionally tied to l-serine synthesis. Substantial flux flows through d-2-HG, being produced by SerA and removed by D2HGDH, ETF, and ETFQO, maintaining d-2-HG homeostasis. Overall, our results uncover that d-2-HG–mediated coupling between SerA and D2HGDH drives bacterial l-serine synthesis. PMID:28827360

The mechanism of the formation of the hemiaminal and Schiff base from the benzaldehyde and triazole studied by means of the topological analysis of electron localisation function and catastrophe theory

NASA Astrophysics Data System (ADS)

Berski, Slawomir; Zbigniew Ciunik, Leszek

2015-04-01

The mechanisms of reaction of benzaldehyde (ald) with 4-amine-4H-1,2,4-triazole (4at), leading to Schiff base (Sch) and water, were investigated using topological analysis of the electron localisation function and catastrophe theory. Two reactions (synthesis of hemiaminal and synthesis of Schiff base) are represented by one catastrophe sequence: ald+4at: 1-14-[FF†F†FFTS1FF†F†FF†F†CF†]-2-9-[C†FFTS3F†F†FFF]-0:Sch+H2O with only fold (F) and cusp (C) catastrophes. The first reaction, in which a molecule of the hemiaminal is formed, consists of 14 steps separated by 13 catastrophes. The mechanism is non-concerted. The covalent bond C-N is formed after the formation of the O-H bond is terminated. The Schiff base formation through the water molecule elimination in the second reaction requires nine steps with eight catastrophes. The mechanism is non-concerted because first the C-O bond is broken and then the proton transfer occurs that results in the O-H bond creation.

On-surface synthesis on a bulk insulator surface

NASA Astrophysics Data System (ADS)

Richter, Antje; Floris, Andrea; Bechstein, Ralf; Kantorovich, Lev; Kühnle, Angelika

2018-04-01

On-surface synthesis has rapidly emerged as a most promising approach to prepare functional molecular structures directly on a support surface. Compared to solution synthesis, performing chemical reactions on a surface offers several exciting new options: due to the absence of a solvent, reactions can be envisioned that are otherwise not feasible due to the insolubility of the reaction product. Perhaps even more important, the confinement to a two-dimensional surface might enable reaction pathways that are not accessible otherwise. Consequently, on-surface synthesis has attracted great attention in the last decade, with an impressive number of classical reactions transferred to a surface as well as new reactions demonstrated that have no classical analogue. So far, the majority of the work has been carried out on conducting surfaces. However, when aiming for electronic decoupling of the resulting structures, e.g. for the use in future molecular electronic devices, non-conducting surfaces are highly desired. Here, we review the current status of on-surface reactions demonstrated on the (10.4) surface of the bulk insulator calcite. Besides thermally induced C-C coupling of halogen-substituted aryls, photochemically induced [2  +  2] cycloaddition has been proven possible on this surface. Moreover, experimental evidence exists for coupling of terminal alkynes as well as diacetylene polymerization. While imaging of the resulting structures with dynamic atomic force microscopy provides a direct means of reaction verification, the detailed reaction pathway often remains unclear. Especially in cases where the presence of metal atoms is known to catalyze the corresponding solution chemistry reaction (e.g. in the case of the Ullmann reaction), disclosing the precise reaction pathway is of importance to understand and generalize on-surface reactivity on a bulk insulator surface. To this end, density-functional theory calculations have proven to provide atomic-scale insights that have greatly contributed to unravelling the details of on-surface synthesis on a bulk insulator surface.

Interdiscipline: Search and Discovery--Systematization, Application, and Transfer.

ERIC Educational Resources Information Center

Bonomo de Zago, Maria

1978-01-01

Discusses efforts to develop an interdisciplinary cybernetic method, its transfer to different fields of group activities, and results achieved internationally. The 1978 program of activities designed for the promotion of the interdisciplinary cybernetic method by the International Association for Synthesis is also presented. (HM)

A viscous solvent enables information transfer from gene-length nucleic acids in a model prebiotic replication cycle

NASA Astrophysics Data System (ADS)

He, Christine; Gállego, Isaac; Laughlin, Brandon; Grover, Martha A.; Hud, Nicholas V.

2017-04-01

Many hypotheses concerning the nature of early life assume that genetic information was once transferred through the template-directed synthesis of RNA, before the emergence of coded enzymes. However, attempts to demonstrate enzyme-free, template-directed synthesis of nucleic acids have been limited by 'strand inhibition', whereby transferring information from a template strand in the presence of its complementary strand is inhibited by the stability of the template duplex. Here, we use solvent viscosity to circumvent strand inhibition, demonstrating information transfer from a gene-length template (>300 nt) within a longer (545 bp or 3 kb) duplex. These results suggest that viscous environments on the prebiotic Earth, generated periodically by water evaporation, could have facilitated nucleic acid replication—particularly of long, structured sequences such as ribozymes. Our approach works with DNA and RNA, suggesting that viscosity-mediated replication is possible for a range of genetic polymers, perhaps even for informational polymers that may have preceded RNA.

The Transfer Function Model as a Tool to Study and Describe Space Weather Phenomena

NASA Technical Reports Server (NTRS)

Porter, Hayden S.; Mayr, Hans G.; Bhartia, P. K. (Technical Monitor)

2001-01-01

The Transfer Function Model (TFM) is a semi-analytical, linear model that is designed especially to describe thermospheric perturbations associated with magnetic storms and substorm. activity. It is a multi-constituent model (N2, O, He H, Ar) that accounts for wind induced diffusion, which significantly affects not only the composition and mass density but also the temperature and wind fields. Because the TFM adopts a semianalytic approach in which the geometry and temporal dependencies of the driving sources are removed through the use of height-integrated Green's functions, it provides physical insight into the essential properties of processes being considered, which are uncluttered by the accidental complexities that arise from particular source geometrie and time dependences. Extending from the ground to 700 km, the TFM eliminates spurious effects due to arbitrarily chosen boundary conditions. A database of transfer functions, computed only once, can be used to synthesize a wide range of spatial and temporal sources dependencies. The response synthesis can be performed quickly in real-time using only limited computing capabilities. These features make the TFM unique among global dynamical models. Given these desirable properties, a version of the TFM has been developed for personal computers (PC) using advanced platform-independent 3D visualization capabilities. We demonstrate the model capabilities with simulations for different auroral sources, including the response of ducted gravity waves modes that propagate around the globe. The thermospheric response is found to depend strongly on the spatial and temporal frequency spectra of the storm. Such varied behavior is difficult to describe in statistical empirical models. To improve the capability of space weather prediction, the TFM thus could be grafted naturally onto existing statistical models using data assimilation.

Facile room-temperature synthesis of carboxylated graphene oxide-copper sulfide nanocomposite with high photodegradation and disinfection activities under solar light irradiation

PubMed Central

Yu, Shuyan; Liu, Jincheng; Zhu, Wenyu; Hu, Zhong-Ting; Lim, Teik-Thye; Yan, Xiaoli

2015-01-01

Carboxylic acid functionalized graphene oxide-copper (II) sulfide nanoparticle composite (GO-COOH-CuS) was prepared from carboxylated graphene oxide and copper precursor in dimethyl sulfoxide (DMSO) by a facile synthesis process at room temperature. The high-effective combination, the interaction between GO-COOH sheets and CuS nanoparticles, and the enhanced visible light absorption were confirmed by transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermo gravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectra (DRS) and Photoluminescence (PL) spectra. The as-synthesized GO-COOH-CuS nanocomposite exhibited excellent photocatalytic degradation performance of phenol and rhodamine B, high antibacterial activity toward E. coli and B. subtilis, and good recovery and reusability. The influence of CuS content, the synergistic reaction between CuS and GO-COOH, and the charge-transfer mechanism were systematically investigated. The facile and low-energy synthesis process combined with the excellent degradation and antibacterial performance signify that the GO-COOH-CuS has a great potential for water treatment application. PMID:26553709

Understanding the Formation of Kinetically Stable Compounds and the Development of Thin Film Pair Distribution Function Analysis

NASA Astrophysics Data System (ADS)

Wood, Suzannah Rebecca

Navigating the synthesis landscape poses many challenges when developing novel solid state materials. Advancements in both synthesis and characterization are necessary to facilitate the targeting of specific materials. This dissertation discusses the formation of chalcogenide heterostructures and their properties in the first part and the development of thin film pair distribution function analysis (tfPDF) in the second part. The heterostructures were formed by the self-assembly of designed precursors deposited by physical vapor deposition in a modulated elemental reactants approach, which provides the control and predictability to synthesis. Specifically, a series of (BiSe)1+delta(TiSe2) n, where n = 2,3,&4, were synthesized to explore the extent of charge transfer from the BiSe to TiSe2 layers. To further explore the role Bi plays in charge donation, a family of structurally similar compounds, (Bix Sn1-xSe)1+deltaTiSe2, where 0≥x≥1, were synthesized and characterized. Electrical measurements show doping efficiency decreases as x increases, correlated with the structural distortion and the formation of periodic antiphase boundaries containing Bi-Bi pairs. The first heterostructures composed of three unique structural types were synthesized and Bi2Se3 layer thickness was used to tune electrical properties and further explore charge transfer. To better understand the potential energy landscape on which these kinetically stable compounds exist, two investigations were undertaken. The first was a study of the formation and subsequent decomposition of [(BiSe)1+delta]n(TiSe2)n compounds, where n= 2&3, the second an investigation of precursor structure for thermodynamically stable FeSb2 and kinetically stable FeSb3. The second section describes the development of thin film pair distribution function analysis, a technique in which total scattering data for pair distribution function (PDF) analysis is obtained from thin films, suitable for local structure analysis. This study illustrates how analysis of the local structure in amorphous precursor films can help to understand the crystallization processes of metastable phases and enables a range of new local structure studies of thin films. tfPDF was then demonstrated on In-Ga-O film materials and compared to traditional powder PDF analysis. This highlights differences between the products, and the utility of tfPDF to determined structural features of amorphous materials. This dissertation includes previously published and unpublished co-authored materials.

The biotin repressor: modulation of allostery by corepressor analogs.

PubMed

Brown, Patrick H; Cronan, John E; Grøtli, Morten; Beckett, Dorothy

2004-04-02

The Escherichia coli biotin repressor functions in biotin retention and regulation of biotin biosynthesis. Biotin retention is accomplished via the two-step biotinylation of the biotin-dependent enzyme, acetyl-CoA carboxylase. In the first step of this reaction the substrates biotin and ATP are utilized in synthesis of the activated biotin, biotinyl-5'-AMP, while in the second step this activated biotin is transferred to a unique lysine residue of the biotin carboxyl carrier protein subunit of the carboxylase. Regulation of biotin biosynthesis is accomplished through binding of the repressor to the transcription control region of the biotin biosynthetic operon. The adenylated or activated biotin functions as the corepressor in this DNA binding process. The activated biotin is a mixed anhydride and thus labile. In efforts to develop tools for structural and thermodynamic studies of the biotin regulatory interactions, two analogs of the adenylate, a sulfamoyl derivative and an ester derivative, have been synthesized and functionally characterized. Results of fluorescence measurements indicate that both analogs bind with high affinity to the repressor and that both are inactive in biotin transfer to the acceptor protein. Functional studies of their corepressor properties indicate that while the sulfamoyl is a weak allosteric activator, the ester closely mimics the physiological corepressor in activation of assembly of the transcription repression complex. Results of these studies also provide further insight into the allosteric mechanism of the biotin repressor.

Converting conformational changes to electrostatic energy in molecular motors: The energetics of ATP synthase.

PubMed

Strajbl, Marek; Shurki, Avital; Warshel, Arieh

2003-12-09

F1-ATPase is the catalytic component of the ATP synthase molecular machine responsible for most of the uphill synthesis of ATP in living systems. The enormous advances in biochemical and structural studies of this machine provide an opportunity for detailed understanding of the nature of its rotary mechanism. However, further quantitative progress in this direction requires development of reliable ways of translating the observed structural changes to the corresponding energies. This requirement is particularly challenging because we are dealing with a large system that couples major structural changes with a chemical process. The present work provides such a structure-function correlation by using the linear response approximation to describe the rotary mechanism. This approach allows one to evaluate the energy of transitions between different conformational states by considering only the changes in the corresponding electrostatic energies of the ligands. The relevant energetics are also obtained by calculating the linear response approximation-based free energies of transferring the ligands from water to the different sites of F1-ATPase in their different conformational states. We also use the empirical valence bond approach to evaluate the actual free-energy profile for the ATP synthesis in the different conformational states of the system. Integrating the information from the different approaches provides a semiquantitative structure-function correlation for F1-ATPase. It is found that the conformational changes are converted to changes in the electrostatic interaction between the protein and its ligands, which drives the ATP synthesis.

Survey of Genes Involved in Biosynthesis, Transport, and Signaling of Phytohormones with Focus on Solanum lycopersicum

PubMed Central

Simm, Stefan; Scharf, Klaus-Dieter; Jegadeesan, Sridharan; Chiusano, Maria Luisa; Firon, Nurit; Schleiff, Enrico

2016-01-01

Phytohormones control the development and growth of plants, as well as their response to biotic and abiotic stress. The seven most well-studied phytohormone classes defined today are as follows: auxins, ethylene, cytokinin, abscisic acid, jasmonic acid, gibberellins, and brassinosteroids. The basic principle of hormone regulation is conserved in all plants, but recent results suggest adaptations of synthesis, transport, or signaling pathways to the architecture and growth environment of different plant species. Thus, we aimed to define the extent to which information from the model plant Arabidopsis thaliana is transferable to other plants such as Solanum lycopersicum. We extracted the co-orthologues of genes coding for major pathway enzymes in A. thaliana from the translated genomes of 12 species from the clade Viridiplantae. Based on predicted domain architecture and localization of the identified proteins from all 13 species, we inspected the conservation of phytohormone pathways. The comparison was complemented by expression analysis of (co-) orthologous genes in S. lycopersicum. Altogether, this information allowed the assignment of putative functional equivalents between A. thaliana and S. lycopersicum but also pointed to some variations between the pathways in eudicots, monocots, mosses, and green algae. These results provide first insights into the conservation of the various phytohormone pathways between the model system A. thaliana and crop plants such as tomato. We conclude that orthologue prediction in combination with analysis of functional domain architecture and intracellular localization and expression studies are sufficient tools to transfer information from model plants to other plant species. Our results support the notion that hormone synthesis, transport, and response for most part of the pathways are conserved, and species-specific variations can be found. PMID:27695302

Low Melt Viscosity Resins for Resin Transfer Molding

NASA Technical Reports Server (NTRS)

Harris, Frank W.

2002-01-01

In recent years, resin transfer molding (RTM) has become one of the methods of choice for high performance composites. Its cost effectiveness and ease of fabrication are major advantages of RTM. RTM process usually requires resins with very low melt viscosity (less than 10 Poise). The optimum RTM resins also need to display high thennal-oxidative stability, high glass transition temperature (T(sub g)), and good toughness. The traditional PMR-type polyimides (e.g. PMR-15) do not fit this requirement, because the viscosities are too high and the nadic endcap cures too fast. High T(sub g), low-melt viscosity resins are highly desirable for aerospace applications and NASA s Reusable Launch Vehicle (RLV) program. The objective of this work is to prepare low-melt viscosity polyimide resins for RTM or resin film infusion (RFI) processes. The approach involves the synthesis of phenylethynyl-terminated imide oligomers. These materials have been designed to minimize their melt viscosity so that they can be readily processed. During the cure, the oligomers undergo both chain extension and crosslinking via the thermal polymerization of the phenylethynyl groups. The Phenylethynyl endcap is preferred over the nadic group due to its high curing temperature, which provides broader processing windows. This work involved the synthesis and polymerization of oligomers containing zig-zag backbones and twisted biphenyl structures. Some A-B type precursors which possessed both nitro and anhydride functionality, or both nitro and amine functionality, were also synthesized in order to obtain the well defined oligomers. The resulting zig-zag structured oligomers were then end-capped with 4-phenylethynylphthalic anhydride (PEPA) for further cure. The properties of these novel imide oligomers are evaluated.

Synthesis and photoluminescence in Yb doped cerium phosphate CePO4

NASA Astrophysics Data System (ADS)

Bhonsule, S. U.; Wankhede, S. P.; Moharil, S. V.

2018-05-01

This paper presents the preparation of CePO4 and Yb doped CePO4 using simple solid state reaction method. PL measurements indicated significant energy transfer from Ce3+ to Yb3+ ions. Further evidence of energy transfer was provided by analysis of Luminescence Decay measurements. Energy transfer efficiency of 50% was obtained for 5%Yb doping. Energy transfer from Ce3+ to Yb3+ ions takes place by Cooperative energy transfer mechanism. Such phosphors can be used in white LED's, Lasers and energy saving fluorescent lamps.

Efficient gene transfer into nondividing cells by adeno-associated virus-based vectors.

PubMed Central

Podsakoff, G; Wong, K K; Chatterjee, S

1994-01-01

Gene transfer vectors based on adeno-associated virus (AAV) are emerging as highly promising for use in human gene therapy by virtue of their characteristics of wide host range, high transduction efficiencies, and lack of cytopathogenicity. To better define the biology of AAV-mediated gene transfer, we tested the ability of an AAV vector to efficiently introduce transgenes into nonproliferating cell populations. Cells were induced into a nonproliferative state by treatment with the DNA synthesis inhibitors fluorodeoxyuridine and aphidicolin or by contact inhibition induced by confluence and serum starvation. Cells in logarithmic growth or DNA synthesis arrest were transduced with vCWR:beta gal, an AAV-based vector encoding beta-galactosidase under Rous sarcoma virus long terminal repeat promoter control. Under each condition tested, vCWR:beta Gal expression in nondividing cells was at least equivalent to that in actively proliferating cells, suggesting that mechanisms for virus attachment, nuclear transport, virion uncoating, and perhaps some limited second-strand synthesis of AAV vectors were present in nondividing cells. Southern hybridization analysis of vector sequences from cells transduced while in DNA synthetic arrest and expanded after release of the block confirmed ultimate integration of the vector genome into cellular chromosomal DNA. These findings may provide the basis for the use of AAV-based vectors for gene transfer into quiescent cell populations such as totipotent hematopoietic stem cells. Images PMID:8057446

Efficient gene transfer into nondividing cells by adeno-associated virus-based vectors.

PubMed

Podsakoff, G; Wong, K K; Chatterjee, S

1994-09-01

Gene transfer vectors based on adeno-associated virus (AAV) are emerging as highly promising for use in human gene therapy by virtue of their characteristics of wide host range, high transduction efficiencies, and lack of cytopathogenicity. To better define the biology of AAV-mediated gene transfer, we tested the ability of an AAV vector to efficiently introduce transgenes into nonproliferating cell populations. Cells were induced into a nonproliferative state by treatment with the DNA synthesis inhibitors fluorodeoxyuridine and aphidicolin or by contact inhibition induced by confluence and serum starvation. Cells in logarithmic growth or DNA synthesis arrest were transduced with vCWR:beta gal, an AAV-based vector encoding beta-galactosidase under Rous sarcoma virus long terminal repeat promoter control. Under each condition tested, vCWR:beta Gal expression in nondividing cells was at least equivalent to that in actively proliferating cells, suggesting that mechanisms for virus attachment, nuclear transport, virion uncoating, and perhaps some limited second-strand synthesis of AAV vectors were present in nondividing cells. Southern hybridization analysis of vector sequences from cells transduced while in DNA synthetic arrest and expanded after release of the block confirmed ultimate integration of the vector genome into cellular chromosomal DNA. These findings may provide the basis for the use of AAV-based vectors for gene transfer into quiescent cell populations such as totipotent hematopoietic stem cells.

Speech coding, reconstruction and recognition using acoustics and electromagnetic waves

DOE Office of Scientific and Technical Information (OSTI.GOV)

Holzrichter, J.F.; Ng, L.C.

The use of EM radiation in conjunction with simultaneously recorded acoustic speech information enables a complete mathematical coding of acoustic speech. The methods include the forming of a feature vector for each pitch period of voiced speech and the forming of feature vectors for each time frame of unvoiced, as well as for combined voiced and unvoiced speech. The methods include how to deconvolve the speech excitation function from the acoustic speech output to describe the transfer function each time frame. The formation of feature vectors defining all acoustic speech units over well defined time frames can be used formore » purposes of speech coding, speech compression, speaker identification, language-of-speech identification, speech recognition, speech synthesis, speech translation, speech telephony, and speech teaching. 35 figs.« less

Direct α-C-H bond functionalization of unprotected cyclic amines

NASA Astrophysics Data System (ADS)

Chen, Weijie; Ma, Longle; Paul, Anirudra; Seidel, Daniel

2018-02-01

Cyclic amines are ubiquitous core structures of bioactive natural products and pharmaceutical drugs. Although the site-selective abstraction of C-H bonds is an attractive strategy for preparing valuable functionalized amines from their readily available parent heterocycles, this approach has largely been limited to substrates that require protection of the amine nitrogen atom. In addition, most methods rely on transition metals and are incompatible with the presence of amine N-H bonds. Here we introduce a protecting-group-free approach for the α-functionalization of cyclic secondary amines. An operationally simple one-pot procedure generates products via a process that involves intermolecular hydride transfer to generate an imine intermediate that is subsequently captured by a nucleophile, such as an alkyl or aryl lithium compound. Reactions are regioselective and stereospecific and enable the rapid preparation of bioactive amines, as exemplified by the facile synthesis of anabasine and (-)-solenopsin A.

Applications of biochar in redox-mediated reactions.

PubMed

Yuan, Yong; Bolan, Nanthi; Prévoteau, Antonin; Vithanage, Meththika; Biswas, Jayanta Kumar; Ok, Yong Sik; Wang, Hailong

2017-12-01

Biochar is chemically more reduced and reactive than the original feedstock biomass. Graphite regions, functional groups, and redox-active metals in biochar contribute to its redox characteristics. While the functional groups such as phenolic species in biochar are the main electron donating moieties (i.e., reducers), the quinones and polycondensed aromatic functional groups are the components accepting electrons (oxidants). The redox capacity of biochar depends on feedstock properties and pyrolysis conditions. This paper aims to review and summarize the various synthesis techniques for biochars and the methods for probing their redox characteristics. We review the abiotic and microbial applications of biochars as electron donors, electron acceptors, or electron shuttles for pollutant degradation, metal(loid)s (im)mobilization, nutrient transformation, and discuss the underlying mechanisms. Furthermore, knowledge gaps that exist in the exploration and differentiation of the electron transfer mechanisms involving biochars are also identified. Copyright © 2017 Elsevier Ltd. All rights reserved.

One Carbon Metabolism in Pregnancy: Impact on Maternal, Fetal and Neonatal Health

PubMed Central

Kalhan, Satish C

2016-01-01

One carbon metabolism or methyl transfer, a crucial component of metabolism in all cells and tissues, supports the critical function of synthesis of purines, thymidylate and methylation via multiple methyl transferases driven by the ubiquitous methyl donor s-adenosylmethionine. Serine is the primary methyl donor to the one carbon pool. Intracellular folates and methionine metabolism are the critical components of one carbon transfer. Methionine metabolism requires vitamin B12, B6 as cofactors and is modulated by endocrine signals and is responsive to nutrient intake. Perturbations in one carbon transfer can have profound effects on cell proliferation, growth and function. Epidemiological studies in humans and experimental model have established a strong relationship between impaired fetal growth and the immediate and long term consequences to the health of the offspring. It is speculated that during development, maternal environmental and nutrient influences by their effects on one carbon transfer can impact the health of the mother, impair growth and reprogram metabolism of the fetus, and cause long term morbidity in the offspring. The potential for such effects is underscored by the unique responses in methionine metabolism in the human mother during pregnancy, the absence of transsulfuration activity in the fetus, ontogeny of methionine metabolism in the placenta and the unique metabolism of serine and glycine in the fetus. Dietary protein restriction in animals and marginal protein intake in humans causes characteristic changes in one carbon metabolism. The impact of perturbations in one carbon metabolism on the health of the mother during pregnancy, on fetal growth and the neonate are discussed and their possible mechanism explored. PMID:27267668

Charge transfer and surface defect healing within ZnO nanoparticle decorated graphene hybrid materials.

PubMed

Pham, Chuyen V; Repp, Sergej; Thomann, Ralf; Krueger, Michael; Weber, Stefan; Erdem, Emre

2016-05-05

To harness the unique properties of graphene and ZnO nanoparticles (NPs) for novel applications, the development of graphene-ZnO nanoparticle hybrid materials has attracted great attention and is the subject of ongoing research. For this contribution, graphene-oxide-ZnO (GO-ZnO) and thiol-functionalized reduced graphene oxide-ZnO (TrGO-ZnO) nanohybrid materials were prepared by novel self-assembly processes. Based on electron paramagnetic resonance (EPR) and photoluminescence (PL) investigations on bare ZnO NPs, GO-ZnO and TrGO-ZnO hybrid materials, we found that several physical phenomena were occurring when ZnO NPs were hybridized with GO and TrGO. The electrons trapped in Zn vacancy defects (VZn(-)) within the core of ZnO NPs vanished by transfer to GO and TrGO in the hybrid materials, thus leading to the disappearance of the core signals in the EPR spectra of ZnO NPs. The thiol groups of TrGO and sulfur can effectively "heal" the oxygen vacancy (VO(+)) related surface defects of ZnO NPs while oxygen-containing functionalities have low healing ability at a synthesis temperature of 100 °C. Photoexcited electron transfer from the conduction band of ZnO NPs to graphene leads to photoluminescence (PL) quenching of near band gap emission (NBE) of both GO-ZnO and TrGO-ZnO. Simultaneously, electron transfer from graphene to defect states of ZnO NPs is the origin of enhanced green defect emission from GO-ZnO. This observation is consistent with the energy level diagram model of hybrid materials.

Multiple roles of genome-attached bacteriophage terminal proteins

DOE Office of Scientific and Technical Information (OSTI.GOV)

Redrejo-Rodríguez, Modesto; Salas, Margarita, E-mail: msalas@cbm.csic.es

2014-11-15

Protein-primed replication constitutes a generalized mechanism to initiate DNA or RNA synthesis in linear genomes, including viruses, gram-positive bacteria, linear plasmids and mobile elements. By this mechanism a specific amino acid primes replication and becomes covalently linked to the genome ends. Despite the fact that TPs lack sequence homology, they share a similar structural arrangement, with the priming residue in the C-terminal half of the protein and an accumulation of positively charged residues at the N-terminal end. In addition, various bacteriophage TPs have been shown to have DNA-binding capacity that targets TPs and their attached genomes to the host nucleoid.more » Furthermore, a number of bacteriophage TPs from different viral families and with diverse hosts also contain putative nuclear localization signals and localize in the eukaryotic nucleus, which could lead to the transport of the attached DNA. This suggests a possible role of bacteriophage TPs in prokaryote-to-eukaryote horizontal gene transfer. - Highlights: • Protein-primed genome replication constitutes a strategy to initiate DNA or RNA synthesis in linear genomes. • Bacteriophage terminal proteins (TPs) are covalently attached to viral genomes by their primary function priming DNA replication. • TPs are also DNA-binding proteins and target phage genomes to the host nucleoid. • TPs can also localize in the eukaryotic nucleus and may have a role in phage-mediated interkingdom gene transfer.« less

Inherently-Forced Tensile Strain in Nanodiamond-Derived Onion-like Carbon: Consequences in Defect-Induced Electrochemical Activation

PubMed Central

Ko, Young-Jin; Cho, Jung-Min; Kim, Inho; Jeong, Doo Seok; Lee, Kyeong-Seok; Park, Jong-Keuk; Baik, Young-Joon; Choi, Heon-Jin; Lee, Seung-Cheol; Lee, Wook-Seong

2016-01-01

We analyzed the nanodiamond-derived onion-like carbon (OLC) as function of synthesis temperature (1000~1400 °C), by high-resolution electron microscopy, electron energy loss spectroscopy, visible-Raman spectroscopy, ultraviolet photoemission spectroscopy, impedance spectroscopy, cyclic voltammetry and differential pulse voltammetry. The temperature dependences of the obtained properties (averaged particle size, tensile strain, defect density, density of states, electron transfer kinetics, and electrochemical oxidation current) unanimously coincided: they initially increased and saturated at 1200 °C. It was attributed to the inherent tensile strains arising from (1) the volume expansion associated with the layer-wise diamond-to-graphite transformation of the core, which caused forced dilation of the outer shells during their thermal synthesis; (2) the extreme curvature of the shells. The former origin was dominant over the latter at the outermost shell, of which the relevant evolution in defect density, DOS and electron transfer kinetics determined the electrochemical performances. In detection of dopamine (DA), uric acid (UA) and ascorbic acid (AA) using the OLC as electrode, their oxidation peak currents were enhanced by factors of 15~60 with annealing temperature. Their limit of detection and the linear range of detection, in the post-treatment-free condition, were as excellent as those of the nano-carbon electrodes post-treated by Pt-decoration, N-doping, plasma, or polymer. PMID:27032957

Molecular Evolution of Aminoacyl tRNA Synthetase Proteins in the Early History of Life

NASA Astrophysics Data System (ADS)

Fournier, Gregory P.; Andam, Cheryl P.; Alm, Eric J.; Gogarten, J. Peter

2011-12-01

Aminoacyl-tRNA synthetases (aaRS) consist of several families of functionally conserved proteins essential for translation and protein synthesis. Like nearly all components of the translation machinery, most aaRS families are universally distributed across cellular life, being inherited from the time of the Last Universal Common Ancestor (LUCA). However, unlike the rest of the translation machinery, aaRS have undergone numerous ancient horizontal gene transfers, with several independent events detected between domains, and some possibly involving lineages diverging before the time of LUCA. These transfers reveal the complexity of molecular evolution at this early time, and the chimeric nature of genomes within cells that gave rise to the major domains. Additionally, given the role of these protein families in defining the amino acids used for protein synthesis, sequence reconstruction of their pre-LUCA ancestors can reveal the evolutionary processes at work in the origin of the genetic code. In particular, sequence reconstructions of the paralog ancestors of isoleucyl- and valyl- RS provide strong empirical evidence that at least for this divergence, the genetic code did not co-evolve with the aaRSs; rather, both amino acids were already part of the genetic code before their cognate aaRSs diverged from their common ancestor. The implications of this observation for the early evolution of RNA-directed protein biosynthesis are discussed.

The Differential Expression of Sucrose Synthase in Relation to Diverse Patterns of Carbon Partitioning in Developing Cotton Seed.

PubMed Central

Ruan, Y. L.; Chourey, P. S.; Delmer, D. P.; Perez-Grau, L.

1997-01-01

Developing cotton (Gossypium hirsutum L.) seed exhibits complex patterns of carbon allocation in which incoming sucrose (Suc) is partitioned to three major sinks: the fibers, seed coat, and cotyledons, which synthesize cellulose, starch, and storage proteins or oils, respectively. In this study we investigated the role of Suc synthase (SuSy) in the mobilization of Suc into such sinks. Assessments of SuSy gene expression at various levels led to the surprising conclusion that, in contrast to that found for other plants, SuSy does not appear to play a role in starch synthesis in the cotton seed. However, our demonstration of functional symplastic connections between the phloem-unloading area and the fiber cells, as well as the SuSy expression pattern in fibers, indicates a major role of SuSy in partitioning carbon to fiber cellulose synthesis. SuSy expression is also high in transfer cells of the seed coat facing the cotyledons. Such high levels of SuSy could contribute to the synthesis of the thickened cell walls and to the energy generation for Suc efflux to the seed apoplast. The expression of SuSy in cotyledons also suggests a role in protein and lipid synthesis. In summary, the developing cotton seed provides an excellent example of the diverse roles played by SuSy in carbon metabolism. PMID:12223814

DNA modification and functional delivery into human cells using Escherichia coli DH10B

PubMed Central

Narayanan, Kumaran; Warburton, Peter E.

2003-01-01

The availability of almost the complete human genome as cloned BAC libraries represents a valuable resource for functional genomic analysis, which, however, has been somewhat limited by the ability to modify and transfer this DNA into mammalian cells intact. Here we report a novel comprehensive Escherichia coli-based vector system for the modification, propagation and delivery of large human genomic BAC clones into mammalian cells. The GET recombination inducible homologous recombination system was used in the BAC host strain E.coli DH10B to precisely insert an EGFPneo cassette into the vector portion of a ∼200 kb human BAC clone, providing a relatively simple method to directly convert available BAC clones into suitable vectors for mammalian cells. GET recombination was also used for the targeted deletion of the asd gene from the E.coli chromosome, resulting in defective cell wall synthesis and diaminopimelic acid auxotrophy. Transfer of the Yersinia pseudotuberculosis invasin gene into E.coli DH10B asd– rendered it competent to invade HeLa cells and deliver DNA, as judged by transient expression of green fluorescent protein and stable neomycin-resistant colonies. The efficiency of DNA transfer and survival of HeLa cells has been optimized for incubation time and multiplicity of infection of invasive E.coli with HeLa cells. This combination of E.coli-based homologous recombination and invasion technologies using BAC host strain E.coli DH10B will greatly improve the utility of the available BAC libraries from the human and other genomes for gene expression and functional genomic studies. PMID:12711696

Characterization and Expression of Glutamate Dehydrogenase in Response to Acute Salinity Stress in the Chinese Mitten Crab, Eriocheir sinensis

PubMed Central

Wang, Yueru; Li, Erchao; Yu, Na; Wang, Xiaodan; Cai, Chunfang; Tang, Boping; Chen, Liqiao; Van Wormhoudt, Alain

2012-01-01

Background Glutamate dehydrogenase (GDH) is a key enzyme for the synthesis and catabolism of glutamic acid, proline and alanine, which are important osmolytes in aquatic animals. However, the response of GDH gene expression to salinity alterations has not yet been determined in macro-crustacean species. Methodology/Principal Findings GDH cDNA was isolated from Eriocheir sinensis. Then, GDH gene expression was analyzed in different tissues from normal crabs and the muscle of crabs following transfer from freshwater (control) directly to water with salinities of 16‰ and 30‰, respectively. Full-length GDH cDNA is 2,349 bp, consisting of a 76 bp 5′- untranslated region, a 1,695 bp open reading frame encoding 564 amino acids and a 578 bp 3′- untranslated region. E. sinensis GDH showed 64–90% identity with protein sequences of mammalian and crustacean species. Muscle was the dominant expression source among all tissues tested. Compared with the control, GDH expression significantly increased at 6 h in crabs transferred to 16‰ and 30‰ salinity, and GDH expression peaked at 48 h and 12 h, respectively, with levels approximately 7.9 and 8.5 fold higher than the control. The free amino acid (FAA) changes in muscle, under acute salinity stress (16‰ and 30‰ salinities), correlated with GDH expression levels. Total FAA content in the muscle, which was based on specific changes in arginine, proline, glycine, alanine, taurine, serine and glutamic acid, tended to increase in crabs following transfer to salt water. Among these, arginine, proline and alanine increased significantly during salinity acclimation and accounted for the highest proportion of total FAA. Conclusions E. sinensis GDH is a conserved protein that serves important functions in controlling osmoregulation. We observed that higher GDH expression after ambient salinity increase led to higher FAA metabolism, especially the synthesis of glutamic acid, which increased the synthesis of proline and alanine to meet the demand of osmoregulation at hyperosmotic conditions. PMID:22615974

Synthesis, Spray Deposition, and Hot-Press Transfer of Copper Nanowires for Flexible Transparent Electrodes.

PubMed

Deshmukh, Rupali; Calvo, Micha; Schreck, Murielle; Tervoort, Elena; Sologubenko, Alla S; Niederberger, Markus

2018-06-20

We report a solution-phase approach to the synthesis of crystalline copper nanowires (Cu NWs) with an aspect ratio >1000 via a new catalytic mechanism comprising copper ions. The synthesis involves the reaction between copper(II) chloride and copper(II) acetylacetonate in a mixture of oleylamine and octadecene. Reaction parameters such as the molar ratio of precursors as well as the volume ratio of solvents offer the possibility to tune the morphology of the final product. A simple low-cost spray deposition method was used to fabricate Cu NW films on a glass substrate. Post-treatment under reducing gas (5% H 2 + 95% N 2 ) atmosphere resulted in Cu NW films with a low sheet resistance of 24.5 Ω/sq, a transmittance of T = 71% at 550 nm (including the glass substrate), and a high oxidation resistance. Moreover, the conducting Cu NW networks on a glass substrate can easily be transferred onto a polycarbonate substrate using a simple hot-press transfer method without compromising on the electrical performance. The resulting flexible transparent electrodes show excellent flexibility ( R/ R o < 1.28) upon bending to curvatures of 1 mm radius.

The role of polymerase III in conjugation between E. coli K12 donor and recipient strains carrying dnaE ts mutation.

PubMed

Blinkowa, A

1976-01-01

The possible role of DNA polimerase III in conjugation was studied in a series of mutants temperature-sensitive for DNA polymerase III synthesis. The temperature-sensitive DNA mutation called dnaE 486 (ts) prohibits vegetative DNA replication at 41-45 degrees. Transfer of episome and chromosome from temperature-sensitive donor, carrying dnaE mutation to wild-type recipient strains, revertants and dnaE recipients was investigated. In the first two cases the number of Lac+ sexductants being even slightly higher at 43 degrees. Conjugational synthesis accompanying transfer involving the combination of dnaE (ts) thymine dependent and thymine independent donor and recipient strains measured by incorporation of 14C thymine was observed at the restrictive temperature. In the case of conjugation with temperaturesensitive recipient strains a drop of Lac+ sexductants and Pro+ recombinants may be as a result of disturbances in the synthesis of complementary strand in recipient, known to be dependent on pol III. However, the episome investigated by centrifugation in neutral CsC1 gradient after its transfer to the recipient with faulty polymerase III was double stranded (replicated) at the restrictive temperature.

An Undergraduate Chemistry Laboratory: Synthesis of Well-Defined Polymers by Low-Catalyst-Concentration ATRP and Postpolymerization Modification to Fluorescent Materials

ERIC Educational Resources Information Center

Tsarevsky, Nicolay V.; Woodruf, Shannon R.; Wisian-Neilson, Patty J.

2016-01-01

A two-session experiment is designed to introduce undergraduate students to concepts in catalysis, transition metal complexes, polymer synthesis, and postpolymerization modifications. In the first session, students synthesize poly(glycidyl methacrylate) via low-catalyst-concentration atom transfer radical polymerization (ATRP). The…

Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization in Undergraduate Polymer Science Lab

ERIC Educational Resources Information Center

Nguyen, T. L. U.; Bennet, Francesca; Stenzel, Martina H.; Barner-Kowollik, Christopher

2008-01-01

This 8-hour experiment (spread over two 4-hour sessions) is designed to equip students with essential skills in polymer synthesis, particularly in synthesizing polymers of well-defined molecular weight. The experiment involves the synthesis and characterization of poly(vinyl neodecanoate) via living free radical polymerization, specifically the…

Plasma glutamine is a minor precursor for the synthesis of citrulline: A multispecies study

USDA-ARS?s Scientific Manuscript database

Glutamine is considered the main precursor for citrulline synthesis in many species, including humans. The transfer of 15N from 2[15N]-glutamine to citrulline has been used as evidence for this precursor-product relationship. However, work in mice has shown that nitrogen and carbon tracers follow di...

Integrated nanoparticle-biomolecule systems for biosensing and bioelectronics.

PubMed

Willner, Itamar; Baron, Ronan; Willner, Bilha

2007-04-15

The similar dimensions of biomolecules such as enzymes, antibodies or DNA, and metallic or semiconductor nanoparticles (NPs) enable the synthesis of biomolecule-NP hybrid systems where the unique electronic, photonic and catalytic properties of NPs are combined with the specific recognition and biocatalytic properties of biomolecules. The unique functions of biomolecule-NP hybrid systems are discussed with several examples: (i) the electrical contacting of redox enzymes with electrodes is the basis for the development of enzymatic electrodes for amperometric biosensors or biofuel cell elements. The reconstitution of the apo-glucose oxidase or apo-glucose dehydrogenase on flavin adenine dinucleotide (FAD)-functionalized Au NPs (1.4 nm) associated with electrodes, or on pyrroloquinoline quinone (PQQ)-functionalized Au NPs (1.4 nm) associated with electrodes, respectively, yields electrically contacted enzyme electrodes. The aligned, reconstituted enzymes on the electrode surfaces reveal effective electrical contacting, and the glucose oxidase and glucose dehydrogenase reveal turnover rates of 5000 and 11,800 s(-1), respectively. (ii) The photoexcitation of semiconductor nanoparticles yields fluorescence with a wavelength controlled by the size of the NPs. The fluorescence functions of semiconductor NPs are used to develop a fluorescence resonance energy transfer (FRET) assay for nucleic acids, and specifically, for analyzing telomerase activity in cancer cells. CdSe-ZnS NPs are functionalized by a primer recognized by telomerase, and this is elongated by telomerase extracted from HeLa cancer cells in the presence of dNTPs and Texas-red-functionalized dUTP. The dye integrated into the telomers allows the FRET process that is intensified as telomerization proceeds. Also, the photoexcited electron-hole pair generated in semiconductor NPs is used to generate photocurrents in a CdS-DNA hybrid system associated with an electrode. A redox-active intercalator, methylene blue, was incorporated into a CdS-duplex DNA monolayer associated with a Au electrode, and this facilitated the electron transfer between the electrode and the CdS NPs. The direction of the photocurrent was controlled by the oxidation state of the intercalator. (iii) Biocatalysts grow metallic NPs, and the absorbance of the NPs provides a means to assay the biocatalytic transformations. This is exemplified with the glucose oxidase-induced growth of Au NPs and with the tyrosinase-stimulated growth of Au NPs, in the presence of glucose or tyrosine, respectively. The biocatalytic growth of the metallic NPs is used to grow nanowires on surfaces. Glucose oxidase or alkaline phosphatase functionalized with Au NPs (1.4 nm) acted as 'biocatalytic inks' for the synthesis of metallic nanowires. The deposition of the Au NP-modified glucose oxidase, or the Au NP-modified alkaline phosphatase on Si surfaces by dip-pen nanolithography led to biocatalytic templates, that after interaction with glucose/AuCl4- or p-aminophenolphosphate/Ag+, allowed the synthesis of Au nanowires or Ag nanowires, respectively.

Biotin-transfer from a trifunctional crosslinker for identification of cell surface receptors of soluble protein ligands

PubMed Central

Tremblay, Tammy-Lynn; Hill, Jennifer J.

2017-01-01

Here we describe a novel crosslinker and its application as a biotin-transfer reagent to identify cell surface receptors of soluble protein ligands on live cells. This crosslinker contains three functional groups: an aldehyde-reactive aminooxy group, a sulfhydryl, and a biotin (ASB). It is readily synthesized via a 3-step addition reaction using standard solid-phase peptide synthesis methods and commercially available intermediates, allowing access to laboratories without specialized synthetic chemistry capabilities. For the biotin-transfer method, ASB is linked to a protein ligand through the sulfhydryl group in a two-step process that allows the introduction of a disulfide bond between the ligand and the crosslinker. Incubation of the labelled ligand with oxidized live cells leads to the formation of crosslinks with aldehyde-containing glycans on the cell surface receptor. Subsequent reduction of the disulfide bond results in biotin transfer from the ligand to the cell surface receptor. Protein biotinylation that is mediated by ligand binding to its receptor is differentiated from background biotinylation events by comparison with a similarly labelled control protein using comparative proteomic mass spectrometry to quantify streptavidin-bound proteins. Using this method, we successfully identified the cell surface receptors of a peptide hormone, a monoclonal antibody, and a single-domain antibody-Fc fusion construct. PMID:28422167

The baculovirus-integrated retrotransposon TED encodes gag and pol proteins that assemble into viruslike particles with reverse transcriptase.

PubMed Central

Lerch, R A; Friesen, P D

1992-01-01

TED is a lepidopteran retrotransposon found inserted within the DNA genome of the Autographa californica nuclear polyhedrosis virus mutant, FP-D. To examine the proteins and functions encoded by this representative of the gypsy family of retrotransposons, the gag- and pol-like open reading frames (ORFs 1 and 2) were expressed in homologous lepidopteran cells by using recombinant baculovirus vectors. Expression of ORF 1 resulted in synthesis of an abundant TED-specific protein (Pr55gag) that assembled into viruslike particles with a diameter of 55 to 60 nm. Expression of ORF 2, requiring a -1 translational frameshift, resulted in synthesis of a protease that mediated cleavage of Pr55gag to generate p37, the major protein component of the resulting particles. Expression of ORF 2 also produced reverse transcriptase that associated with these particles. Both protease and reverse transcriptase activities mapped to domains within ORF 2 that contain sequence similarities with the corresponding functional domains of the pol gene of the vertebrate retroviruses. These results indicated that TED ORFs 1 and 2 functionally resemble the retrovirus gag and pol genes and demonstrated for the first time that an invertebrate member of the gypsy family of elements encodes active forms of the structural and enzymatic functions necessary for transposition via an RNA intermediate. TED integration within the baculovirus genome thus represents one of the first examples of transposon-mediated transfer of host-derived genes to an eukaryotic virus. Images PMID:1371168

Enantioselective synthesis of anti-β-hydroxy-α-amido esters via transfer hydrogenation.

PubMed

Seashore-Ludlow, Brinton; Villo, Piret; Häcker, Christine; Somfai, Peter

2010-11-19

The asymmetric transfer hydrogenation of α-amido-β-keto esters to provide the corresponding anti-β-hydroxy-α-amido esters in good to excellent yields, diastereoselectivity, and enantioselectivity is reported. The procedure is operationally simple, and delicate handling of the catalyst is not necessary.

Magnetic Silica-Supported Ruthenium Nanoparticles: An Efficient Catalyst for Transfer Hydrogenation of Carbonyl Compounds

EPA Science Inventory

One-pot synthesis of ruthenium nanoparticles on magnetic silica is described which involve the in situ generation of magnetic silica (Fe3O4@ SiO2) and ruthenium nano particles immobilization; the hydration of nitriles and transfer hydrogenation of carbonyl compounds occurs in hi...

Synthesis and Functional Reconstitution of Light-Harvesting Complex II into Polymeric Membrane Architectures.

PubMed

Zapf, Thomas; Tan, Cherng-Wen Darren; Reinelt, Tobias; Huber, Christoph; Shaohua, Ding; Geifman-Shochat, Susana; Paulsen, Harald; Sinner, Eva-Kathrin

2015-12-01

One of most important processes in nature is the harvesting and dissipation of solar energy with the help of light-harvesting complex II (LHCII). This protein, along with its associated pigments, is the main solar-energy collector in higher plants. We aimed to generate stable, highly controllable, and sustainable polymer-based membrane systems containing LHCII-pigment complexes ready for light harvesting. LHCII was produced by cell-free protein synthesis based on wheat-germ extract, and the successful integration of LHCII and its pigments into different membrane architectures was monitored. The unidirectionality of LHCII insertion was investigated by protease digestion assays. Fluorescence measurements indicated chlorophyll integration in the presence of LHCII in spherical as well as planar bilayer architectures. Surface plasmon enhanced fluorescence spectroscopy (SPFS) was used to reveal energy transfer from chlorophyll b to chlorophyll a, which indicates native folding of the LHCII proteins. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

tRNA travels from the cytoplasm to organelles

PubMed Central

Rubio, Mary Anne T.; Hopper, Anita K.

2011-01-01

Transfer RNAs (tRNAs) encoded by the nuclear genome are surprisingly dynamic. Although tRNAs function in protein synthesis occurring on cytoplasmic ribosomes, tRNAs can transit from the cytoplasm to the nucleus and then again return to the cytoplasm by a process known as the tRNA retrograde process. Subsets of the cytoplasmic tRNAs are also imported into mitochondria and function in mitochondrial protein synthesis. The numbers of tRNA species that are imported into mitchondria differ among organisms, ranging from just a few to the entire set needed to decode mitochondrially encoded mRNAs. For some tRNAs, import is dependent on the mitochondrial protein import machinery, whereas the majority of tRNA mitochondrial import is independent of this machinery. Although cytoplasmic proteins and proteins located on the mitochondrial surface participating in the tRNA import process have been described for several organisms, the identity of these proteins differ among organisms. Likewise, the tRNA determinants required for mitochondrial import differ among tRNA species and organisms. Here, we present an overview and discuss the current state of knowledge regarding the mechanisms involved in the tRNA retrograde process and continue with an overview of tRNA import into mitochondria. Finally, we highlight areas of future research to understand the function and regulation of movement of tRNAs between the cytoplasm and organelles. PMID:21976284

Alcohols as alkylating agents in heteroarene C–H functionalization

PubMed Central

Jin, Jian; MacMillan, David W. C.

2015-01-01

Redox processes and radical intermediates are found in many biochemical processes, including deoxyribonucleotide synthesis and oxidative DNA damage1. One of the core principles that underlies DNA biosynthesis is the radical-mediated elimnation of H2O to deoxygenate ribonucleotides, an example of ‘spin-center shift’ (SCS)2, during which an alcohol C–O bond is cleaved, resulting in a carbon-centered radical intermediate. While SCS is a well-understood biochemical process, it is underutilized by the synthetic organic chemistry community. We wondered whether it would be possible to take advantage of this naturally occurring process to accomplish mild, non-traditional alkylations using alcohols as radical precursors. Considering traditional radical-based alkylation methods require the use of stoichiometric oxidants, elevated temperatures, or peroxides3–7, the development of a mild protocol using simple and abundant alkylating agents would have significant utility in the synthesis of diversely functionalized pharmacophores. In this manuscript, we describe the successful execution of this idea via the development of a dual catalytic alkylation of heteroarenes using alcohols as mild alkylating reagents. This method represents the first broadly applicable use of unactivated alcohols as latent alkylating reagents, achieved via the successful merger of photoredox and hydrogen atom transfer (HAT) catalysis. The utility of this multi-catalytic protocol has been demonstrated through the late-stage functionalization of the medicinal agents, fasudil and milrinone. PMID:26308895

Advanced space program studies. Overall executive summary

NASA Technical Reports Server (NTRS)

Wolfe, M. G.

1977-01-01

NASA and DoD requirements and planning data were used in multidiscipline advanced planning investigations of space operations and associated elements (including man), identification of potential low cost approaches, vehicle design, cost synthesis techniques, technology forecasting and opportunities for DoD technology transfer, and the development near-, mid-, and far-term space initiatives and development plans with emphasis on domestic and military commonality. An overview of objectives and results are presented for the following studies: advanced space planning and conceptual analysis, shuttle users, technology assessment and new opportunities, standardization and program practice, integrated STS operations planning, solid spinning upper stage, and integrated planning support functions.

Demonstration of neuron-glia transfer of precursors for GABA biosynthesis in a co-culture system of dissociated mouse cerebral cortex.

PubMed

Leke, Renata; Bak, Lasse K; Schousboe, Arne; Waagepetersen, Helle S

2008-12-01

Co-cultures of neurons and astrocytes were prepared from dissociated embryonic mouse cerebral cortex and cultured for 7 days. To investigate if these cultures may serve as a functional model system to study neuron-glia interaction with regard to GABA biosynthesis, the cells were incubated either in media containing [U-(13)C]glutamine (0.1, 0.3 and 0.5 mM) or 1 mM acetate plus 2.5 mM glucose plus 1 mM lactate. In the latter case one of the 3 substrates was uniformly (13)C labeled. Cellular contents and (13)C labeling of glutamate, GABA, aspartate and glutamine were determined in the cells after an incubation period of 2.5 h. The GABA biosynthetic machinery exhibited the expected complexity with regard to metabolic compartmentation and involvement of TCA cycle activity as seen in other culture systems containing GABAergic neurons. Metabolism of acetate clearly demonstrated glial synthesis of glutamine and its transfer to the neuronal compartment. It is concluded that this co-culture system serves as a reliable model in which functional and pharmacological aspects of GABA biosynthesis can be investigated.

31P-Magnetization Transfer Magnetic Resonance Spectroscopy Measurements of In Vivo Metabolism

PubMed Central

Befroy, Douglas E.; Rothman, Douglas L.; Petersen, Kitt Falk; Shulman, Gerald I.

2012-01-01

Magnetic resonance spectroscopy offers a broad range of noninvasive analytical methods for investigating metabolism in vivo. Of these, the magnetization-transfer (MT) techniques permit the estimation of the unidirectional fluxes associated with metabolic exchange reactions. Phosphorus (31P) MT measurements can be used to examine the bioenergetic reactions of the creatine-kinase system and the ATP synthesis/hydrolysis cycle. Observations from our group and others suggest that the inorganic phosphate (Pi) → ATP flux in skeletal muscle may be modulated by certain conditions, including aging, insulin resistance, and diabetes, and may reflect inherent alterations in mitochondrial metabolism. However, such effects on the Pi → ATP flux are not universally observed under conditions in which mitochondrial function, assessed by other techniques, is impaired, and recent articles have raised concerns about the absolute magnitude of the measured reaction rates. As the application of 31P-MT techniques becomes more widespread, this article reviews the methodology and outlines our experience with its implementation in a variety of models in vivo. Also discussed are potential limitations of the technique, complementary methods for assessing oxidative metabolism, and whether the Pi → ATP flux is a viable biomarker of metabolic function in vivo. PMID:23093656

Redox-Active Star Molecules Incorporating the 4-Benzoylpyridinium Cation - Implications for the Charge Transfer Along Branches vs. Across the Perimeter in Dendrimer

NASA Technical Reports Server (NTRS)

Leventis, Nicholas; Yang, Jinua; Fabrizio,Even F.; Rawashdeh, Abdel-Monem M.; Oh, Woon Su; Sotiriou-Leventis, Chariklia

2004-01-01

Dendrimers are self-repeating globular branched star molecules, whose fractal structure continues to fascinate, challenge, and inspire. Functional dendrimers may incorporate redox centers, and potential applications include antennae molecules for light harvesting, sensors, mediators, and artificial biomolecules. We report the synthesis and redox properties of four star systems incorporating the 4-benzoyl-N-alkylpyridinium cation; the redox potential varies along the branches but remains constant at fixed radii. Bulk electrolysis shows that at a semi-infinite time scale all redox centers are electrochemically accessible. However, voltammetric analysis (cyclic voltammetry and differential pulse voltammetry) shows that on1y two of the three redox-active centers in the perimeter are electrochemically accessible during potential sweeps as slow as 20 mV/s and as fast as 10 V/s. On the contrary, both redox centers along branches are accessible electrochemically within the same time frame. These results are explained in terms of slow through-space charge transfer and the globular 3-D folding of the molecules and are discussed in terms of their implications on the design of efficient redox functional dendrimers.

Insights into proton translocation in cbb3 oxidase from MD simulations.

PubMed

Carvalheda, Catarina A; Pisliakov, Andrei V

2017-05-01

Heme-copper oxidases are membrane protein complexes that catalyse the final step of the aerobic respiration, namely the reduction of oxygen to water. The energy released during catalysis is coupled to the active translocation of protons across the membrane, which contributes to the establishment of an electrochemical gradient that is used for ATP synthesis. The distinctive C-type (or cbb 3 ) cytochrome c oxidases, which are mostly present in proteobacteria, exhibit a number of unique structural and functional features, including high catalytic activity at low oxygen concentrations. At the moment, the functioning mechanism of C-type oxidases, in particular the proton transfer/pumping mechanism presumably via a single proton channel, is still poorly understood. In this work we used all-atom molecular dynamics simulations and continuum electrostatics calculations to obtain atomic-level insights into the hydration and dynamics of a cbb 3 oxidase. We provide the details of the water dynamics and proton transfer pathways for both the "chemical" and "pumped" protons, and show that formation of protonic connections is strongly affected by the protonation state of key residues, namely H243, E323 and H337. Copyright © 2017 Elsevier B.V. All rights reserved.

Automating multistep flow synthesis: approach and challenges in integrating chemistry, machines and logic

PubMed Central

Shukla, Chinmay A

2017-01-01

The implementation of automation in the multistep flow synthesis is essential for transforming laboratory-scale chemistry into a reliable industrial process. In this review, we briefly introduce the role of automation based on its application in synthesis viz. auto sampling and inline monitoring, optimization and process control. Subsequently, we have critically reviewed a few multistep flow synthesis and suggested a possible control strategy to be implemented so that it helps to reliably transfer the laboratory-scale synthesis strategy to a pilot scale at its optimum conditions. Due to the vast literature in multistep synthesis, we have classified the literature and have identified the case studies based on few criteria viz. type of reaction, heating methods, processes involving in-line separation units, telescopic synthesis, processes involving in-line quenching and process with the smallest time scale of operation. This classification will cover the broader range in the multistep synthesis literature. PMID:28684977

Value-added Synthesis of Graphene: Recycling Industrial Carbon Waste into Electrodes for High-Performance Electronic Devices

PubMed Central

Seo, Hong-Kyu; Kim, Tae-Sik; Park, Chibeom; Xu, Wentao; Baek, Kangkyun; Bae, Sang-Hoon; Ahn, Jong-Hyun; Kim, Kimoon; Choi, Hee Cheul; Lee, Tae-Woo

2015-01-01

We have developed a simple, scalable, transfer-free, ecologically sustainable, value-added method to convert inexpensive coal tar pitch to patterned graphene films directly on device substrates. The method, which does not require an additional transfer process, enables direct growth of graphene films on device substrates in large area. To demonstrate the practical applications of the graphene films, we used the patterned graphene grown on a dielectric substrate directly as electrodes of bottom-contact pentacene field-effect transistors (max. field effect mobility ~0.36 cm2·V−1·s−1), without using any physical transfer process. This use of a chemical waste product as a solid carbon source instead of commonly used explosive hydrocarbon gas sources for graphene synthesis has the dual benefits of converting the waste to a valuable product, and reducing pollution. PMID:26567845

Value-added Synthesis of Graphene: Recycling Industrial Carbon Waste into Electrodes for High-Performance Electronic Devices

NASA Astrophysics Data System (ADS)

Seo, Hong-Kyu; Kim, Tae-Sik; Park, Chibeom; Xu, Wentao; Baek, Kangkyun; Bae, Sang-Hoon; Ahn, Jong-Hyun; Kim, Kimoon; Choi, Hee Cheul; Lee, Tae-Woo

2015-11-01

We have developed a simple, scalable, transfer-free, ecologically sustainable, value-added method to convert inexpensive coal tar pitch to patterned graphene films directly on device substrates. The method, which does not require an additional transfer process, enables direct growth of graphene films on device substrates in large area. To demonstrate the practical applications of the graphene films, we used the patterned graphene grown on a dielectric substrate directly as electrodes of bottom-contact pentacene field-effect transistors (max. field effect mobility ~0.36 cm2·V-1·s-1), without using any physical transfer process. This use of a chemical waste product as a solid carbon source instead of commonly used explosive hydrocarbon gas sources for graphene synthesis has the dual benefits of converting the waste to a valuable product, and reducing pollution.

Value-added Synthesis of Graphene: Recycling Industrial Carbon Waste into Electrodes for High-Performance Electronic Devices.

PubMed

Seo, Hong-Kyu; Kim, Tae-Sik; Park, Chibeom; Xu, Wentao; Baek, Kangkyun; Bae, Sang-Hoon; Ahn, Jong-Hyun; Kim, Kimoon; Choi, Hee Cheul; Lee, Tae-Woo

2015-11-16

We have developed a simple, scalable, transfer-free, ecologically sustainable, value-added method to convert inexpensive coal tar pitch to patterned graphene films directly on device substrates. The method, which does not require an additional transfer process, enables direct growth of graphene films on device substrates in large area. To demonstrate the practical applications of the graphene films, we used the patterned graphene grown on a dielectric substrate directly as electrodes of bottom-contact pentacene field-effect transistors (max. field effect mobility ~0.36 cm(2)·V(-1)·s(-1)), without using any physical transfer process. This use of a chemical waste product as a solid carbon source instead of commonly used explosive hydrocarbon gas sources for graphene synthesis has the dual benefits of converting the waste to a valuable product, and reducing pollution.

Light- induced electron transfer and ATP synthesis in a carotene synthesizing insect

NASA Astrophysics Data System (ADS)

Valmalette, Jean Christophe; Dombrovsky, Aviv; Brat, Pierre; Mertz, Christian; Capovilla, Maria; Robichon, Alain

2012-08-01

A singular adaptive phenotype of a parthenogenetic insect species (Acyrthosiphon pisum) was selected in cold conditions and is characterized by a remarkable apparition of a greenish colour. The aphid pigments involve carotenoid genes well defined in chloroplasts and cyanobacteria and amazingly present in the aphid genome, likely by lateral transfer during evolution. The abundant carotenoid synthesis in aphids suggests strongly that a major and unknown physiological role is related to these compounds beyond their canonical anti-oxidant properties. We report here that the capture of light energy in living aphids results in the photo induced electron transfer from excited chromophores to acceptor molecules. The redox potentials of molecules involved in this process would be compatible with the reduction of the NAD+ coenzyme. This appears as an archaic photosynthetic system consisting of photo-emitted electrons that are in fine funnelled into the mitochondrial reducing power in order to synthesize ATP molecules.

Protein migration from transplanted nuclei in Amoeba proteus. I. The relation to the cell cycle and RNA migration, as studied by autoradiography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mills, K.I.; Bell, L.G.

1982-11-01

Autoradiography has been used to examine the migration of proteins from a radioactivity labelled amoeba nucleus following transplantation into an unlabelled homophasic amoeba. Nuclei were transferred at three times in the cell cycle coinciding with DNA synthesis (4 h post-division); a peak of RNA synthesis (25 h); and a relative lull in synthetic activity (43 h). Six amino acids were added individually to the culture medium to label the nuclear proteins. Migration of the proteins from the donor nucleui and least with proteins labelled with the basic amino acids. All amino acids exhibited the greatest extent of migration following themore » 25-h transfers, i.e., coinciding with a peak of RNA synthesis at 26-27.5 h. Actinomycin D (actD) inhibition of RNA synthesis reduced, but did not eliminate the extent of protein migration from the transplanted nucleus, thus indicating the existence of two classes of migratory proteins. Firstly, proteins, associated with RNA transport, which migrated mainly into the host cytoplasm. The second class migrated into the host nucleus from the transplanted nucleus, irrespective of RNA synthesis. The shuttling character of the latter class of proteins is consistent with a role of regulation of nuclear activity.« less

Precursor Ion–Ion Aggregation in the Brust–Schiffrin Synthesis of Alkanethiol Nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Graham, Trent R.; Renslow, Ryan; Govind, Niranjan

Tetraoctylammonium bromide is used in the Brust-Schiffrin nanoparticle synthesis to phase-transfer chloroaurate ions from the aqueous phase to the organic phase. While it is established that the quaternary ammonium complex self-associates in the organic phase, the actual self-assembled structure is debated. We have confirmed the presence of ion-ion aggregates through quantitative 1H Nuclear Magnetic Resonance spectroscopy (NMR), pulsed field gradient, diffusion-ordered NMR (DOSY-NMR) and density functional theory (DFT) based NMR shift calculations. Tetraoctylammonium complexes (TOA-X, where X = Br, Cl, AuCl4-xBrx, AuBr4/Br and AuCl4-xBrx/Br) were investigated to measure the extraction of water into the organic phase. 1H NMR and DFTmore » based NMR shielding calculations indicated that deshielding of water is due to hydration of the anion and not the formation of the aqueous core of a reverse micelle. DOSYNMR results were consistent with the formation of small aggregates at typical Brust-Schiffrin synthesis concentrations. The extent of aggregation correlated with the size and electronegativity of the anion and was analyzed with a modified, isodesmic, indefinite aggregation model. The substitution of bromoauric acid for chlororoauric acid at conditions emulating the Brust-Schiffrin synthesis increased the aggregation of the quaternary ammonium complex. The increase in aggregation corresponded with an increase in the size of the produced nanoparticles from 4.3 to 4.6 nm. Understanding the selfassembly and supramolecular structure of precursors in the Brust-Schiffrin synthesis will enable further refinement of models that predict the growth of noble metal nanoparticles.« less

Synthesis of Fuels and Value-Added Nitrogen-Containing Compounds from N2

DTIC Science & Technology

2014-11-24

The Haber - Bosch ammonia synthesis is one of the great technological achievements of the 20th century, having revolutionized agriculture and hence the...catalytic synthesis of ammonia or hydrazine compatible with renewable (CO2-free) hydrogen. N Ph N Ph N V Ar iPr iPr N THF N N Ph N Ph N V Ar Ar THF...atom transfer from renewable H2. Concurrent with these efforts, we have also been exploring related molybdenum platforms for ammonia oxidation. The

Quinazoline derivatives: synthesis and bioactivities

PubMed Central

2013-01-01

Owing to the significant biological activities, quinazoline derivatives have drawn more and more attention in the synthesis and bioactivities research. This review summarizes the recent advances in the synthesis and biological activities investigations of quinazoline derivatives. According to the main method the authors adopted in their research design, those synthetic methods were divided into five main classifications, including Aza-reaction, Microwave-assisted reaction, Metal-mediated reaction, Ultrasound-promoted reaction and Phase-transfer catalysis reaction. The biological activities of the synthesized quinazoline derivatives also are discussed. PMID:23731671

Functional copolymer/organo-MMT nanoarchitectures. VI. Synthesis and characterization of novel nanocomposites by interlamellar controlled/living radical copolymerization via preintercalated RAFT-agent/organoclay complexes.

PubMed

Rzayev, Zakir M O; Söylemez, A Ernur

2011-04-01

We have developed a new approach for the synthesis of polymer nanocomposites using a bifunctional reversible addition-fragmentation chain transfer (RAFT) agent, two types of organo-montmorillonites, such as a non-reactive dimethyldodecyl ammonium (DMDA)-MMT and a reactive octadecylamine (ODA)-MMT organoclays, and a radical initiator. The method includes the following stages: (1) synthesis of RAFT intercalated O-MMTs by a physical or chemical interaction of the RAFT agent having two pendant carboxylic groups [S,S-bis(alpha,alpha'-dimethyl-alpha"-acetic acid)trithiocarbonate] with surface alkyl amines of O-MMT containing tertiary ammonium cation or primary amine groups through strong H-bonding and complexing/amidization reactions, respectively, and (2) utilization of these well-dispersed and intercalated RAFT ... O-MMT complexes and their amide derivatives as new modified RAFT agents in radical-initiated interlamellar controlled/living copolymerization of itaconic acid (IA)-n-butylmethacrylate (BMA) monomer pair. The structure and compositions of the synthesized RAFT ... O-MMT complexes and functional copolymer/O-MMT hybrids were confirmed by FTIR, XRD, thermal (DSC-TGA), SEM and TEM morphology analyses. It was demonstrated that the degree of interaction/exfoliation, morphology and thermal behavior of nanocomposites significantly depended on the type of organoclay and in situ interaction, as well as on the content of flexible butyl-ester linkages as a internal plasticizer. The results of the comparative analysis of the nanocomposites structure-composition-property relations show that the functional copolymer-organoclay hybrids prepared with reactive RAFT ... ODA-MMT complex and containing a combination of partially intercalated and predominantly exfoliated nano-structures exhibit relatively higher thermal stability and fine dispersed morphology. These effects were explained by in situ interfacial chemical reactions through amidization of RAFT with surface alkyl amine of MMT clay in interlamellar copolymerization. This simple and versatile method can be applied to a wide range of functional monomer/comonomer systems and mono- and bifunctional RAFT compounds for preparation new generation of nanomaterials.

Synthesis and Hydrogenation of Disubstituted Chalcones: A Guided-Inquiry Organic Chemistry Project

ERIC Educational Resources Information Center

Mohrig, Jerry R.; Hammond, Christina Noring; Schatz, Paul F.; Davidson, Tammy A.

2009-01-01

Guided-inquiry experiments offer the same opportunities to participate in the process of science as classical organic qualitative analysis used to do. This three-week guided-inquiry project involves an aldol-dehydration synthesis of a chalcone chosen from a set of nine, followed by a catalytic transfer hydrogenation reaction using ammonium formate…

WATER-BORNE BLOCK COPOLYMER SYNTHESIS AND A SIMPLE AND EFFECTIVE ONE-POT SYNTHESIS OF ACRYLATE-METHACRYLATE BLOCK COPOLYMERS BY ATOM TRANSFER RADICAL POLYMERIZATION. (R826735)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

A meta-synthesis of factors influencing nursing home staff decisions to transfer residents to hospital.

PubMed

Laging, Bridget; Ford, Rosemary; Bauer, Michael; Nay, Rhonda

2015-10-01

To report a meta-synthesis of qualitative research studies exploring the role of nursing home staff in decisions to transfer residents to hospital. Nurses and nurse assistants provide the majority of care to residents living in nursing homes and may be the only health workers present when a resident deteriorates. To inform future strategies, it is vital to understand the role of nursing home staff in decisions to transfer to hospital. A systematic review identified 17 studies to be included. The process of meta-synthesis was undertaken using the Joanna Briggs Institute's guidelines. Qualitative research papers published between January 1989-October 2012 were identified in key databases including Cinahl, Embase, Medline and PsycInfo. Nursing home staff members play a key role in decision-making at the time of a resident's deterioration. Multiple factors influence decisions to transfer to hospital including an unclear expectation of the nursing home role; limited staffing capacity; fear of working outside their scope of practice; poor access to multidisciplinary support and difficulties communicating with other decision-makers. There is a lack of consensus regarding the role of the nursing home when a resident's health deteriorates. Nursing home staff would benefit from a clear prescription of their expected minimum clinical skill set; a staffing capacity that allows for the increased requirements to manage residents on-site, greater consistency in access to outside resources and further confidence and skills to optimize their role in resident advocacy. © 2015 John Wiley & Sons Ltd.

Information transfer satellite concept study. Volume 3: Appendices

NASA Technical Reports Server (NTRS)

Bergin, P.; Kincade, C.; Kurpiewski, D.; Leinhaupel, F.; Millican, F.; Onstad, R.

1971-01-01

Briefly reviewed are the various documents which supply background information for the information transfer satellite study. The sixteen papers reviewed are evaluated in terms of: (1) the category of service or demand being treated; (2) the extent to which information transfer predictions are quantified; (3) the degree to which the data supplied is adequate for the purposes of system synthesis; (4) some assessment as to the overall utility of the data presented in the paper.

Intramolecular Charge Transfer of Conjugated Liquid Crystal Ferrocene Macromolecules - Synthesis and Characterization

DTIC Science & Technology

2016-04-12

AFRL-AFOSR-CL-TR-2016-0012 Intramolecular Charge Transfer of Conjugated Liquid Crystal Ferrocene Macromolecules Ronald Ziolo CIQA Final Report 07/07...3. DATES COVERED (From - To)  15 Aug 2014 to 14 Jan 2016 4. TITLE AND SUBTITLE Intramolecular Charge Transfer of Conjugated Liquid Crystal Ferrocene...characterization of a new series of conjugated macromolecules bearing ferrocene as a highly efficient electron donor material coupled to 2,5-di(alcoxy) benzene

A Report on Transfers from L.A.C.C. to the Various Campuses of the California State University and Colleges, 1976-1977. Research Study #77-11.

ERIC Educational Resources Information Center

Gold, Ben K.

In 1976-77, Los Angeles City College (LACC) received the annual reports from 14 of the 19 campuses of the California State University and College System on the performance of LACC transfers. A synthesis of these reports produced the following highlights: (1) 856 transfers were reported; (2) the Los Angeles (65%), Northridge (17%), Long Beach (7%),…

Valence and charge-transfer optical properties for some SinCm (m, n ≤ 12) clusters: Comparing TD-DFT, complete-basis-limit EOMCC, and benchmarks from spectroscopy.

PubMed

Lutz, Jesse J; Duan, Xiaofeng F; Ranasinghe, Duminda S; Jin, Yifan; Margraf, Johannes T; Perera, Ajith; Burggraf, Larry W; Bartlett, Rodney J

2018-05-07

Accurate optical characterization of the closo-Si 12 C 12 molecule is important to guide experimental efforts toward the synthesis of nano-wires, cyclic nano-arrays, and related array structures, which are anticipated to be robust and efficient exciton materials for opto-electronic devices. Working toward calibrated methods for the description of closo-Si 12 C 12 oligomers, various electronic structure approaches are evaluated for their ability to reproduce measured optical transitions of the SiC 2 , Si 2 C n (n = 1-3), and Si 3 C n (n = 1, 2) clusters reported earlier by Steglich and Maier [Astrophys. J. 801, 119 (2015)]. Complete-basis-limit equation-of-motion coupled-cluster (EOMCC) results are presented and a comparison is made between perturbative and renormalized non-iterative triples corrections. The effect of adding a renormalized correction for quadruples is also tested. Benchmark test sets derived from both measurement and high-level EOMCC calculations are then used to evaluate the performance of a variety of density functionals within the time-dependent density functional theory (TD-DFT) framework. The best-performing functionals are subsequently applied to predict valence TD-DFT excitation energies for the lowest-energy isomers of Si n C and Si n-1 C 7-n (n = 4-6). TD-DFT approaches are then applied to the Si n C n (n = 4-12) clusters and unique spectroscopic signatures of closo-Si 12 C 12 are discussed. Finally, various long-range corrected density functionals, including those from the CAM-QTP family, are applied to a charge-transfer excitation in a cyclic (Si 4 C 4 ) 4 oligomer. Approaches for gauging the extent of charge-transfer character are also tested and EOMCC results are used to benchmark functionals and make recommendations.

Synthesis of selenium nano-composite (t-Se@PS) by surface initiated atom transfer radical polymerization.

PubMed

Wang, Michael C P; Gates, Byron D

2012-09-04

Selenium nanostructures, which are otherwise susceptible to oxidative damage, were encapsulated with a thin layer of polystyrene. The thin layer of polystyrene was grafted onto the surfaces of selenium by a surface initiated atom transfer radical polymerization reaction. These encapsulated nanostructures demonstrate an enhanced resistance towards corrosion.

ATP Synthesis in the Extremely Halophilic Bacteria

NASA Technical Reports Server (NTRS)

Hochstein, Lawrence I.; Morrison, David (Technical Monitor)

1994-01-01

The proton-translocating ATPases are multimeric enzymes that carry out a multitude of essential functions. Their origin and evolution represent a seminal event in the early evolution of life. Amino acid sequences of the two largest subunits from archaeal ATPases (A-ATPases), vacuolar ATPases (V-ATPases), and FOF1-ATP syntheses (FATPases) suggest these ATPases evolved from an ancestral vacuolar-like ATP syntheses. A necessary consequence of this notion is that the A-ATPases are ATP syntheses. With the possible exception of the A-ATPase from Halobacterium salinarium. no A-ATPase has been demonstrated to synthesize ATP. The evidence for this case is dubious since ATP synthesis occurs only when conditions are distinctively unphysiological. We demonstrated that ATP synthesis in H.saccharovorum is inconsistent with the operation of an A-type ATPase. In order to determine if this phenomenon was unique to H. saccharovorum, ATP synthesis was examined in various extremely halophilic bacteria with the goal of ascertaining if it resembled what occurred in a. saccharovorum, or was consistent with the operation of an A-type ATPase. A-, V-, and F-type ATPases respond singularly to certain inhibitors. Therefore, the effect of these inhibitors on ATP synthesis in several extreme halophiles was determined. Inhibitors that either blocked or collapsed proton-gradients inhibited the steady state synthesis of ATP thus verifying that synthesis took place at the expense of a proton gradient. Azide, an inhibitor of F-ATPases inhibited ATP synthesis. Since the arginine-dependent synthesis of ATP, which occurs by way of substrate-level phosphorylation, was unaffected by azide, it was unlikely that azide acted as an "uncoupler." N -ethylmaleimide and nitrate, which inhibit V- and A-ATPases, either did not inhibit ATP synthesis or resulted in higher steady-state levels of ATP. These results suggest there are two types of proton-motive ATPases in the extreme halophiles (and presumably in other Archaea). One, the V-like enzyme which, provides protons that are subsequently used for solute translocation. The other ATPase is the familiar and ubiquitous F-ATPase that functions as a reversible proton pump and is the ATP Synthase in the extreme halophiles. Thus, while the suggested evolution of the proton -translocating ATPases accounts for the relationship among these ATPases, this scheme does not account for the presence of F-ATPases in the Archaea. Discounting lateral gene transfer, perhaps an F-type ATPase evolved before the eucaryal-archaeal and bacterial bifurcation. The presence of V-type ATPases in the Bacterial Domain is consistent with this suggestion. Finally, it is of interest to note that if an F-type ATPase appeared before the bifurcation, an endosymbiotic event need not be invoked to explain the presence of F-ATPases in the Eucarya.

Evidence for a "metabolically inactive" inorganic phosphate pool in adenosine triphosphate synthase reaction using localized 31P saturation transfer magnetic resonance spectroscopy in the rat brain at 11.7 T.

PubMed

Tiret, Brice; Brouillet, Emmanuel; Valette, Julien

2016-09-01

With the increased spectral resolution made possible at high fields, a second, smaller inorganic phosphate resonance can be resolved on (31)P magnetic resonance spectra in the rat brain. Saturation transfer was used to estimate de novo adenosine triphosphate synthesis reaction rate. While the main inorganic phosphate pool is used by adenosine triphosphate synthase, the second pool is inactive for this reaction. Accounting for this new pool may not only help us understand (31)P magnetic resonance spectroscopy metabolic profiles better but also better quantify adenosine triphosphate synthesis. © The Author(s) 2016.

Transfer of metabolites across the peroxisomal membrane.

PubMed

Antonenkov, Vasily D; Hiltunen, J Kalervo

2012-09-01

Peroxisomes perform a large variety of metabolic functions that require a constant flow of metabolites across the membranes of these organelles. Over the last few years it has become clear that the transport machinery of the peroxisomal membrane is a unique biological entity since it includes nonselective channels conducting small solutes side by side with transporters for 'bulky' solutes such as ATP. Electrophysiological experiments revealed several channel-forming activities in preparations of plant, mammalian, and yeast peroxisomes and in glycosomes of Trypanosoma brucei. The properties of the first discovered peroxisomal membrane channel - mammalian Pxmp2 protein - have also been characterized. The channels are apparently involved in the formation of peroxisomal shuttle systems and in the transmembrane transfer of various water-soluble metabolites including products of peroxisomal β-oxidation. These products are processed by a large set of peroxisomal enzymes including carnitine acyltransferases, enzymes involved in the synthesis of ketone bodies, thioesterases, and others. This review discusses recent data pertaining to solute permeability and metabolite transport systems in peroxisomal membranes and also addresses mechanisms responsible for the transfer of ATP and cofactors such as an ATP transporter and nudix hydrolases. Copyright © 2012 Elsevier B.V. All rights reserved.

The Endoplasmic Reticulum Coat Protein II Transport Machinery Coordinates Cellular Lipid Secretion and Cholesterol Biosynthesis*

PubMed Central

Fryer, Lee G. D.; Jones, Bethan; Duncan, Emma J.; Hutchison, Claire E.; Ozkan, Tozen; Williams, Paul A.; Alder, Olivia; Nieuwdorp, Max; Townley, Anna K.; Mensenkamp, Arjen R.; Stephens, David J.; Dallinga-Thie, Geesje M.; Shoulders, Carol C.

2014-01-01

Triglycerides and cholesterol are essential for life in most organisms. Triglycerides serve as the principal energy storage depot and, where vascular systems exist, as a means of energy transport. Cholesterol is essential for the functional integrity of all cellular membrane systems. The endoplasmic reticulum is the site of secretory lipoprotein production and de novo cholesterol synthesis, yet little is known about how these activities are coordinated with each other or with the activity of the COPII machinery, which transports endoplasmic reticulum cargo to the Golgi. The Sar1B component of this machinery is mutated in chylomicron retention disorder, indicating that this Sar1 isoform secures delivery of dietary lipids into the circulation. However, it is not known why some patients with chylomicron retention disorder develop hepatic steatosis, despite impaired intestinal fat malabsorption, and why very severe hypocholesterolemia develops in this condition. Here, we show that Sar1B also promotes hepatic apolipoprotein (apo) B lipoprotein secretion and that this promoting activity is coordinated with the processes regulating apoB expression and the transfer of triglycerides/cholesterol moieties onto this large lipid transport protein. We also show that although Sar1A antagonizes the lipoprotein secretion-promoting activity of Sar1B, both isoforms modulate the expression of genes encoding cholesterol biosynthetic enzymes and the synthesis of cholesterol de novo. These results not only establish that Sar1B promotes the secretion of hepatic lipids but also adds regulation of cholesterol synthesis to Sar1B's repertoire of transport functions. PMID:24338480

Synthesis of Stable Interfaces on SnO2 Surfaces for Charge-Transfer Applications

NASA Astrophysics Data System (ADS)

Benson, Michelle C.

The commercial market for solar harvesting devices as an alternative energy source requires them to be both low-cost and efficient to replace or reduce the dependence on fossil fuel burning. Over the last few decades there has been promising efforts towards improving solar devices by using abundant and non-toxic metal oxide nanomaterials. One particular metal oxide of interest has been SnO2 due to its high electron mobility, wide-band gap, and aqueous stability. However SnO2 based solar cells have yet to reach efficiency values of other metal oxides, like TiO2. The advancement of SnO2 based devices is dependent on many factors, including improved methods of surface functionalization that can yield stable interfaces. This work explores the use of a versatile functionalization method through the use of the Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. The CuAAC reaction is capable of producing electrochemically, photochemically, and electrocatalytically active surfaces on a variety of SnO2 materials. The resulting charge-transfer characteristics were investigated as well as an emphasis on understanding the stability of the resulting molecular linkage. We determined the CuAAC reaction is able to proceed through both azide-modified and alkyne-modified surfaces. The resulting charge-transfer properties showed that the molecular tether was capable of supporting charge separation at the interface. We also investigated the enhancement of electron injection upon the introduction of an ultra-thin ZrO2 coating on SnO2. Several complexes were used to fully understand the charge-transfer capabilities, including model systems of ferrocene and a ruthenium coordination complex, a ruthenium mononuclear water oxidation catalyst, and a commercial ruthenium based dye.

Catalytic alkylation of remote C-H bonds enabled by proton-coupled electron transfer

NASA Astrophysics Data System (ADS)

Choi, Gilbert J.; Zhu, Qilei; Miller, David C.; Gu, Carol J.; Knowles, Robert R.

2016-11-01

Despite advances in hydrogen atom transfer (HAT) catalysis, there are currently no molecular HAT catalysts that are capable of homolysing the strong nitrogen-hydrogen (N-H) bonds of N-alkyl amides. The motivation to develop amide homolysis protocols stems from the utility of the resultant amidyl radicals, which are involved in various synthetically useful transformations, including olefin amination and directed carbon-hydrogen (C-H) bond functionalization. In the latter process—a subset of the classical Hofmann-Löffler-Freytag reaction—amidyl radicals remove hydrogen atoms from unactivated aliphatic C-H bonds. Although powerful, these transformations typically require oxidative N-prefunctionalization of the amide starting materials to achieve efficient amidyl generation. Moreover, because these N-activating groups are often incorporated into the final products, these methods are generally not amenable to the direct construction of carbon-carbon (C-C) bonds. Here we report an approach that overcomes these limitations by homolysing the N-H bonds of N-alkyl amides via proton-coupled electron transfer. In this protocol, an excited-state iridium photocatalyst and a weak phosphate base cooperatively serve to remove both a proton and an electron from an amide substrate in a concerted elementary step. The resultant amidyl radical intermediates are shown to promote subsequent C-H abstraction and radical alkylation steps. This C-H alkylation represents a catalytic variant of the Hofmann-Löffler-Freytag reaction, using simple, unfunctionalized amides to direct the formation of new C-C bonds. Given the prevalence of amides in pharmaceuticals and natural products, we anticipate that this method will simplify the synthesis and structural elaboration of amine-containing targets. Moreover, this study demonstrates that concerted proton-coupled electron transfer can enable homolytic activation of common organic functional groups that are energetically inaccessible using traditional HAT-based approaches.

Catalytic alkylation of remote C-H bonds enabled by proton-coupled electron transfer.

PubMed

Choi, Gilbert J; Zhu, Qilei; Miller, David C; Gu, Carol J; Knowles, Robert R

2016-11-10

Despite advances in hydrogen atom transfer (HAT) catalysis, there are currently no molecular HAT catalysts that are capable of homolysing the strong nitrogen-hydrogen (N-H) bonds of N-alkyl amides. The motivation to develop amide homolysis protocols stems from the utility of the resultant amidyl radicals, which are involved in various synthetically useful transformations, including olefin amination and directed carbon-hydrogen (C-H) bond functionalization. In the latter process-a subset of the classical Hofmann-Löffler-Freytag reaction-amidyl radicals remove hydrogen atoms from unactivated aliphatic C-H bonds. Although powerful, these transformations typically require oxidative N-prefunctionalization of the amide starting materials to achieve efficient amidyl generation. Moreover, because these N-activating groups are often incorporated into the final products, these methods are generally not amenable to the direct construction of carbon-carbon (C-C) bonds. Here we report an approach that overcomes these limitations by homolysing the N-H bonds of N-alkyl amides via proton-coupled electron transfer. In this protocol, an excited-state iridium photocatalyst and a weak phosphate base cooperatively serve to remove both a proton and an electron from an amide substrate in a concerted elementary step. The resultant amidyl radical intermediates are shown to promote subsequent C-H abstraction and radical alkylation steps. This C-H alkylation represents a catalytic variant of the Hofmann-Löffler-Freytag reaction, using simple, unfunctionalized amides to direct the formation of new C-C bonds. Given the prevalence of amides in pharmaceuticals and natural products, we anticipate that this method will simplify the synthesis and structural elaboration of amine-containing targets. Moreover, this study demonstrates that concerted proton-coupled electron transfer can enable homolytic activation of common organic functional groups that are energetically inaccessible using traditional HAT-based approaches.

Radical-initiated controlled synthesis of homo- and copolymers based on acrylonitrile

NASA Astrophysics Data System (ADS)

Grishin, D. F.; Grishin, I. D.

2015-07-01

Data on the controlled synthesis of polyacrylonitrile and acrylonitrile copolymers with other (meth)acrylic and vinyl monomers upon radical initiation and metal complex catalysis are analyzed. Primary attention is given to the use of metal complexes for the synthesis of acrylonitrile-based (co)polymers with defined molecular weight and polydispersity in living mode by atom transfer radical polymerization. The prospects for using known methods of controlled synthesis of macromolecules for the preparation of acrylonitrile homo- and copolymers as carbon fibre precursors are estimated. The major array of published data analyzed in the review refers to the last decade. The bibliography includes 175 references.

Interaction between the PH and START domains of ceramide transfer protein competes with phosphatidylinositol 4-phosphate binding by the PH domain

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prashek, Jennifer; Bouyain, Samuel; Fu, Mingui

De novo synthesis of the sphingolipid sphingomyelin requires non-vesicular transport of ceramide from the endoplasmic reticulum to the Golgi by the multidomain protein ceramide transfer protein (CERT). CERT's N-terminal pleckstrin homology (PH) domain targets it to the Golgi by binding to phosphatidylinositol 4-phosphate (PtdIns(4)P) in the Golgi membrane, whereas its C-terminal StAR-related lipid transfer domain (START) carries out ceramide transfer. Hyperphosphorylation of a serine-rich motif immediately after the PH domain decreases both PtdIns(4)P binding and ceramide transfer by CERT. This down-regulation requires both the PH and START domains, suggesting a possible inhibitory interaction between the two domains. In this studymore » we show that isolated PH and START domains interact with each other. The crystal structure of a PH–START complex revealed that the START domain binds to the PH domain at the same site for PtdIns(4)P-binding, suggesting that the START domain competes with PtdIns(4)P for association with the PH domain. We further report that mutations disrupting the PH–START interaction increase both PtdIns(4)P-binding affinity and ceramide transfer activity of a CERT-serine–rich phosphorylation mimic. We also found that these mutations increase the Golgi localization of CERT inside the cell, consistent with enhanced PtdIns(4)P binding of the mutant. Collectively, our structural, biochemical, and cellular investigations provide important structural insight into the regulation of CERT function and localization.« less

A simple single-step approach towards synthesis of nanofluids containing cuboctahedral cuprous oxide particles using glucose reduction

NASA Astrophysics Data System (ADS)

Shenoy, U. Sandhya; Shetty, A. Nityananda

2018-03-01

Enhancement of thermal properties of conventional heat transfer fluids has become one of the important technical challenges. Since nanofluids offer a promising help in this regard, development of simpler and hassle free routes for their synthesis is of utmost importance. Synthesis of nanofluids using a hassle free route with greener chemicals has been reported. The single-step chemical approach reported here overcomes the drawbacks of the two-step procedures in the synthesis of nanofluids. The resulting Newtonian nanofluids prepared contained cuboctahedral particles of cuprous oxide and exhibited a thermal conductivity of 2.852 W·m-1·K-1. Polyvinylpyrrolidone (PVP) used during the synthesis acted as a stabilizing agent rendering the nanofluid a stability of 9 weeks.

Amino Acid Control over Deoxyribonucleic Acid Synthesis in Escherichia coli Infected With T-Even Bacteriophage

PubMed Central

Donini, Pierluigi

1970-01-01

Starvation for a required amino acid of normal or RCstrEscherichia coli infected with T-even phages arrests further synthesis of phage deoxyribonucleic acid (DNA). This amino acid control over phage DNA synthesis does not occur in RCrelE. coli mutants. Heat inactivation of a temperature-sensitive aminoacyl-transfer ribonucleic acid (RNA) synthetase similarly causes an arrest of phage DNA synthesis in infected cells of RCstr phenotype but not in cells of RCrel phenotype. Inhibition of phage DNA synthesis in amino acid-starved RCstr host cells can be reversed by addition of chloramphenicol to the culture. Thus, the general features of amino acid control over T-even phage DNA synthesis are entirely analogous to those known for amino acid control over net RNA synthesis of uninfected bacteria. This analogy shows that the bacterial rel locus controls a wider range of macromolecular syntheses than had been previously thought. PMID:4914067

Density functional theory molecular modeling, chemical synthesis, and antimicrobial behaviour of selected benzimidazole derivatives

NASA Astrophysics Data System (ADS)

Marinescu, Maria; Tudorache, Diana Gabriela; Marton, George Iuliu; Zalaru, Christina-Marie; Popa, Marcela; Chifiriuc, Mariana-Carmen; Stavarache, Cristina-Elena; Constantinescu, Catalin

2017-02-01

Eco-friendly, one-pot, solvent-free synthesis of biologically active 2-substituted benzimidazoles is presented and discussed herein. Novel N-Mannich bases are synthesized from benzimidazoles, secondary amines and formaldehyde, and their structures are confirmed by 1H nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR), and elemental analysis. All benzimidazole derivatives are evaluated by qualitative and quantitative methods against 9 bacterial strains. The largest microbicide and anti-biofilm effect is observed for the 2-(1-hydroxyethyl)-compounds. Density functional theory (DFT) modeling of the molecular structure and frontier molecular orbitals, i.e. highest occupied molecular orbital and lowest unoccupied molecular orbital (HOMO/LUMO), is accomplished by using the GAMESS 2012 software. Antimicrobial activity is correlated with the electronic parameters (chemical hardness, electronic chemical potential, global electrophilicity index), Mullikan atomic charges and geometric parameters of the benzimidazole compounds. The planarity of the compound, symmetry of the molecule, and the presence of a nucleophilic group, are advantages for a high antimicrobial activity. Finally, we briefly show that further accurate processing of such compounds into thin films and hybrid structures, e.g. by laser ablation matrix-assisted pulsed laser evaporation and/or laser-induced forward transfer, may indeed provide simple and environmental friendly, state-of-the-art solutions for antimicrobial coatings.

Density-functional theory study of dimethyl carbonate synthesis by methanol oxidative carbonylation on single-atom Cu1/graphene catalyst

NASA Astrophysics Data System (ADS)

Sun, Wei; Shi, Ruina; Wang, Xuhui; Liu, Shusen; Han, Xiaoxia; Zhao, Chaofan; Li, Zhong; Ren, Jun

2017-12-01

The mechanism for dimethyl carbonate (DMC) synthesis by oxidation carbonylation of methanol on a single-atom Cu1/graphene catalyst was investigated by density-functional theory calculations. Carbon vacancies in graphene can significantly enhance the interaction between Cu atoms and graphene supports, and provide an increased transfer of electrons from Cu atoms to the graphene sheet. Compared with Cu-doped divacancy graphene (Cu/DG), Cu-doped monovacancy graphene (Cu/MG) provides a stronger interaction between adsorbents and the catalyst surface. Among the reaction processes over Cu1/graphene catalysts, CO insertion into methoxide was more favorable than dimethoxide. The rate-limiting step on the Cu/DG surface is the carbomethoxide reaction with methoxide, which is exothermic by 164.6 kJ mol-1 and has an activation barrier of 190.9 kJ mol-1 energy. Compared with that on the Cu crystal surface, Cu4 and Cu3Rh clusters, and the Cu2O(111) surface, the rate-determining step for DMC formation on Cu/MG, which is CO insertion into methoxide, needs to overcome the lowest barrier of 73.5 kJ mol-1 and is exothermic by 44.6 kJ mol-1. Therefore, Cu/MG was beneficial to the formation of DMC as a single-atom catalyst.

Synthesis and Exciton Dynamics of Donor-Orthogonal Acceptor Conjugated Polymers: Reducing the Singlet-Triplet Energy Gap.

PubMed

Freeman, David M E; Musser, Andrew J; Frost, Jarvist M; Stern, Hannah L; Forster, Alexander K; Fallon, Kealan J; Rapidis, Alexandros G; Cacialli, Franco; McCulloch, Iain; Clarke, Tracey M; Friend, Richard H; Bronstein, Hugo

2017-08-16

The presence of energetically low-lying triplet states is a hallmark of organic semiconductors. Even though they present a wealth of interesting photophysical properties, these optically dark states significantly limit optoelectronic device performance. Recent advances in emissive charge-transfer molecules have pioneered routes to reduce the energy gap between triplets and "bright" singlets, allowing thermal population exchange between them and eliminating a significant loss channel in devices. In conjugated polymers, this gap has proved resistant to modification. Here, we introduce a general approach to reduce the singlet-triplet energy gap in fully conjugated polymers, using a donor-orthogonal acceptor motif to spatially separate electron and hole wave functions. This new generation of conjugated polymers allows for a greatly reduced exchange energy, enhancing triplet formation and enabling thermally activated delayed fluorescence. We find that the mechanisms of both processes are driven by excited-state mixing between π-π*and charge-transfer states, affording new insight into reverse intersystem crossing.

Chemoselective reduction and oxidation of ketones in water through control of the electron transfer pathway

PubMed Central

Kim, Sun Min; Yoo, Ho Sung; Hosono, Hideo; Yang, Jung Woon; Kim, Sung Wng

2015-01-01

The selective synthesis of different products from the same starting materials in water, which is the most abundant solvent in nature, is a crucial issue as it maximizes the utilization of materials. Realizing such reactions for ketones is of considerable importance because numerous organic functionalities can be obtained via nucleophilic addition reactions. Herein, we report chemoselective reduction and oxidation reactions of 1,2-diketones in water, which initiates anionic electron transfer from the inorganic electride [Ca24Al28O64]4+·4e−, through controlling the pathway of the electrons to substrates. The generation of different radical species for transient intermediates was the key process required to control the reaction selectivity, which was achieved by reacting the anionic electrons with either diketones or O2, leading to the formation of ketyl dianion and superoxide radicals in the reduction and oxidation reactions, respectively. This methodology that utilizes electrides may provide an alternative to the pulse radiolysis of water in synthetic chemistry. PMID:26020413

Supported Single-Site Ti(IV) on a Metal–Organic Framework for the Hydroboration of Carbonyl Compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Zhiyuan; Liu, Dong; Camacho-Bunquin, Jeffrey

ABSTRACT: A stable and structurally well-defined titanium alkoxide catalyst supported on a metal-organic-framework (MOF) of UiO-67 topology (ANL1-Ti(OiPr)2) was synthesized and fully characterized by a variety of analytical and spectroscopic techniques, including BET, TGA, PXRD, XAS, DRIFT, SEM, and DFT computations. The Ti-functionalized MOF was demonstrated active for the catalytic hydroboration of a wide range of aldehydes and ketones with HBpin as the boron source. Compared to traditional homogeneous and supported hydroboration catalysts, ANL1-Ti(OiPr)2 is completely recyclable and reusable, making it a promising hydroboration catalyst alternative for green and sustainable chemical synthesis. DFT calculations suggest that the catalytic hydroboration proceedsmore » via a (1) hydride transfer between the active Ti-hydride species and a carbonyl moiety (rate determining step), and (2) alkoxide transfer (intramolecular σ-bond metathesis) to generate the boronate ester product.« less

Measurement of host-to-activator transfer efficiency in nano-crystalline Y{sub 2}O{sub 3}:Eu{sup 3+} under VUV excitation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Waite, Christopher; Mann, Rusty; Diaz, Anthony L., E-mail: DiazA@cwu.edu

2013-02-15

We have conducted a systematic study of the excitation and reflectance spectra of nano-crystalline Y{sub 2}O{sub 3}:Eu prepared by combustion synthesis. Excitation through the host lattice becomes relatively more efficient as the firing temperature of the precursor is increased, while reflectance properties remain essentially unchanged. Using these data, host-to-activator transfer efficiencies were calculated for excitation at the band edge of Y{sub 2}O{sub 3}, and evaluated using a competition kinetics model. From this analysis we conclude that the relatively low luminous efficiency of these materials is due more to poor bulk crystallinity than to surface loss effects. - Graphical abstract: Themore » low luminous efficiency of nano-crystalline Y{sub 2}O{sub 3}:Eu{sup 3+} prepared by combustion synthesis is due to poor bulk crystallinity rather than surface loss effects. Highlights: Black-Right-Pointing-Pointer We report on the optical properties of Y{sub 2}O{sub 3}:Eu{sup 3+} prepared by combustion synthesis. Black-Right-Pointing-Pointer Host-to-activator transfer efficiencies under VUV excitation were calculated. Black-Right-Pointing-Pointer The low luminous efficiency of these materials is due to poor bulk crystallinity.« less

Water-Soluble Phosphine-Protected Au₁₁ Clusters: Synthesis, Electronic Structure, and Chiral Phase Transfer in a Synergistic Fashion.

PubMed

Yao, Hiroshi; Iwatsu, Mana

2016-04-05

Synthesis of atomically precise, water-soluble phosphine-protected gold clusters is still currently limited probably due to a stability issue. We here present the synthesis, magic-number isolation, and exploration of the electronic structures as well as the asymmetric conversion of triphenylphosphine monosulfonate (TPPS)-protected gold clusters. Electrospray ionization mass spectrometry and elemental analysis result in the primary formation of Au11(TPPS)9Cl undecagold cluster compound. Magnetic circular dichroism (MCD) spectroscopy clarifies that extremely weak transitions are present in the low-energy region unresolved in the UV-vis absorption, which can be due to the Faraday B-terms based on the magnetically allowed transitions in the cluster. Asymmetric conversion without changing the nuclearity is remarkable by the chiral phase transfer in a synergistic fashion, which yields a rather small anisotropy factor (g-factor) of at most (2.5-7.0) × 10(-5). Quantum chemical calculations for model undecagold cluster compounds are then used to evaluate the optical and chiroptical responses induced by the chiral phase transfer. On this basis, we find that the Au core distortion is ignorable, and the chiral ion-pairing causes a slight increase in the CD response of the Au11 cluster.

Autonomous frequency domain identification: Theory and experiment

NASA Technical Reports Server (NTRS)

Yam, Yeung; Bayard, D. S.; Hadaegh, F. Y.; Mettler, E.; Milman, M. H.; Scheid, R. E.

1989-01-01

The analysis, design, and on-orbit tuning of robust controllers require more information about the plant than simply a nominal estimate of the plant transfer function. Information is also required concerning the uncertainty in the nominal estimate, or more generally, the identification of a model set within which the true plant is known to lie. The identification methodology that was developed and experimentally demonstrated makes use of a simple but useful characterization of the model uncertainty based on the output error. This is a characterization of the additive uncertainty in the plant model, which has found considerable use in many robust control analysis and synthesis techniques. The identification process is initiated by a stochastic input u which is applied to the plant p giving rise to the output. Spectral estimation (h = P sub uy/P sub uu) is used as an estimate of p and the model order is estimated using the produce moment matrix (PMM) method. A parametric model unit direction vector p is then determined by curve fitting the spectral estimate to a rational transfer function. The additive uncertainty delta sub m = p - unit direction vector p is then estimated by the cross spectral estimate delta = P sub ue/P sub uu where e = y - unit direction vectory y is the output error, and unit direction vector y = unit direction vector pu is the computed output of the parametric model subjected to the actual input u. The experimental results demonstrate the curve fitting algorithm produces the reduced-order plant model which minimizes the additive uncertainty. The nominal transfer function estimate unit direction vector p and the estimate delta of the additive uncertainty delta sub m are subsequently available to be used for optimization of robust controller performance and stability.

Acylation, Diastereoselective Alkylation, and Cleavage of an Oxazolidinone Chiral Auxiliary: A Multistep Asymmetric Synthesis Experiment for Advanced Undergraduates

ERIC Educational Resources Information Center

Smith, Thomas E.; Richardson, David P.; Truran, George A.; Belecki, Katherine; Onishi, Megumi

2008-01-01

An introduction to the concepts and experimental techniques of diastereoselective synthesis using a chiral auxiliary is described. The 4-benzyl-2-oxazolidinone chiral auxiliary developed by Evans is acylated with propionic anhydride under mild conditions using DMAP as an acyl transfer catalyst. Deprotonation with NaN(TMS)[subscript 2] at -78…

Sulfonated amphiphilic block copolymers : synthesis, self-assembly in water, and application as stabilizer in emulsion polymerization

Treesearch

Jiguang Zhang; Matthew R. Dubay; Carl J. Houtman; Steven J. Severtson

2009-01-01

Described is the synthesis of diblock copolymers generated via sequential atom transfer radical polymerization (ATRP) of poly(n-butyl acrylate) (PnBA) followed by chain augmentation with either sulfonated poly(2-hydroxyethyl methacrylate) (PHEMA) or poly(2-hydroxyethyl acrylate) (PHEA) blocks. ATRP of PHEMA or PHEA from PnBA macroinitiator was conducted in acetone/...

Theoretical investigation of the charge-transfer properties in different meso-linked zinc porphyrins for highly efficient dye-sensitized solar cells.

PubMed

Namuangruk, Supawadee; Sirithip, Kanokkorn; Rattanatwan, Rattanawelee; Keawin, Tinnagon; Kungwan, Nawee; Sudyodsuk, Taweesak; Promarak, Vinich; Surakhot, Yaowarat; Jungsuttiwong, Siriporn

2014-06-28

The charge transfer effect of different meso-substituted linkages on porphyrin analogue 1 (A1, B1 and C1) was theoretically investigated using density functional theory (DFT) and time-dependent DFT (TDDFT) calculations. The calculated geometry parameters and natural bond orbital analysis reveal that the twisted conformation between porphyrin macrocycle and meso-substituted linkages leads to blocking of the conjugation of the conjugated backbone, and the frontier molecular orbital plot shows that the intramolecular charge transfer of A1, B1 and C1 hardly takes place. In an attempt to improve the photoinduced intramolecular charge transfer ability of the meso-linked zinc porphyrin sensitizer, a strong electron-withdrawing group (CN) was introduced into the anchoring group of analogue 1 forming analogue 2 (A2, B2 and C2). The density difference plot of A2, B2 and C2 shows that the charge transfer properties dramatically improved. The electron injection process has been performed using TDDFT; the direct charge-transfer transition in the A2-(TiO2)38 interacting system takes place; our results strongly indicated that introducing electron-withdrawing groups into the acceptor part of porphyrin dyes can fine-tune the effective conjugation length of the π-spacer and improve intramolecular charge transfer properties, consequently inducing the electron injection process from the anchoring group of the porphyrin dye to the (TiO2)38 surface which may improve the conversion efficiency of the DSSCs. Our calculated results can provide valuable information and a promising outlook for computation-aided sensitizer design with anticipated good properties in further experimental synthesis.

Pulmonary fatty acid synthesis. I. Mitochondrial acetyl transfer by rat lung in vitro.

PubMed

Evans, R M; Scholz, R W

1977-04-01

Incorporation of tritiated water into fatty acids by rat adipose tissue and lung tissue slices incubated with 5 mM glucose indicated a level of fatty acid synthesis in rat lung approximately 15% that observed in adipose tissue in vitro. (-)-Hydroxycitrate, and inhibitor of ATP citrate lyase, markedly reduced tritiated water incorporation into fatty acids by lung tissue slices. The effects of (-)-hydroxycitrate and n-butymalonate on the incorporation of 14C-labeled glucose, pyruvate, acetate, and citrate suggested that citrate is a major acetyl carrier for de novo fatty acid synthesis in lung tissue. Alternative mechanisms to citrate as an acetyl carrier were also considered. Lung mitochondrial preparations formed significant levels of acetylcarnitine in the presence of pyruvate and carnitine. However, the effect of carnitine on the incorporation of 14C-labeled glucose, pyruvate, acetate, and citrate into fatty acids by lung tissue slices indicated that acetylcarnitine may not be a significant acetyl carrier for fatty acid synthesis but may serve as an acetyl "buffer" in the control of mitochondrial acetyl-CoA levels. Additionally, it appears unlikely that either acetylaspartate or acetoacetate are of major importance in acetyl transfer in lung tissue.

Precision synthesis of functional materials via RAFT polymerization and click-type chemical reactions

NASA Astrophysics Data System (ADS)

Flores, Joel Diez

2011-12-01

The need to tailor polymeric architectures with specific physico-chemical properties via the simplest, cleanest, and most efficient synthetic route possible has become the ultimate goal in polymer synthesis. Recent progress in macromolecular science, such as the discoveries of controlled/"living" free radical polymerization (CRP) methods, has brought about synthetic capabilities to prepare (co)polymers with advanced topologies, predetermined molecular weights, narrow molecular weight distributions, and precisely located functional groups. In addition, the establishment of click chemistry has redefined the selected few highly efficient chemical reactions that become highly useful in post-polymerization modification strategies. Hence, the ability to make well-defined topologies afforded by controlled polymerization techniques and the facile incorporation of functionalities along the chain via click-type reactions have yielded complex architectures, allowing the investigation of physical phenomena which otherwise could not be studied with systems prepared via conventional methods. The overarching theme of the research work described in this dissertation is the fusion of the excellent attributes of reversible addition-fragmentation chain transfer (RAFT) polymerization method, which is one of the CRP techniques, and click-type chemical reactions in the precision of synthesis of advanced functional materials. Chapter IV is divided into three sections. In Section I, the direct RAFT homopolymerization of 2-(acryloyloxy)ethyl isocyanate (AOI) and subsequent post-polymerization modifications are described. The polymerization conditions were optimized in terms of the choice of RAFT chain transfer agent (CTA), polymerization temperature and the reaction medium. Direct RAFT polymerization of AOI requires a neutral CTA, and relatively low reaction temperature to yield AOI homopolymers with low polydispersities. Efficient side-chain functionalization of PAOI homopolymers was achieved via reaction with model amine, thiol and alcohol compounds yielding urea, thiourethane and urethane derivatives, respectively. Reactions with amines and thiols (in the presence of base) were rapid, quantitative and efficient. However, the reaction with alcohols catalyzed by dibutyltin dilaurate (DBTDL) was relatively slow but proceeded to completion. Selective reaction pathways for the addition of difunctional ethanolamine and mercaptoethanol were also investigated. A related strategy is described in Section II wherein a hydroxyl-containing diblock copolymer precursor was transformed into a library of functional copolymers via two sequential post-polymerization modification reactions. A diblock copolymer scaffold, poly[(N,N-dimethylacrylamide)-b-( N-(2-hydroxyethyl)acrylamide] (PDMA-b-PHEA) was first prepared. The hydroxyl groups of the HEA block were then reacted with 2-(acryloyloxy)ethylisocyanate (AOI) and allylisocyanate (AI) resulting in acrylate- and allyl-functionalized copolymer precursors, respectively. The efficiencies of Michael-type and free radical thiol addition reactions were investigated using selected thiols having alkyl, aryl, hydroxyl, carboxylic acid, amine and amino acid functionalities. The steps of RAFT polymerization, isocyanate-hydroxyl coupling and thiol-ene addition are accomplished under mild conditions, thus offering facile and modular routes to synthesize functional copolymers. The synthesis and solution studies of pH- and salt-responsive triblock copolymer are described in Section III. This system is capable of forming self-locked micellar structures which may be controlled by changing solution pH as well as ionic strength. A triblock copolymer containing a permanently hydrophilic poly(N,N-dimethylacrylamide) (PDMA) outer block, a salt-sensitive zwitterionic poly(3[2-(N-methylacrylamido)ethyl dimethylammonio]propanesulfonate) (PMAEDAPS) middle block and a pH-responsive 3-acrylamido-3-methylbutanoic acid (PAMBA) core block was synthesized using aqueous RAFT polymerization. A facile formation of "self-locking" shell cross-linked micelles is achieved by changing solution pH and salt concentration. The reversible "self-locking" is attained from the interactions of zwitterionic groups in the middle block that constitutes the shell of the micelles. The structure slowly dissociates into unimers in 2-3 days at pH above the pKa of the PAMBA block.

Structural and Functional Characterization of a Short-Chain Flavodoxin Associated with a Noncanonical 1,2-Propanediol Utilization Bacterial Microcompartment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Plegaria, Jefferson S.; Sutter, Markus; Ferlez, Bryan

Bacterial microcompartments (BMCs) are proteinaceous organelles that encapsulate enzymes involved in CO2 fixation (carboxysomes). or carbon catabolism (metabolosomes). Metabolosomes share a common core of enzymes and a distinct signature enzyme for substrate degradation that defines the function of the BMC (e,g., propanediol or ethanolamine utilization BMCs, or glycyl-radical enzyme microcompartments). Loci encoding metabolosomes also typically contain genes for proteins that support organelle function, such as regulation, transport of substrate, and cofactor (e.g., vitamin B-12) synthesis and recycling. Flavoproteins are frequently among these ancillary gene products, suggesting that these redox active proteins play an undetermined function in many metabolosomes. Here, wemore » report the first characterization of a BMC-associated flavodoxin (Fld1C), a small flavoprotein, derived from the noncanonical 1,2-propanediol utilization BMC locus (PDU1C) of Lactobacillus reuteri. The 2.0 angstrom X-ray structure of Fld1C displays the alpha/beta flavodoxin fold, which noncovalently binds a single flavin mononucleotide molecule. Fld1C is a short-chain flavodoxin with redox potentials of -240 +/- 3 mV oxidized/semiquinone and -344 +/- 1 mV semiquinone/hydroquinone versus the standard hydrogen electrode at pH 7.5. It can participate in an electron transfer reaction with a photoreductant to form a stable semiquinone species. Collectively, our structural and functional results suggest that PDU1C BMCs encapsulate Fld1C to store and transfer electrons for the reactivation and/or recycling of the B-12 cofactor utilized by the signature enzyme.« less

Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst

PubMed Central

Yeow, Jonathan; Xu, Jiangtao; Boyer, Cyrille

2016-01-01

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins with the synthesis of a hydrophilic poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) homopolymer using reversible addition-fragmentation chain-transfer (RAFT) polymerization. Under mild visible light irradiation (λ = 460 nm, 0.7 mW/cm2), this macro-chain transfer agent (macro-CTA) in the presence of a ruthenium based photoredox catalyst, Ru(bpy)3Cl2 can be chain extended with a second monomer to form a well-defined block copolymer in a process known as Photoinduced Electron Transfer RAFT (PET-RAFT). When PET-RAFT is used to chain extend POEGMA with benzyl methacrylate (BzMA) in ethanol (EtOH), polymeric nanoparticles with different morphologies are formed in situ according to a polymerization-induced self-assembly (PISA) mechanism. Self-assembly into nanoparticles presenting POEGMA chains at the corona and poly(benzyl methacrylate) (PBzMA) chains in the core occurs in situ due to the growing insolubility of the PBzMA block in ethanol. Interestingly, the formation of highly pure worm-like micelles can be readily monitored by observing the onset of a highly viscous gel in situ due to nanoparticle entanglements occurring during the polymerization. This process thereby allows for a more reproducible synthesis of worm-like micelles simply by monitoring the solution viscosity during the course of the polymerization. In addition, the light stimulus can be intermittently applied in an ON/OFF manner demonstrating temporal control over the nanoparticle morphology. PMID:27340940

Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst.

PubMed

Yeow, Jonathan; Xu, Jiangtao; Boyer, Cyrille

2016-06-08

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins with the synthesis of a hydrophilic poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) homopolymer using reversible addition-fragmentation chain-transfer (RAFT) polymerization. Under mild visible light irradiation (λ = 460 nm, 0.7 mW/cm(2)), this macro-chain transfer agent (macro-CTA) in the presence of a ruthenium based photoredox catalyst, Ru(bpy)3Cl2 can be chain extended with a second monomer to form a well-defined block copolymer in a process known as Photoinduced Electron Transfer RAFT (PET-RAFT). When PET-RAFT is used to chain extend POEGMA with benzyl methacrylate (BzMA) in ethanol (EtOH), polymeric nanoparticles with different morphologies are formed in situ according to a polymerization-induced self-assembly (PISA) mechanism. Self-assembly into nanoparticles presenting POEGMA chains at the corona and poly(benzyl methacrylate) (PBzMA) chains in the core occurs in situ due to the growing insolubility of the PBzMA block in ethanol. Interestingly, the formation of highly pure worm-like micelles can be readily monitored by observing the onset of a highly viscous gel in situ due to nanoparticle entanglements occurring during the polymerization. This process thereby allows for a more reproducible synthesis of worm-like micelles simply by monitoring the solution viscosity during the course of the polymerization. In addition, the light stimulus can be intermittently applied in an ON/OFF manner demonstrating temporal control over the nanoparticle morphology.

The cellular and compartmental profile of mouse retinal glycolysis, tricarboxylic acid cycle, oxidative phosphorylation, and ~P transferring kinases

PubMed Central

Rueda, Elda M.; Johnson, Jerry E.; Giddabasappa, Anand; Swaroop, Anand; Brooks, Matthew J.; Sigel, Irena; Chaney, Shawnta Y.

2016-01-01

Purpose The homeostatic regulation of cellular ATP is achieved by the coordinated activity of ATP utilization, synthesis, and buffering. Glucose is the major substrate for ATP synthesis through glycolysis and oxidative phosphorylation (OXPHOS), whereas intermediary metabolism through the tricarboxylic acid (TCA) cycle utilizes non-glucose-derived monocarboxylates, amino acids, and alpha ketoacids to support mitochondrial ATP and GTP synthesis. Cellular ATP is buffered by specialized equilibrium-driven high-energy phosphate (~P) transferring kinases. Our goals were twofold: 1) to characterize the gene expression, protein expression, and activity of key synthesizing and regulating enzymes of energy metabolism in the whole mouse retina, retinal compartments, and/or cells and 2) to provide an integrative analysis of the results related to function. Methods mRNA expression data of energy-related genes were extracted from our whole retinal Affymetrix microarray data. Fixed-frozen retinas from adult C57BL/6N mice were used for immunohistochemistry, laser scanning confocal microscopy, and enzymatic histochemistry. The immunoreactivity levels of well-characterized antibodies, for all major retinal cells and their compartments, were obtained using our established semiquantitative confocal and imaging techniques. Quantitative cytochrome oxidase (COX) and lactate dehydrogenase (LDH) activity was determined histochemically. Results The Affymetrix data revealed varied gene expression patterns of the ATP synthesizing and regulating enzymes found in the muscle, liver, and brain. Confocal studies showed differential cellular and compartmental distribution of isozymes involved in glucose, glutamate, glutamine, lactate, and creatine metabolism. The pattern and intensity of the antibodies and of the COX and LDH activity showed the high capacity of photoreceptors for aerobic glycolysis and OXPHOS. Competition assays with pyruvate revealed that LDH-5 was localized in the photoreceptor inner segments. The combined results indicate that glycolysis is regulated by the compartmental expression of hexokinase 2, pyruvate kinase M1, and pyruvate kinase M2 in photoreceptors, whereas the inner retinal neurons exhibit a lower capacity for glycolysis and aerobic glycolysis. Expression of nucleoside diphosphate kinase, mitochondria-associated adenylate kinase, and several mitochondria-associated creatine kinase isozymes was highest in the outer retina, whereas expression of cytosolic adenylate kinase and brain creatine kinase was higher in the cones, horizontal cells, and amacrine cells indicating the diversity of ATP-buffering strategies among retinal neurons. Based on the antibody intensities and the COX and LDH activity, Müller glial cells (MGCs) had the lowest capacity for glycolysis, aerobic glycolysis, and OXPHOS. However, they showed high expression of glutamate dehydrogenase, alpha-ketoglutarate dehydrogenase, succinate thiokinase, GABA transaminase, and ~P transferring kinases. This suggests that MGCs utilize TCA cycle anaplerosis and cataplerosis to generate GTP and ~P transferring kinases to produce ATP that supports MGC energy requirements. Conclusions Our comprehensive and integrated results reveal that the adult mouse retina expresses numerous isoforms of ATP synthesizing, regulating, and buffering genes; expresses differential cellular and compartmental levels of glycolytic, OXPHOS, TCA cycle, and ~P transferring kinase proteins; and exhibits differential layer-by-layer LDH and COX activity. New insights into cell-specific and compartmental ATP and GTP production, as well as utilization and buffering strategies and their relationship with known retinal and cellular functions, are discussed. Developing therapeutic strategies for neuroprotection and treating retinal deficits and degeneration in a cell-specific manner will require such knowledge. This work provides a platform for future research directed at identifying the molecular targets and proteins that regulate these processes. PMID:27499608

The cellular and compartmental profile of mouse retinal glycolysis, tricarboxylic acid cycle, oxidative phosphorylation, and ~P transferring kinases.

PubMed

Rueda, Elda M; Johnson, Jerry E; Giddabasappa, Anand; Swaroop, Anand; Brooks, Matthew J; Sigel, Irena; Chaney, Shawnta Y; Fox, Donald A

2016-01-01

The homeostatic regulation of cellular ATP is achieved by the coordinated activity of ATP utilization, synthesis, and buffering. Glucose is the major substrate for ATP synthesis through glycolysis and oxidative phosphorylation (OXPHOS), whereas intermediary metabolism through the tricarboxylic acid (TCA) cycle utilizes non-glucose-derived monocarboxylates, amino acids, and alpha ketoacids to support mitochondrial ATP and GTP synthesis. Cellular ATP is buffered by specialized equilibrium-driven high-energy phosphate (~P) transferring kinases. Our goals were twofold: 1) to characterize the gene expression, protein expression, and activity of key synthesizing and regulating enzymes of energy metabolism in the whole mouse retina, retinal compartments, and/or cells and 2) to provide an integrative analysis of the results related to function. mRNA expression data of energy-related genes were extracted from our whole retinal Affymetrix microarray data. Fixed-frozen retinas from adult C57BL/6N mice were used for immunohistochemistry, laser scanning confocal microscopy, and enzymatic histochemistry. The immunoreactivity levels of well-characterized antibodies, for all major retinal cells and their compartments, were obtained using our established semiquantitative confocal and imaging techniques. Quantitative cytochrome oxidase (COX) and lactate dehydrogenase (LDH) activity was determined histochemically. The Affymetrix data revealed varied gene expression patterns of the ATP synthesizing and regulating enzymes found in the muscle, liver, and brain. Confocal studies showed differential cellular and compartmental distribution of isozymes involved in glucose, glutamate, glutamine, lactate, and creatine metabolism. The pattern and intensity of the antibodies and of the COX and LDH activity showed the high capacity of photoreceptors for aerobic glycolysis and OXPHOS. Competition assays with pyruvate revealed that LDH-5 was localized in the photoreceptor inner segments. The combined results indicate that glycolysis is regulated by the compartmental expression of hexokinase 2, pyruvate kinase M1, and pyruvate kinase M2 in photoreceptors, whereas the inner retinal neurons exhibit a lower capacity for glycolysis and aerobic glycolysis. Expression of nucleoside diphosphate kinase, mitochondria-associated adenylate kinase, and several mitochondria-associated creatine kinase isozymes was highest in the outer retina, whereas expression of cytosolic adenylate kinase and brain creatine kinase was higher in the cones, horizontal cells, and amacrine cells indicating the diversity of ATP-buffering strategies among retinal neurons. Based on the antibody intensities and the COX and LDH activity, Müller glial cells (MGCs) had the lowest capacity for glycolysis, aerobic glycolysis, and OXPHOS. However, they showed high expression of glutamate dehydrogenase, alpha-ketoglutarate dehydrogenase, succinate thiokinase, GABA transaminase, and ~P transferring kinases. This suggests that MGCs utilize TCA cycle anaplerosis and cataplerosis to generate GTP and ~P transferring kinases to produce ATP that supports MGC energy requirements. Our comprehensive and integrated results reveal that the adult mouse retina expresses numerous isoforms of ATP synthesizing, regulating, and buffering genes; expresses differential cellular and compartmental levels of glycolytic, OXPHOS, TCA cycle, and ~P transferring kinase proteins; and exhibits differential layer-by-layer LDH and COX activity. New insights into cell-specific and compartmental ATP and GTP production, as well as utilization and buffering strategies and their relationship with known retinal and cellular functions, are discussed. Developing therapeutic strategies for neuroprotection and treating retinal deficits and degeneration in a cell-specific manner will require such knowledge. This work provides a platform for future research directed at identifying the molecular targets and proteins that regulate these processes.

Synthesis and characterization of TiO₂ and TiO₂/Ag for use in photodegradation of methylviologen, with kinetic study by laser flash photolysis.

PubMed

Ramos, Dayana Doffinger; Bezerra, Paula C S; Quina, Frank H; Dantas, Renato F; Casagrande, Gleison A; Oliveira, Silvio C; Oliveira, Márcio R S; Oliveira, Lincoln C S; Ferreira, Valdir S; Oliveira, Samuel L; Machulek, Amilcar

2015-01-01

This paper reports the synthesis, characterization, and application of TiO2 and TiO2/Ag nanoparticles for use in photocatalysis, employing the herbicide methylviologen (MV) as a substrate for photocatalytic activity testing. At suitable metal to oxide ratios, increases in silver surface coating on TiO2 enhanced the efficiency of heterogeneous photocatalysis by increasing the electron transfer constant. The sol-gel method was used for TiO2 synthesis. P25 TiO2 was the control material. Both oxides were subjected to the same silver incorporation process. The materials were characterized by conventional spectroscopy, SEM micrography, X-ray diffraction, calculation of surface area per mass of catalyst, and thermogravimetry. Also, electron transfers between TiO2 or TiO2/Ag and MV in the absence and presence of sodium formate were investigated using laser flash photolysis. Oxides synthesized with 2.0 % silver exhibited superior photocatalytic activity for MV degradation.

Diphenylbutadienes Syntheses by Means of the Wittig Reaction: Experimental Introduction to the Use of Phase Transfer Catalysis.

ERIC Educational Resources Information Center

Gillois, J.; And Others

1980-01-01

The synthesis of 1,4-diphenylbutadiene by means of the Wittig reaction is presented as suitable for organic chemistry students at the end of a basic laboratory program to apply laboratory skills and display understanding of the use of phase transfer catalysis and its application in syntheses. (CS)

Space transfer concepts and analysis for exploration missions

NASA Technical Reports Server (NTRS)

1991-01-01

Covered here is the second phase of a broad scoped and systematic study of space transfer concepts for human lunar and Mars missions. The study addressed issues that were raised during Phase 1, developed generic Mars missions profile analysis data, and conducted preliminary analysis of the Mars in-space transportation requirements and implementation from the Stafford Committee Synthesis Report.

Inpatient transfer to a care home for end-of-life care: What are the views and experiences of patients and their relatives? A systematic review and narrative synthesis of the UK literature.

PubMed

Thomas, Tabitha; Kuhn, Isla; Barclay, Stephen

2017-02-01

Transfers from hospital or 'hospice palliative care units' to care homes for end-of-life care are an increasingly common part of clinical practice but are a source of anxiety and distress for patients, relatives and healthcare professionals. To understand the experiences of patients discharged to care homes for end-of-life care. Systematic review and narrative synthesis of the UK literature concerning inpatient transfer from a hospital or hospice palliative care unit to a care home for end-of-life care. The published literature is very limited: only three papers and one conference abstract were identified, all of low quality using Gough's weight of evidence assessment. No papers examined transfer from hospital: all were of transfers from hospices and were retrospective case note reviews. Many patients were reported to have been negative or ambivalent about moving and experienced feelings of anxiety or abandonment when transferred. Relatives were often either vehemently opposed or ambivalent. Although some came to accept transfer, others reported the transfer to have seriously affected their loved one's quality of life and that the process of finding a care home had been traumatic. No studies investigated patients' views prospectively, the views of staff or the processes of decision-making. The UK literature is very limited, despite such transfers being an increasingly common part of clinical practice and a source of concern to patients, relatives and staff alike. Further research is urgently needed in this area, especially studies of patients themselves, in order to understand their experiences and views.

Experimental verification of orbital engineering at the atomic scale: Charge transfer and symmetry breaking in nickelate heterostructures

NASA Astrophysics Data System (ADS)

Phillips, Patrick J.; Rui, Xue; Georgescu, Alexandru B.; Disa, Ankit S.; Longo, Paolo; Okunishi, Eiji; Walker, Fred; Ahn, Charles H.; Ismail-Beigi, Sohrab; Klie, Robert F.

2017-05-01

Epitaxial strain, layer confinement, and inversion symmetry breaking have emerged as powerful new approaches to control the electronic and atomic-scale structural properties of complex metal oxides. Trivalent rare-earth (RE) nickelate R E NiO3 heterostructures have been shown to be exemplars since the orbital occupancy, degeneracy, and, consequently, electronic/magnetic properties can be altered as a function of epitaxial strain, layer thickness, and superlattice structure. One recent example is the tricomponent LaTiO3-LaNiO3-LaAlO3 superlattice which exhibits charge transfer and orbital polarization as the result of its interfacial dipole electric field. A crucial step towards control of these parameters for future electronic and magnetic device applications is to develop an understanding of both the magnitude and range of the octahedral network's response towards interfacial strain and electric fields. An approach that provides atomic-scale resolution and sensitivity towards the local octahedral distortions and orbital occupancy is therefore required. Here, we employ atomic-resolution imaging coupled with electron spectroscopies and first-principles theory to examine the role of interfacial charge transfer and symmetry breaking in a tricomponent nickelate superlattice system. We find that nearly complete charge transfer occurs between the LaTiO3 and LaNiO3 layers, resulting in a mixed Ni2 +/Ni3 + valence state. We further demonstrate that this charge transfer is highly localized with a range of about 1 unit cell within the LaNiO3 layers. We also show how Wannier-function-based electron counting provides a simple physical picture of the electron distribution that connects directly with formal valence charges. The results presented here provide important feedback to synthesis efforts aimed at stabilizing new electronic phases that are not accessible by conventional bulk or epitaxial film approaches.

Conditional immortalization of Gunn rat hepatocytes: an ex vivo model for evaluating methods for bilirubin-UDP-glucuronosyltransferase gene transfer.

PubMed

Fox, I J; Chowdhury, N R; Gupta, S; Kondapalli, R; Schilsky, M L; Stockert, R J; Chowdhury, J R

1995-03-01

Viral vectors and protein carriers utilizing asialoglycoprotein receptor (ASGR)-mediated endocytosis are being developed to transfer genes for the correction of bilirubin-UDP-glucuronosyltransferase (bilirubin-UGT) deficiency. Ex vivo evaluation of these gene transfer vectors would be facilitated by a cell system that lacks bilirubin-UGT, but expresses differentiated liver functions, including ASGR. We immortalized primary Gunn rat hepatocytes by transduction with a recombinant Moloney murine leukemia virus expressing a thermolabile mutant SV40 large T antigen (tsA58). At 33 degrees C, the immortalized hepatocyte clones expressed SV40 large T antigen, synthesized DNA, and doubled in number every 2 to 3 days. At this temperature, differentiated hepatocyte markers, e.g., albumin, ASGR, and androsterone-UGT, were expressed at 5% to 10% of the levels found in primary hepatocytes maintained in culture for 24 hours. Glutathione-S-transferase Yp (GST-Yp), an oncofetal protein, was expressed in these cells at 33 degrees C, but was undetectable in primary hepatocytes. In contrast, when the cells were cultured at 39 degrees C or 37 degrees C, the large T antigen was degraded, DNA synthesis and cell growth stopped, and morphologic characteristics of differentiated hepatocytes were observed. The expression of albumin, ASGR, and androsterone-UGT, and their corresponding mRNAs, increased to 25% to 40% of the level in primary hepatocytes, whereas GST-Yp expression decreased. Functionality of ASGR was demonstrated by internalization of Texas red-labeled asialoorosomucoid, and binding and degradation of 125I-asialoorosomucoid. After liposome-mediated transfer of a plasmid containing the coding region of human bilirubin-UGT1, driven by the SV40 large T promoter, active human bilirubin-UGT1 was expressed in these cells. The immortalized cells were not tumorigenic after transplantation into severe combined immunodeficiency mice. These conditionally immortalized cells will be useful for ex vivo evaluation of bilirubin-UGT gene transfer vectors.

Facile green synthesis of functional nanoscale zero-valent iron and studies of its activity toward ultrasound-enhanced decolorization of cationic dyes.

PubMed

Wang, Xiangyu; Wang, Anqi; Ma, Jun; Fu, Minglai

2017-01-01

For the first time, an integrated green technology by coupling functional nanoscale zero-valent iron (NZVI) with ultrasound (US) was innovatively developed for the enhanced decolorization of malachite green (MG) and methylene blue (MB). The functional NZVI (TP-Fe) was successfully fabricated via a facile, one-step and environmentally-benign approach by directly introducing high pure tea polyphenol (TP), where TP contenting abundant epicatechin was employed as reductant, dispersant and capping agent. Note that neither additional extraction procedure nor protection gas was needed during the entire synthesis process. Affecting factors (including US frequency, initial pH, dye concentration, and reaction temperature) were investigated. Results show that TP-Fe exhibited enhanced activity, antioxidizability and stability over the reaction course, which could be attributed to the functionalization of TP on NZVI and the invigorating effect of US (i.e., improving the mass transfer rate, breaking up the aggregates of TP-Fe nanoparticles, and maintaining the TP-Fe surface activity). The kinetics for MG and MB decolorization by the TP-Fe/US system could be well described by a two-parameter pseudo-first-order decay model, and the activation energies of MG and MB decolorization in this new system were determined to be 21 kJ mol -1 and 24 kJ mol -1 , respectively. In addition, according to the identified reaction products, a possible mechanism associated with MG and MB decolorization with the TP-Fe/US system was proposed. Copyright © 2016 Elsevier Ltd. All rights reserved.

Relationships between the decoupled and coupled transfer functions: Theoretical studies and experimental validation

NASA Astrophysics Data System (ADS)

Wang, Zengwei; Zhu, Ping; Liu, Zhao

2018-01-01

A generalized method for predicting the decoupled transfer functions based on in-situ transfer functions is proposed. The method allows predicting the decoupled transfer functions using coupled transfer functions, without disassembling the system. Two ways to derive relationships between the decoupled and coupled transfer functions are presented. Issues related to immeasurability of coupled transfer functions are also discussed. The proposed method is validated by numerical and experimental case studies.

Glia to axon RNA transfer.

PubMed

Sotelo, José Roberto; Canclini, Lucía; Kun, Alejandra; Sotelo-Silveira, José Roberto; Calliari, Aldo; Cal, Karina; Bresque, Mariana; Dipaolo, Andrés; Farias, Joaquina; Mercer, John A

2014-03-01

The existence of RNA in axons has been a matter of dispute for decades. Evidence for RNA and ribosomes has now accumulated to a point at which it is difficult to question, much of the disputes turned to the origin of these axonal RNAs. In this review, we focus on studies addressing the origin of axonal RNAs and ribosomes. The neuronal soma as the source of most axonal RNAs has been demonstrated and is indisputable. However, the surrounding glial cells may be a supplemental source of axonal RNAs, a matter scarcely investigated in the literature. Here, we review the few papers that have demonstrated that glial-to-axon RNA transfer is not only feasible, but likely. We describe this process in both invertebrate axons and vertebrate axons. Schwann cell to axon ribosomes transfer was conclusively demonstrated (Court et al. [2008]: J. Neurosci 28:11024-11029; Court et al. [2011]: Glia 59:1529-1539). However, mRNA transfer still remains to be demonstrated in a conclusive way. The intercellular transport of mRNA has interesting implications, particularly with respect to the integration of glial and axonal function. This evolving field is likely to impact our understanding of the cell biology of the axon in both normal and pathological conditions. Most importantly, if the synthesis of proteins in the axon can be controlled by interacting glia, the possibilities for clinical interventions in injury and neurodegeneration are greatly increased. Copyright © 2013 Wiley Periodicals, Inc.

Nanocomposites based on self-assembly poly(hydroxypropyl methacrylate)-block-poly(N-phenylmaleimide) and Fe3O4-NPs. Thermal stability, morphological characterization and optical properties

NASA Astrophysics Data System (ADS)

Pizarro, Guadalupe del C.; Marambio, Oscar G.; Jeria-Orell, Manuel; Sánchez, Julio; Oyarzún, Diego P.

2018-02-01

The current work presents the synthesis, characterization and preparation of organic-inorganic hybrid polymer films that contain inorganic magnetic nanoparticles (NPs). The block copolymer, prepared by Atom-Transfer Radical Polymerization (ATRP), was used as a nanoreactor for iron oxide NPs. The NPs were embedded in poly(hydroxypropyl methacrylate)-block-poly(N-phenylmaleimide) matrix. The following topographical modifications of the surface of the film were specially analyzed: control of pore features and changes in surface roughness. Finally, the NPs functionality inside the polymer matrix and how it may affect the thermal and optical properties of the films were assessed.

Catalytic Nitrene Transfer To Alkynes: A Novel and Versatile Route for the Synthesis of Sulfinamides and Isothiazoles.

PubMed

Rodríguez, Manuel R; Beltrán, Álvaro; Mudarra, Ángel L; Álvarez, Eleuterio; Maseras, Feliu; Díaz-Requejo, M Mar; Pérez, Pedro J

2017-10-09

A novel transformation is reported for the reaction of terminal or internal alkynes with the nitrene precursor PhI=NTs (Ts=p-toluenesulfonyl) in the presence of catalytic amounts of Tp Br3 Cu(NCMe) (Tp Br3 =hydrotris(3,4,5-tribromo-pyrazolylborate). Two products containing an imine functionality have been isolated from the reaction mixtures, identified as sulfinamides and isothiazoles. The former correspond to the formal reduction of the sulfone group into sulfoxide, whereas the latter involves the insertion of an alkyne carbon atom into the aromatic ring of the N-tosyl moiety. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The logic of automated glycan assembly.

PubMed

Seeberger, Peter H

2015-05-19

Carbohydrates are the most abundant biopolymers on earth and part of every living creature. Glycans are essential as materials for nutrition and for information transfer in biological processes. To date, in few cases a detailed correlation between glycan structure and glycan function has been established. A molecular understanding of glycan function will require pure glycans for biological, immunological, and structural studies. Given the immense structural complexity of glycans found in living organisms and the lack of amplification methods or expression systems, chemical synthesis is the only means to access usable quantities of pure glycan molecules. While the solid-phase synthesis of DNA and peptides has become routine for decades, access to glycans has been technically difficult, time-consuming and confined to a few expert laboratories. In this Account, the development of a comprehensive approach to the automated synthesis of all classes of mammalian glycans, including glycosaminoglycans and glycosylphosphatidyl inositol (GPI) anchors, as well as bacterial and plant carbohydrates is described. A conceptual advance concerning the logic of glycan assembly was required in order to enable automated execution of the synthetic process. Based on the central glycosidic bond forming reaction, a general concept for the protecting groups and leaving groups has been developed. Building blocks that can be procured on large scale, are stable for prolonged periods of time, but upon activation result in high yields and selectivities were identified. A coupling-capping and deprotection cycle was invented that can be executed by an automated synthesis instrument. Straightforward postsynthetic protocols for cleavage from the solid support as well as purification of conjugation-ready oligosaccharides have been established. Introduction of methods to install selectively a wide variety of glycosidic linkages has enabled the rapid assembly of linear and branched oligo- and polysaccharides as large as 30-mers. Fast, reliable access to defined glycans that are ready for conjugation has given rise to glycan arrays, glycan probes, and synthetic glycoconjugate vaccines. While an ever increasing variety of glycans are accessible by automated synthesis, further methodological advances in carbohydrate chemistry are needed to make all possible glycans found in nature. These tools begin to fundamentally impact the medical but also materials aspects of the glycosciences.

Biotin and Lipoic Acid: Synthesis, Attachment and Regulation

PubMed Central

Cronan, John E.

2014-01-01

Summary Two vitamins, biotin and lipoic acid, are essential in all three domains of life. Both coenzymes function only when covalently attached to key metabolic enzymes. There they act as “swinging arms” that shuttle intermediates between two active sites (= covalent substrate channeling) of key metabolic enzymes. Although biotin was discovered over 100 years ago and lipoic acid 60 years ago, it was not known how either coenzyme is made until recently. In Escherichia coli the synthetic pathways for both coenzymes have now been worked out for the first time. The late steps of biotin synthesis, those involved in assembling the fused rings, were well-described biochemically years ago, although recent progress has been made on the BioB reaction, the last step of the pathway in which the biotin sulfur moiety is inserted. In contrast, the early steps of biotin synthesis, assembly of the fatty acid-like “arm” of biotin were unknown. It has now been demonstrated that the arm is made by using disguised substrates to gain entry into the fatty acid synthesis pathway followed by removal of the disguise when the proper chain length is attained. The BioC methyltransferase is responsible for introducing the disguise and the BioH esterase for its removal. In contrast to biotin, which is attached to its cognate proteins as a finished molecule, lipoic acid is assembled on its cognate proteins. An octanoyl moiety is transferred from the octanoyl-ACP of fatty acid synthesis to a specific lysine residue of a cognate protein by the LipB octanoyl transferase followed by sulfur insertion at carbons C6 and C8 by the LipA lipoyl synthetase. Assembly on the cognate proteins regulates the amount of lipoic acid synthesized and thus there is no transcriptional control of the synthetic genes. In contrast transcriptional control of the biotin synthetic genes is wielded by a remarkably sophisticated, yet simple, system, exerted through BirA a dual function protein that both represses biotin operon transcription and ligates biotin to its cognate protein. PMID:26442940

Polyisobutylene chain end transformations: Block copolymer synthesis and click chemistry functionalizations

NASA Astrophysics Data System (ADS)

Magenau, Andrew Jackson David

The primary objectives of this research were twofold: (1) development of synthetic procedures for combining quasiliving carbocationic polymerization (QLCCP) of isobutylene (IB) and reversible addition fragmentation chain transfer (RAFT) polymerization for block copolymer synthesis; (2) utilization of efficient, robust, and modular chemistries for facile functionalization of polyisobutylene (PIB). In the first study block copolymers consisting of PIB, and either PMMA or PS block segments, were synthesized by a site transformation approach combining living cationic and reversible addition-fragmentation chain transfer (RAFT) polymerizations. The initial PIB block was synthesized via quasiliving cationic polymerization using the TMPCl/TiCl4 initiation system and was subsequently converted into a hydroxylterminated PIB. Site transformation of the hydroxyl-terminated PIB into a macro chain transfer agent (PIB-CTA) was accomplished by N,N'-dicyclohexylcarbodiimide/dimethylaminopyridine-catalyzed esterification with 4-cyano-4-(dodecylsulfanylthiocarbonylsulfanyl)pentanoic acid. In the second study another site transformation approach was developed to synthesize a novel block copolymer, composed of PIB and PNIPAM segments. The PIB block was prepared via quasiliving cationic polymerization and end functionalized by in-situ quenching to yield telechelic halogen-terminated PIB. Azido functionality was obtained by displacement of the terminal halogen through nucleophilic substitution, which was confirmed by both 1H and 13C NMR. Coupling of an alkyne-functional chain transfer agent (CTA) to azido PIB was successfully accomplished through a copper catalyzed click reaction. Structure of the resulting PIB-based macro-CTA was verified with 1H NMR, FTIR, and GPC; whereas coupling reaction kinetics were monitored by real time variable temperature (VT) 1H NMR. In a third study, a click chemistry functionalization procedure was developed based upon the azide-alkyne 1,3-dipolar cycloaddition reaction. 1-(o-Azidoalkyl)pyrrolyl-terminated PIB was successfully synthesized both by substitution of the terminal halide of 1-(o-haloalkyl)pyrrolyl-terminated PIB with sodium azide and by in situ quenching of quasiliving PIB with a 1-(o-azidoalkyl)pyrrole. GPC indicated the absence of coupled PIB under optimized conditions, confirming exclusive mono-substitution on each pyrrole ring. In a fourth study, radical thiol-ene hydrothiolation "Click" chemistry was explored and adapted to easily and rapidly modify exo -olefin PIB with an array of thiol compounds bearing useful functionalities, including primary halogen, primary amine, primary hydroxyl, and carboxylic acid. The thiol-ene "click" procedure was shown to be applicable to both mono and difunctional exo-olefin polyisobutylene. Telechelic mono- and difunctional exo-olefin PIBs were synthesized via quasiliving cationic polymerization followed by quenching with the hindered amine, 1,2,2,6,6-pentamethylpiperidine. Lower reaction temperatures were found to increase exo-olefin conversion to near quantitative amounts. In the fifth study, thiol-terminated polyisobutylene (PIB-SH) was synthesized by reaction of thiourea with alpha,o-bromine-terminated PIB in a three step one-pot procedure. First the alkylisothiouronium salt was produced using a 1:1 (v:v) DMF:heptane cosolvent mixture at 90°C. Hydrolysis of the salt by aqueous base produced thiolate chain ends, which were then acidified to form the desired thiol functional group. An extension of this reaction was performed by a sequential thiol-ene/thiol-yne procedure to produce tetra-hydroxy functionalized PIB. 1H NMR was used to confirm formation of both alkyne and tetrahydroxyl functional species. Further utility of PIB-SH was demonstrated by base catalyzed thiol-isocyanate reactions. A model reaction was conducted with phenyl isocyanate in THF using triethylamine as the catalyst. Last, conversion of PIB-SH directly into a RAFT macro-CTA was accomplished, as shown by 1H NMR, by treatment of PIB-SH with triethylamine in carbon disulfide and subsequent alkylation with 2-bromopropionic acid. (Abstract shortened by UMI.)

Role of cerebellar cortical protein synthesis in transfer of memory trace of cerebellum-dependent motor learning.

PubMed

Okamoto, Takehito; Endo, Shogo; Shirao, Tomoaki; Nagao, Soichi

2011-06-15

We developed a new protocol that induces long-term adaptation of horizontal optokinetic response (HOKR) eye movement by hours of spaced training and examined the role of protein synthesis in the cerebellar cortex in the formation of memory of adaptation. Mice were trained to view 800 cycles of screen oscillation either by 1 h of massed training or by 2.5 h to 8 d of training with 0.5 h to 1 d space intervals. The HOKR gains increased similarly by 20-30% at the end of training; however, the gains increased by 1 h of massed training recovered within 24 h, whereas the gains increased by spaced training were sustained over 24 h. Bilateral floccular lidocaine microinfusions immediately after the end of training recovered the gains increased by 1 h of massed training but did not affect the gains increased by 4 h of spaced training, suggesting that the memory trace of adaptation was transferred from the flocculus to the vestibular nuclei within 4 h of spaced training. Blockade of floccular protein synthesis, examined by bilateral floccular microinfusions of anisomycin or actinomycin D 1-4 h before the training, impaired the gains increased by 4 h of spaced training but did not affect the gains increased by 1 h of massed training. These findings suggest that the transfer of the memory trace of adaptation occurs within 4 h of spaced training, and proteins synthesized in the flocculus during training period may play an important role in memory transfer.

In the eye of the beholder: Helmholtzian perception and the origins of Freud's 1900 theory of transference.

PubMed

Makari, G J

1994-01-01

Freud's 1900 theory of transference was indebted to the convergence of philosophy and physiology found in nineteenth-century theories of visual perception. The author maps out the post-Kantian philosophical and German physiological currents that gave rise to Hermann von Helmholtz's influential work on perception, and proposes that Freud's 1900 theory of transference was a creative synthesis of novel notions like unconscious wishing and psychic defense with a Helmholtzian model of visual illusion.

Concise synthesis of the bryostatin A-ring via consecutive C-C bond forming transfer hydrogenations.

PubMed

Lu, Yu; Krische, Michael J

2009-07-16

Under the conditions of C-C bond forming transfer hydrogenation, 1,3-propanediol 1 engages in double asymmetric carbonyl allylation to furnish the C(2)-symmetric diol 2. Double ozonolysis of 2 followed by TBS protection delivers aldehyde 3, which is subject to catalyst directed carbonyl reverse prenylation via transfer hydrogenation to deliver neopentyl alcohol 4 and, ultimately, the bryostatin A-ring 7. Through use of two consecutive C-C bond forming transfer hydrogenations, the Evans' bryostatin A-ring 7 is prepared in less than half the manipulations previously reported.

Solid phase synthesis of phosphorothioate oligonucleotides utilizing diethyldithiocarbonate disulfide (DDD) as an efficient sulfur transfer reagent.

PubMed

Cheruvallath, Zacharia S; Kumar, R Krishna; Rentel, Claus; Cole, Douglas L; Ravikumar, Vasulinga T

2003-04-01

Diethyldithiodicarbonate (DDD), a cheap and easily prepared compound, is found to be a rapid and efficient sulfurizing reagent in solid phase synthesis of phosphorothioate oligodeoxyribonucleotides via the phosphoramidite approach. Product yield and quality based on IP-LC-MS compares well with high quality oligonucleotides synthesized using phenylacetyl disulfide (PADS) which is being used for manufacture of our antisense drugs.

Synthesis and Properties of Chelating N-Heterocyclic Carbene Rhodium(I) Complexes: Synthetic Experiments in Current Organometallic Chemistry

ERIC Educational Resources Information Center

Mata, Jose A.; Poyatos, Macarena; Mas-Marza, Elena

2011-01-01

The preparation and characterization of two air-stable Rh(I) complexes bearing a chelating N-heterocyclic carbene (NHC) ligand is described. The synthesis involves the preparation of a Ag(I)-NHC complex and its use as carbene transfer agent to a Rh(I) precursor. The so obtained complex can be further reacted with carbon monoxide to give the…

Genetic Assay for Transcription Errors: Methods to Monitor Treatments or Chemicals that Increase the Error Rate of RNA synthesis | NCI Technology Transfer Center | TTC

Cancer.gov

Researchers at the National Cancer Institute (NCI) developed a genetic assay for detecting transcription errors in RNA synthesis. This new assay extends the familiar concept of an Ames test which monitors DNA damage and synthesis errors to the previously inaccessible issue of RNA synthesis fidelity. The FDA requires genetic DNA focused tests for all drug approval as it assesses the in vivo mutagenic and carcinogenic potential of a drug. The new assay will open an approach to monitoring the impact of treatments on the accuracy of RNA synthesis. Errors in transcription have been hypothesized to be a component of aging and age-related diseases. The National Cancer Institute (NCI) seeks licensing partners for the genetic assay.

Synthesis and transfer of galactolipids in the chloroplast envelope membranes of Arabidopsis thaliana.

PubMed

Kelly, Amélie A; Kalisch, Barbara; Hölzl, Georg; Schulze, Sandra; Thiele, Juliane; Melzer, Michael; Roston, Rebecca L; Benning, Christoph; Dörmann, Peter

2016-09-20

Galactolipids [monogalactosyldiacylglycerol (MGDG) and digalactosyldiacylglycerol (DGDG)] are the hallmark lipids of photosynthetic membranes. The galactolipid synthases MGD1 and DGD1 catalyze consecutive galactosyltransfer reactions but localize to the inner and outer chloroplast envelopes, respectively, necessitating intermembrane lipid transfer. Here we show that the N-terminal sequence of DGD1 (NDGD1) is required for galactolipid transfer between the envelopes. Different diglycosyllipid synthases (DGD1, DGD2, and Chloroflexus glucosyltransferase) were introduced into the dgd1-1 mutant of Arabidopsis in fusion with N-terminal extensions (NDGD1 and NDGD2) targeting to the outer envelope. Reconstruction of DGDG synthesis in the outer envelope membrane was observed only with diglycosyllipid synthase fusion proteins carrying NDGD1, indicating that NDGD1 enables galactolipid translocation between envelopes. NDGD1 binds to phosphatidic acid (PA) in membranes and mediates PA-dependent membrane fusion in vitro. These findings provide a mechanism for the sorting and selective channeling of lipid precursors between the galactolipid pools of the two envelope membranes.

Thermal Timescale Mass Transfer In Binary Population Synthesis

NASA Astrophysics Data System (ADS)

Justham, S.; Kolb, U.

2004-07-01

Studies of binary evolution have, until recently, neglected thermal timescale mass transfer (TTMT). Recent work has suggested that this previously poorly studied area is crucial in the understanding of systems across the compact binary spectrum. We use the state-of-the-art binary population synthesis code BiSEPS (Willems and Kolb, 2002, MNRAS 337 1004-1016). However, the present treatment of TTMT is incomplete due to the nonlinear behaviour of stars in their departure from gravothermal `equilibrium'. Here we show work that should update the ultrafast stellar evolution algorithms within BiSEPS to make it the first pseudo-analytic code that can follow TTMT properly. We have generated fits to a set of over 300 Case B TTMT sequences with a range of intermediate-mass donors. These fits produce very good first approximations to both HR diagrams and mass-transfer rates (see figures 1 and 2), which we later hope to improve and extend. They are already a significant improvement over the previous fits.

Preparation and Structural Studies on Hybrid Core-Shell Nanoparticles Consisting of Silica Core and Conjugated Block Copolymer Shell Prepared by Surface-Initiated Polymerization

NASA Astrophysics Data System (ADS)

Chatterjee, Sourav; Karam, Tony; Rosu, Cornelia; Li, Xin; Do, Changwoo; Youm, Sang Gil; Haber, Louis; Russo, Paul; Nesterov, Evgueni

Controlled Kumada catalyst-transfer polymerization occurring by chain-growth mechanism was developed for the synthesis of conjugated polymers and block copolymers from the surface of inorganic substrates such as silica nanoparticles. Although synthesis of conjugated polymers via Kumada polymerization became an established method for solution polymerization, carrying out the same reaction in heterogeneous conditions to form monodisperse polymer chains still remains a challenge. We developed and described a simple and efficient approach to the preparation of surface-immobilized layer of catalytic Ni(II) initiator, and demonstrated using it to prepare polymers and block copolymers on silica nanoparticle. The structure of the resulting hybrid nanostructures was thoroughly studied using small-angle neutron and X-ray scattering, thermal analysis, and optical spectroscopy. The photoexcitation energy transfer processes in the conjugated polymer shell were studied via steady-state and time resolved transient absorption spectroscopy. This study uncovered important details of the energy transfer, which will be discussed in this presentation.

Direct integration of polycrystalline graphene into light emitting diodes by plasma-assisted metal-catalyst-free synthesis.

PubMed

Kim, Yong Seung; Joo, Kisu; Jerng, Sahng-Kyoon; Lee, Jae Hong; Moon, Daeyoung; Kim, Jonghak; Yoon, Euijoon; Chun, Seung-Hyun

2014-03-25

The integration of graphene into devices is a challenging task because the preparation of a graphene-based device usually includes graphene growth on a metal surface at elevated temperatures (∼1000 °C) and a complicated postgrowth transfer process of graphene from the metal catalyst. Here we report a direct integration approach for incorporating polycrystalline graphene into light emitting diodes (LEDs) at low temperature by plasma-assisted metal-catalyst-free synthesis. Thermal degradation of the active layer in LEDs is negligible at our growth temperature, and LEDs could be fabricated without a transfer process. Moreover, in situ ohmic contact formation is observed between DG and p-GaN resulting from carbon diffusion into the p-GaN surface during the growth process. As a result, the contact resistance is reduced and the electrical properties of directly integrated LEDs outperform those of LEDs with transferred graphene electrodes. This relatively simple method of graphene integration will be easily adoptable in the industrialization of graphene-based devices.

One-step synthesis of pyridines and dihydropyridines in a continuous flow microwave reactor

PubMed Central

Fusillo, Vincenzo; Jenkins, Robert L; Lubinu, M Caterina; Mason, Christopher

2013-01-01

Summary The Bohlmann–Rahtz pyridine synthesis and the Hantzsch dihydropyridine synthesis can be carried out in a microwave flow reactor or using a conductive heating flow platform for the continuous processing of material. In the Bohlmann–Rahtz reaction, the use of a Brønsted acid catalyst allows Michael addition and cyclodehydration to be carried out in a single step without isolation of intermediates to give the corresponding trisubstituted pyridine as a single regioisomer in good yield. Furthermore, 3-substituted propargyl aldehydes undergo Hantzsch dihydropyridine synthesis in preference to Bohlmann–Rahtz reaction in a very high yielding process that is readily transferred to continuous flow processing. PMID:24204407

Synthesis of ent-kaurane diterpene monoglycosides.

PubMed

Chaturvedula, Venkata Sai Prakash; Klucik, Josef; Upreti, Mani; Prakash, Indra

2011-10-03

Synthesis of two ent-kaurane diterpene glycosides, steviol 19-O-β-D-glucopyranosiduronic acid (steviol glucuronide, 5), and 13-hydroxy ent-kaur-16-en-19-oic acid-β-D-glucopyranosyl ester (7) has been achieved from a common starting material, steviol, using phase transfer catalyst. Also, synthesis of an additional 17-nor-ent-kaurane glycoside, namely 13-methyl-16-oxo-17-nor-ent-kauran-19-oic acid-β-D-glucopyranosyl ester (10) was performed using the starting material isosteviol and similar synthetic methodology. Synthesis of all three steviol glycosides was performed using straightforward chemistry and their structures were characterized on the basis of 1D and 2D NMR as well as mass spectral (MS) data.

Pollination in Nicotiana alata stimulates synthesis and transfer to the stigmatic surface of NaStEP, a vacuolar Kunitz proteinase inhibitor homologue

PubMed Central

Busot, Grethel Yanet; McClure, Bruce; Ibarra-Sánchez, Claudia Patricia; Jiménez-Durán, Karina; Vázquez-Santana, Sonia; Cruz-García, Felipe

2008-01-01

After landing on a wet stigma, pollen grains hydrate and germination generally occurs. However, there is no certainty of the pollen tube growth through the style to reach the ovary. The pistil is a gatekeeper that evolved in many species to recognize and reject the self-pollen, avoiding endogamy and encouraging cross-pollination. However, recognition is a complex process, and specific factors are needed. Here the isolation and characterization of a stigma-specific protein from N. alata, NaStEP (N. alata Stigma Expressed Protein), that is homologous to Kunitz-type proteinase inhibitors, are reported. Activity gel assays showed that NaStEP is not a functional serine proteinase inhibitor. Immunohistochemical and protein blot analyses revealed that NaStEP is detectable in stigmas of self-incompatible (SI) species N. alata, N. forgetiana, and N. bonariensis, but not in self-compatible (SC) species N. tabacum, N. plumbaginifolia, N. benthamiana, N. longiflora, and N. glauca. NaStEP contains the vacuolar targeting sequence NPIVL, and immunocytochemistry experiments showed vacuolar localization in unpollinated stigmas. After self-pollination or pollination with pollen from the SC species N. tabacum or N. plumbaginifolia, NaStEP was also found in the stigmatic exudate. The synthesis and presence in the stigmatic exudate of this protein was strongly induced in N. alata following incompatible pollination with N. tabacum pollen. The transfer of NaStEP to the stigmatic exudate was accompanied by perforation of the stigmatic cell wall, which appeared to release the vacuolar contents to the apoplastic space. The increase in NaStEP synthesis after pollination and its presence in the stigmatic exudates suggest that this protein may play a role in the early pollen–stigma interactions that regulate pollen tube growth in Nicotiana. PMID:18689443

Novel Strategy for Photopatterning Emissive Polymer Brushes for Organic Light Emitting Diode Applications

PubMed Central

2017-01-01

A light-mediated methodology to grow patterned, emissive polymer brushes with micron feature resolution is reported and applied to organic light emitting diode (OLED) displays. Light is used for both initiator functionalization of indium tin oxide and subsequent atom transfer radical polymerization of methacrylate-based fluorescent and phosphorescent iridium monomers. The iridium centers play key roles in photocatalyzing and mediating polymer growth while also emitting light in the final OLED structure. The scope of the presented procedure enables the synthesis of a library of polymers with emissive colors spanning the visible spectrum where the dopant incorporation, position of brush growth, and brush thickness are readily controlled. The chain-ends of the polymer brushes remain intact, affording subsequent chain extension and formation of well-defined diblock architectures. This high level of structure and function control allows for the facile preparation of random ternary copolymers and red–green–blue arrays to yield white emission. PMID:28691078

Novel Strategy for Photopatterning Emissive Polymer Brushes for Organic Light Emitting Diode Applications.

PubMed

Page, Zachariah A; Narupai, Benjaporn; Pester, Christian W; Bou Zerdan, Raghida; Sokolov, Anatoliy; Laitar, David S; Mukhopadhyay, Sukrit; Sprague, Scott; McGrath, Alaina J; Kramer, John W; Trefonas, Peter; Hawker, Craig J

2017-06-28

A light-mediated methodology to grow patterned, emissive polymer brushes with micron feature resolution is reported and applied to organic light emitting diode (OLED) displays. Light is used for both initiator functionalization of indium tin oxide and subsequent atom transfer radical polymerization of methacrylate-based fluorescent and phosphorescent iridium monomers. The iridium centers play key roles in photocatalyzing and mediating polymer growth while also emitting light in the final OLED structure. The scope of the presented procedure enables the synthesis of a library of polymers with emissive colors spanning the visible spectrum where the dopant incorporation, position of brush growth, and brush thickness are readily controlled. The chain-ends of the polymer brushes remain intact, affording subsequent chain extension and formation of well-defined diblock architectures. This high level of structure and function control allows for the facile preparation of random ternary copolymers and red-green-blue arrays to yield white emission.

Mussel-Inspired Polydopamine Functionalized Plasmonic Nanocomposites for Single-Particle Catalysis.

PubMed

Wang, Jun-Gang; Hua, Xin; Li, Meng; Long, Yi-Tao

2017-01-25

Polydopamine functionalized plasmonic nanocomposites with well-distributed catalytically active small gold nanoislands around large gold core were fabricated without using any chemical reductant or surfactant. The optical properties, surface molecular structures, and ensemble catalytic activity of the gold nanocomposites were investigated by time-of-flight secondary ion mass spectrometry and UV-vis spectroscopy, respectively. Moreover, the considerable catalytic activity of the nanocomposites toward 4-nitrophenol reduction was real time monitored by dark-field spectroscopy techniques at the single-nanoparticle level avoiding averaging effects in bulk systems. According to the obtained plasmonic signals from individual nanocomposites, the electron charging and discharging rates for these nanocomposites during the catalytic process were calculated. Our results offer new insights into the design and synthesis of plasmonic nanocomposites for future catalytic applications as well as a further mechanistic understanding of the electron transfer during the catalytic process at the single-nanoparticle level.

Heat-inducible hygromycin resistance in transgenic tobacco.

PubMed

Severin, K; Schöffl, F

1990-12-01

We have constructed a chimaeric gene consisting of the promoter of the soybean heat shock (hs) gene Gmhsp17, 6-L, the coding region of a hygromycin phosphotransferase (hpt) gene, and the termination sequence of the nopaline synthase (nos) gene. This gene fusion was introduced into tobacco by Agrobacterium-mediated gene transfer. Heat-inducible synthesis of mRNA was shown by northern hybridization, and translation of this RNA into a functional protein was indicated by plant growth on hygromycin-containing media in a temperature-dependent fashion. One hour incubation at 40 degrees C per day, applied for several weeks, was sufficient to express the resistant phenotype in transgenic plants containing the chimaeric hs-hpt gene. These data suggest that the hygromycin resistance gene is functional and faithfully controlled by the soybean hs promoter. The suitability of these transgenic plants for selection of mutations that alter the hs response is discussed.

"Super-Reducing" Photocatalysis: Consecutive Energy and Electron Transfers with Polycyclic Aromatic Hydrocarbons.

PubMed

Brasholz, Malte

2017-08-21

Donation welcome: Recent developments in visible-light photocatalysis allow the utilization of increasingly negative reduction potentials. Successive energy and electron transfer with polycyclic aromatic hydrocarbons enables the catalytic formation of strongly reducing arene radical anions, classical stoichiometric reagents for one-electron reduction in organic synthesis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Efficient transfer of information from hexitol nucleic acids to RNA during nonenzymatic oligomerization

NASA Technical Reports Server (NTRS)

Kozlov, I. A.; De Bouvere, B.; Van Aerschot, A.; Herdewijn, P.; Orgel, L. E.

1999-01-01

Hexitol nucleic acids (HNAs) are DNA analogues that contain the standard nucleoside bases attached to a phosphorylated 1,5-anhydrohexitol backbone. We find that HNAs support efficient information transfer in nonensymatic template-directed reactions. HNA heterosequences appeared to be superior to the corresponding DNA heterosequences in facilitating synthesis of complementary oligonucleotides from nucleoside-5'-phosphoro-2-methyl imidazolides.

2012 Gordon Research Conference, Electron donor-acceptor interactions, August 5-10 2012

DOE Office of Scientific and Technical Information (OSTI.GOV)

McCusker, James

The upcoming incarnation of the Gordon Research Conference on Electron Donor Acceptor Interactions will feature sessions on classic topics including proton-coupled electron transfer, dye-sensitized solar cells, and biological electron transfer, as well as emerging areas such as quantum coherence effects in donor-acceptor interactions, spintronics, and the application of donor-acceptor interactions in chemical synthesis.

Controlling the Internal Heat Transfer Coefficient by the Characteristics of External Flows

NASA Astrophysics Data System (ADS)

Zhuromskii, V. M.

2018-01-01

The engineering-physical fundamentals of substance synthesis in a boiling apparatus are presented. We have modeled a system of automatic stabilization of the maximum internal heat transfer coefficient in such an apparatus by the characteristics of external flows on the basis of adaptive seeking algorithms. The results of operation of the system in the shop are presented.

The physiological basis of Glottal electromagnetic micropower sensors (GEMS) and their use in defining an excitation function for the human vocal tract

NASA Astrophysics Data System (ADS)

Burnett, Gregory Clell

1999-10-01

The definition, use, and physiological basis of Glottal Electromagnetic Micropower Sensors (GEMS) is presented. These sensors are a new type of low power (<20 milliwatts radiated) microwave regime (900 MHz to 2.5 GHz) multi-purpose motion sensor developed at the Lawrence Livermore National Laboratory. The GEMS are sensitive to movement in an adjustable field of view (FOV) surrounding the antennae. In this thesis, the GEMS has been utilized for speech research, targeted to receive motion signals from the subglottal region of the trachea. The GEMS signal is analyzed to determine the physiological source of the signal, and this information is used to calculate the subglottal pressure, effectively an excitation function for the human vocal tract. For the first time, an excitation function may be calculated in near real time using a noninvasive procedure. Several experiments and models are presented to demonstrate that the GEMS signal is representative of the motion of the subglottal posterior wall of the trachea as it vibrates in response to the pressure changes caused by the folds as they modulate the airflow supplied by the lungs. The vibrational properties of the tracheal wall are modeled using a lumped-element circuit model. Taking the output of the vocal tract to be the audio pressure captured by a microphone and the input to be the subglottal pressure, the transfer function of the vocal tract (including the nasal cavities) can be approximated every 10-30 milliseconds using an autoregressive moving-average model. Unlike the currently utilized method of transfer function approximation, this new method only involves noninvasive GEMS measurements and digital signal processing and does not demand the difficult task of obtaining precise physical measurements of the tract and subsequent estimation of the transfer function using its cross-sectional area. The ability to measure the physical motion of the trachea enables a significant number of potential applications, ranging from very accurate pitch detection to speech synthesis, speaker verification, and speech recognition.

Synthesis, Spectra, and Theoretical Investigations of 1,3,5-Triazines Compounds as Ultraviolet Rays Absorber Based on Time-Dependent Density Functional Calculations and three-Dimensional Quantitative Structure-Property Relationship.

PubMed

Wang, Xueding; Xu, Yilian; Yang, Lu; Lu, Xiang; Zou, Hao; Yang, Weiqing; Zhang, Yuanyuan; Li, Zicheng; Ma, Menglin

2018-03-01

A series of 1,3,5-triazines were synthesized and their UV absorption properties were tested. The computational chemistry methods were used to construct quantitative structure-property relationship (QSPR), which was used to computer aided design of new 1,3,5-triazines ultraviolet rays absorber compounds. The experimental UV absorption data are in good agreement with those predicted data using the Time-dependent density functional theory (TD-DFT) [B3LYP/6-311 + G(d,p)]. A suitable forecasting model (R > 0.8, P < 0.0001) was revealed. Predictive three-dimensional quantitative structure-property relationship (3D-QSPR) model was established using multifit molecular alignment rule of Sybyl program, which conclusion is consistent with the TD-DFT calculation. The exceptional photostability mechanism of such ultraviolet rays absorber compounds was studied and confirmed as principally banked upon their ability to undergo excited-state deactivation via an ultrafast excited-state proton transfer (ESIPT). The intramolecular hydrogen bond (IMHB) of 1,3,5-triazines compounds is the basis for the excited state proton transfer, which was explored by IR spectroscopy, UV spectra, structural and energetic aspects of different conformers and frontier molecular orbitals analysis.

Functional characterization of electron-transferring flavoprotein and its dehydrogenase required for fungal development and plant infection by the rice blast fungus

PubMed Central

Li, Ya; Zhu, Jindong; Hu, Jiexiong; Meng, Xiuli; Zhang, Qi; Zhu, Kunpeng; Chen, Xiaomin; Chen, Xuehang; Li, Guangpu; Wang, Zonghua; Lu, Guodong

2016-01-01

Electron-transferring flavoprotein (ETF) and its dehydrogenase (ETFDH) are highly conserved electron carriers which mainly function in mitochondrial fatty acid β oxidation. Here, we report the identification and characterization of ETF α and β subunit encoding genes (ETFA and ETFB) and ETFDH encoding gene (ETFDH) in the rice blast fungus Magnaporthe oryzae. It was demonstrated that, by impacting fatty acid metabolism, ETF and ETFDH mutations led to severe growth and conidiation defects, which could be largely rescued by exogenous acetate or carbonate. Furthermore, although conidium germination and appressorium formation appeared to be normal in ETF and ETFDH mutants, most appressoria failed to penetrate the host epidermis due to low turgor pressure. The few appressoria that succeeded in penetration were severely restricted in invasive growth and consequently failed to cause disease. Moreover, ETF mutant etfb− induced ROS accumulation in infected host cells and exogenous antioxidant GSH accelerated mutant invading growth without increasing the penetration rate. In addition, mutant etfb− displayed elevated lipid body accumulation and reduced ATP synthesis. Taken together, ETF and ETFDH play an important role in fungal development and plant infection in M. oryzae by regulation of fatty acid metabolism, turgor establishment and induction of host ROS accumulation. PMID:27113712

Functional characterization of electron-transferring flavoprotein and its dehydrogenase required for fungal development and plant infection by the rice blast fungus.

PubMed

Li, Ya; Zhu, Jindong; Hu, Jiexiong; Meng, Xiuli; Zhang, Qi; Zhu, Kunpeng; Chen, Xiaomin; Chen, Xuehang; Li, Guangpu; Wang, Zonghua; Lu, Guodong

2016-04-26

Electron-transferring flavoprotein (ETF) and its dehydrogenase (ETFDH) are highly conserved electron carriers which mainly function in mitochondrial fatty acid β oxidation. Here, we report the identification and characterization of ETF α and β subunit encoding genes (ETFA and ETFB) and ETFDH encoding gene (ETFDH) in the rice blast fungus Magnaporthe oryzae. It was demonstrated that, by impacting fatty acid metabolism, ETF and ETFDH mutations led to severe growth and conidiation defects, which could be largely rescued by exogenous acetate or carbonate. Furthermore, although conidium germination and appressorium formation appeared to be normal in ETF and ETFDH mutants, most appressoria failed to penetrate the host epidermis due to low turgor pressure. The few appressoria that succeeded in penetration were severely restricted in invasive growth and consequently failed to cause disease. Moreover, ETF mutant etfb(-) induced ROS accumulation in infected host cells and exogenous antioxidant GSH accelerated mutant invading growth without increasing the penetration rate. In addition, mutant etfb(-) displayed elevated lipid body accumulation and reduced ATP synthesis. Taken together, ETF and ETFDH play an important role in fungal development and plant infection in M. oryzae by regulation of fatty acid metabolism, turgor establishment and induction of host ROS accumulation.

Multiple functionalization of fluorescent nanoparticles for specific biolabeling and drug delivery of dopamine

NASA Astrophysics Data System (ADS)

Malvindi, Maria Ada; di Corato, Riccardo; Curcio, Annalisa; Melisi, Daniela; Rimoli, Maria Grazia; Tortiglione, Claudia; Tino, Angela; George, Chandramohan; Brunetti, Virgilio; Cingolani, Roberto; Pellegrino, Teresa; Ragusa, Andrea

2011-12-01

The development of fluorescent biolabels for specific targeting and controlled drug release is of paramount importance in biological applications due to their potential in the generation of novel tools for simultaneous diagnosis and treatment of diseases. Dopamine is a neurotransmitter involved in several neurological diseases, such as Parkinson's disease and attention deficit hyperactivity disorder (ADHD), and the controlled delivery of its agonists already proved to have beneficial effects both in vitro and in vivo. Here, we report the synthesis and multiple functionalization of highly fluorescent CdSe/CdS quantum rods for specific biolabeling and controlled drug release. After being transferred into aqueous media, the nanocrystals were made highly biocompatible through PEG conjugation and covered by a carbohydrate shell, which allowed specific GLUT-1 recognition. Controlled attachment of dopamine through an ester bond also allowed hydrolysis by esterases, yielding a smart nanotool for specific biolabeling and controlled drug release.The development of fluorescent biolabels for specific targeting and controlled drug release is of paramount importance in biological applications due to their potential in the generation of novel tools for simultaneous diagnosis and treatment of diseases. Dopamine is a neurotransmitter involved in several neurological diseases, such as Parkinson's disease and attention deficit hyperactivity disorder (ADHD), and the controlled delivery of its agonists already proved to have beneficial effects both in vitro and in vivo. Here, we report the synthesis and multiple functionalization of highly fluorescent CdSe/CdS quantum rods for specific biolabeling and controlled drug release. After being transferred into aqueous media, the nanocrystals were made highly biocompatible through PEG conjugation and covered by a carbohydrate shell, which allowed specific GLUT-1 recognition. Controlled attachment of dopamine through an ester bond also allowed hydrolysis by esterases, yielding a smart nanotool for specific biolabeling and controlled drug release. Electronic supplementary information (ESI) available: TEM images, absorption and emission spectra, ζ-potential and DLS graphics, gel electrophoresis images, cyclic voltammograms, western blot and RT-PCR data. See DOI: 10.1039/c1nr10797f

Competitive Energy and Electron Transfer in β-Functionalized Free-Base Porphyrin-Zinc Porphyrin Dimer Axially Coordinated to C60 : Synthesis, Supramolecular Formation and Excited-State Processes.

PubMed

Hu, Yi; Thomas, Michael B; Jinadasa, R G Waruna; Wang, Hong; D'Souza, Francis

2017-09-18

Simultaneous occurrence of energy and electron transfer events involving different acceptor sites in a newly assembled supramolecular triad comprised of covalently linked free-base porphyrin-zinc porphyrin dyad, H 2 P-ZnP axially coordinated to electron acceptor fullerene, has been successfully demonstrated. The dyad was connected through the β-pyrrole positions of the porphyrin macrocycle instead of the traditionally used meso-positions for better electronic communication. Interestingly, the β-pyrrole functionalization modulated the optical properties to such an extent that it was possible to almost exclusively excite the zinc porphyrin entity in the supramolecular triad. The measured binding constant for the complex with 1:1 molecular stoichiometry was in the order of 10 4  m -1 revealing moderately stable complex formation. An energy level diagram constructed using optical, electrochemical and computational results suggested that both the anticipated energy and electron events are thermodynamically feasible in the triad. Consequently, it was possible to demonstrate occurrence of excited state energy transfer to the covalently linked H 2 P, and electron transfer to the coordinated ImC 60 from studies involving steady-state and time-resolved emission, and femto- and nanosecond transient absorption studies. The estimated energy transfer was around 67 % in the dyad with a rate constant of 1.1×10 9  s -1 . In the supramolecular triad, the charge separated state was rather long-lived although it was difficult to arrive the exact lifetime of charge separated state from nanosecond transient spectral studies due to overlap of strong triplet excited signals of porphyrin in the monitoring wavelength window. Nevertheless, simultaneous occurrence of energy and electron transfer in the appropriately positioned energy and electron acceptor entities in a supramolecular triad was possible to demonstrate in the present study, a step forward to unraveling the complex photochemical events occurring in natural photosynthesis and its implications in building light energy harvesting devices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantum dot-decorated semiconductor micro- and nanoparticles: A review of their synthesis, characterization and application in photocatalysis.

PubMed

Bajorowicz, Beata; Kobylański, Marek P; Gołąbiewska, Anna; Nadolna, Joanna; Zaleska-Medynska, Adriana; Malankowska, Anna

2018-06-01

Quantum dot (QD)-decorated semiconductor micro- and nanoparticles are a new class of functional nanomaterials that have attracted considerable interest for their unique structural, optical and electronic properties that result from the large surface-to-volume ratio and the quantum confinement effect. In addition, because of QDs' excellent light-harvesting capacity, unique photoinduced electron transfer, and up-conversion behaviour, semiconductor nanoparticles decorated with quantum dots have been used widely in photocatalytic applications for the degradation of organic pollutants in both the gas and aqueous phases. This review is a comprehensive overview of the recent progress in synthesis methods for quantum dots and quantum dot-decorated semiconductor composites with an emphasis on their composition, morphology and optical behaviour. Furthermore, various approaches used for the preparation of QD-based composites are discussed in detail with respect to visible and UV light-induced photoactivity. Finally, an outlook on future development is proposed with the goal of overcoming challenges and stimulating further research into this promising field. Copyright © 2018 Elsevier B.V. All rights reserved.

Synthesis and Characterization of 2-D Materials

NASA Astrophysics Data System (ADS)

Pazos, S.; Sahoo, P.; Afaneh, T.; Rodriguez Gutierrez, H.

Atomically thin transition-metal dichacogenides (TMD), graphene, and boron nitride (BN) are two-dimensional materials where the charge carriers (electrons and holes) are confined to move in a plane. They exhibit distinctive optoelectronic properties compared to their bulk layered counterparts. When combined into heterostructures, these materials open more possibilities in terms of new properties and device functionality. In this work, WSe2 and graphene were grown using Chemical Vapor Deposition (CVD) and Physical Vapor Deposition (PVD) techniques. The quality and morphology of each material was checked using Raman, Photoluminescence Spectroscopy, and Scanning Electron Microscopy. Graphene had been successfully grown homogenously, characterized, and transferred from copper to silicon dioxide substrates; these films will be used in future studies to build 2-D devices. Different morphologies of WSe2 2-D islands were successfully grown on SiO2 substrates. Depending on the synthesis conditions, the material on each sample had single layer, double layer, and multi-layer areas. A variety of 2-D morphologies were also observed in the 2-D islands. This project is supported by the NSF REU Grant #1560090 and NSF Grant #DMR-1557434.

Photoinduced, copper-catalyzed alkylation of amides with unactivated secondary alkyl halides at room temperature.

PubMed

Do, Hien-Quang; Bachman, Shoshana; Bissember, Alex C; Peters, Jonas C; Fu, Gregory C

2014-02-05

The development of a mild and general method for the alkylation of amides with relatively unreactive alkyl halides (i.e., poor substrates for SN2 reactions) is an ongoing challenge in organic synthesis. We describe herein a versatile transition-metal-catalyzed approach: in particular, a photoinduced, copper-catalyzed monoalkylation of primary amides. A broad array of alkyl and aryl amides (as well as a lactam and a 2-oxazolidinone) couple with unactivated secondary (and hindered primary) alkyl bromides and iodides using a single set of comparatively simple and mild conditions: inexpensive CuI as the catalyst, no separate added ligand, and C-N bond formation at room temperature. The method is compatible with a variety of functional groups, such as an olefin, a carbamate, a thiophene, and a pyridine, and it has been applied to the synthesis of an opioid receptor antagonist. A range of mechanistic observations, including reactivity and stereochemical studies, are consistent with a coupling pathway that includes photoexcitation of a copper-amidate complex, followed by electron transfer to form an alkyl radical.

Anti-Melanogenic Activity of Gagunin D, a Highly Oxygenated Diterpenoid from the Marine Sponge Phorbas sp., via Modulating Tyrosinase Expression and Degradation

PubMed Central

Lee, Ho Yeon; Jang, Eun Jeong; Bae, Song Yi; Jeon, Ju-eun; Park, Hyen Joo; Shin, Jongheon; Lee, Sang Kook

2016-01-01

Tyrosinase is the rate-limiting enzyme critical for melanin synthesis and controls pigmentation in the skin. The inhibition of tyrosinase is currently the most common approach for the development of skin-whitening cosmetics. Gagunin D (GD), a highly oxygenated diterpenoid isolated from the marine sponge Phorbas sp., has exhibited cytotoxicity toward human leukemia cells. However, the effect of GD on normal cells and the molecular mechanisms remain to be elucidated. In the present study, we identified for the first time the anti-melanogenic activity of GD and its precise underlying mechanisms in mouse melan-a cells. GD significantly inhibited melanin synthesis in the melan-a cells and a reconstructed human skin model. Further analysis revealed that GD suppressed the expression of tyrosinase and increased the rate of tyrosinase degradation. GD also inhibited tyrosinase enzymatic activity. In addition, GD effectively suppressed the expression of proteins associated with melanosome transfer. These findings suggest that GD is a potential candidate for cosmetic formulations due to its multi-functional properties. PMID:27869664

Accelerated Combinatorial High Throughput Star Polymer Synthesis via a Rapid One-Pot Sequential Aqueous RAFT (rosa-RAFT) Polymerization Scheme.

PubMed

Cosson, Steffen; Danial, Maarten; Saint-Amans, Julien Rosselgong; Cooper-White, Justin J

2017-04-01

Advanced polymerization methodologies, such as reversible addition-fragmentation transfer (RAFT), allow unprecedented control over star polymer composition, topology, and functionality. However, using RAFT to produce high throughput (HTP) combinatorial star polymer libraries remains, to date, impracticable due to several technical limitations. Herein, the methodology "rapid one-pot sequential aqueous RAFT" or "rosa-RAFT," in which well-defined homo-, copolymer, and mikto-arm star polymers can be prepared in very low to medium reaction volumes (50 µL to 2 mL) via an "arm-first" approach in air within minutes, is reported. Due to the high conversion of a variety of acrylamide/acrylate monomers achieved during each successive short reaction step (each taking 3 min), the requirement for intermediary purification is avoided, drastically facilitating and accelerating the star synthesis process. The presented methodology enables RAFT to be applied to HTP polymeric bio/nanomaterials discovery pipelines, in which hundreds of complex polymeric formulations can be rapidly produced, screened, and scaled up for assessment in a wide range of applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modularity of Plant Metabolic Gene Clusters: A Trio of Linked Genes That Are Collectively Required for Acylation of Triterpenes in Oat[W][OA

PubMed Central

Mugford, Sam T.; Louveau, Thomas; Melton, Rachel; Qi, Xiaoquan; Bakht, Saleha; Hill, Lionel; Tsurushima, Tetsu; Honkanen, Suvi; Rosser, Susan J.; Lomonossoff, George P.; Osbourn, Anne

2013-01-01

Operon-like gene clusters are an emerging phenomenon in the field of plant natural products. The genes encoding some of the best-characterized plant secondary metabolite biosynthetic pathways are scattered across plant genomes. However, an increasing number of gene clusters encoding the synthesis of diverse natural products have recently been reported in plant genomes. These clusters have arisen through the neo-functionalization and relocation of existing genes within the genome, and not by horizontal gene transfer from microbes. The reasons for clustering are not yet clear, although this form of gene organization is likely to facilitate co-inheritance and co-regulation. Oats (Avena spp) synthesize antimicrobial triterpenoids (avenacins) that provide protection against disease. The synthesis of these compounds is encoded by a gene cluster. Here we show that a module of three adjacent genes within the wider biosynthetic gene cluster is required for avenacin acylation. Through the characterization of these genes and their encoded proteins we present a model of the subcellular organization of triterpenoid biosynthesis. PMID:23532069

Theory of long binding events in single-molecule–controlled rotation experiments on F1-ATPase

PubMed Central

Volkán-Kacsó, Sándor; Marcus, Rudolph A.

2017-01-01

The theory of elastic group transfer for the binding and release rate constants for nucleotides in F1-ATPase as a function of the rotor angle is further extended in several respects. (i) A method is described for predicting the experimentally observed lifetime distribution of long binding events in the controlled rotation experiments by taking into account the hydrolysis and synthesis reactions occurring during these events. (ii) A method is also given for treating the long binding events in the experiments and obtaining the rate constants for the hydrolysis and synthesis reactions occurring during these events. (iii) The theory in the previous paper is given in a symmetric form, an extension that simplifies the application of the theory to experiments. It also includes a theory-based correction of the reported “on” and “off” rates by calculating the missed events. A near symmetry of the data about the angle of −40° and a “turnover” in the binding rate data vs. rotor angle for angles greater than ∼40° is also discussed. PMID:28652332

Role of Escherichia coli dnaG function in coliphage M13 DNA synthesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dasgupta, S.; Mitra, S.

Examination of the role of Escherichia coli dnaG function in different stages of M13 phage DNA synthesis by ultracentrifugal analysis of intracellular phage DNA in a thermosensitive dnaG mutant shows that: (a) the formation of parental double-strand replicative-form DNA (rfDNA) from the infecting virus is independent of dnaG function; (b) the synthesis of progeny rfDNA requires dnaG product; (c) after a pool of rfDNA is made up, dnaG function is not required for the progeny single-strand DNA (ssDNA) synthesis. The ssDNAs produced under nonpermissive condition are mostly circular and biologically functional.

History of L-carnitine: implications for renal disease.

PubMed

Matera, Mario; Bellinghieri, Guido; Costantino, Giuseppe; Santoro, Domenico; Calvani, Menotti; Savica, Vincenzo

2003-01-01

L-carnitine (LC) plays an essential metabolic role that consists in transferring the long chain fatty acids (LCFAs) through the mitochondrial barrier, thus allowing their energy-yielding oxidation. Other functions of LC are protection of membrane structures, stabilizing a physiologic coenzyme-A (CoA)-sulfate hydrate/acetyl-CoA ratio, and reduction of lactate production. On the other hand, numerous observations have stressed the carnitine ability of influencing, in several ways, the control mechanisms of the vital cell cycle. Much evidence suggests that apoptosis activated by palmitate or stearate addition to cultured cells is correlated with de novo ceramide synthesis. Investigations in vitro strongly support that LC is able to inhibit the death planned, most likely by preventing sphingomyelin breakdown and consequent ceramide synthesis; this effect seems to be specific for acidic sphingomyelinase. The reduction of ceramide generation and the increase in the serum levels of insulin-like growth factor (IGF)-1, could represent 2 important mechanisms underlying the observed antiapoptotic effects of acetyl-LC. Primary carnitine deficiency is an uncommon inherited disorder, related to functional anomalies in a specific organic cation/carnitine transporter (hOCTN2). These conditions have been classified as either systemic or myopathic. Secondary forms also are recognized. These are present in patients with renal tubular disorders, in which excretion of carnitine may be excessive, and in patients on hemodialysis. A lack of carnitine in hemodialysis patients is caused by insufficient carnitine synthesis and particularly by the loss through dialytic membranes, leading, in some patients, to carnitine depletion with a relative increase in esterified forms. Many studies have shown that LC supplementation leads to improvements in several complications seen in uremic patients, including cardiac complications, impaired exercise and functional capacities, muscle symptoms, increased symptomatic intradialytic hypotension, and erythropoietin-resistant anemia, normalizing the reduced carnitine palmitoyl transferase activity in red cells. Copyright 2003 by the National Kidney Foundation, Inc.

Evidence for glycosylation as a regulator of the pigmentary system: key roles of sialyl(α2-6)gal/GalNAc-terminated glycans in melanin synthesis and transfer.

PubMed

Diwakar, Ganesh; Klump, Vincent; Lazova, Rossitza; Pawelek, John

2015-08-01

The major regulators of melanogenesis are glycoproteins, however no role for glycosylation in the pathway has yet been described. We stained skin biopsies and melanocyte-keratinocyte co-cultures with a panel of 20 lectins as oligosaccharide markers. Notably, the Elderberry Bark Lectin (EBL/SNA) stained melanocytes in both systems. EBL binds the sequence Neu5Ac(α(2-6)Gal/GalNAc)- at the termini of some oligosaccharide antennae. We used inhibitors of synthesis and/or binding of this sequence to assess effects on pigmentation. Cell culture, lectin histochemistry, siRNA transfection, and assays for dopa oxidase and melanin were carried out by standard techniques. 6'-sialyllactose, a short homolog of the sequence in question, anti-sialyltransferase 6 (ST6) siRNA, and cytidine, a sialyltransferase (ST) inhibitor, each inhibited EBL binding, melanogenesis and melanosome transfer. Unexpectedly, 3'-sialyllactose and siRNA for ST3, chosen as a negative controls, also inhibited these processes. Though strong inhibitors of melanization, none of the agents affected tyrosinase/dopa oxidase activity, indicating previously unrecognized post-tyrosinase regulation of melanization. We report for the first time that Neu5Ac (α(2-6)Gal/GalNAc)- and possibly Neu5Ac(α(2-3)Gal/GalNAc)-terminated oligosaccharides play multiple roles in melanin synthesis and transfer.

Methylene blue stimulates substrate-level phosphorylation catalysed by succinyl-CoA ligase in the citric acid cycle.

PubMed

Komlódi, T; Tretter, L

2017-09-01

Methylene blue (MB), a potential neuroprotective agent, is efficient in various neurodegenerative disease models. Beneficial effects of MB have been attributed to improvements in mitochondrial functions. Substrate-level phosphorylation (SLP) results in the production of ATP independent from the ATP synthase (ATP-ase). In energetically compromised mitochondria, ATP produced by SLP can prevent the reversal of the adenine nucleotide translocase and thus the hydrolysis of glycolytic ATP. The aim of the present study was to investigate the effect of MB on mitochondrial SLP catalysed by succinyl-CoA ligase. Measurements were carried out on isolated guinea pig cortical mitochondria respiring on α-ketoglutarate, glutamate, malate or succinate. The mitochondrial functions and parameters like ATP synthesis, oxygen consumption, membrane potential, and NAD(P)H level were followed online, in parallel with the redox state of MB. SLP-mediated ATP synthesis was measured in the presence of inhibitors for ATP-ase and adenylate kinase. In the presence of the ATP-ase inhibitor oligomycin MB stimulated respiration with all of the respiratory substrates. However, the rate of ATP synthesis increased only with substrates α-ketoglutarate and glutamate (forming succinyl-CoA). MB efficiently stimulated SLP and restored the membrane potential in mitochondria also with the combined inhibition of Complex I and ATP synthase. ATP formed by SLP alleviated the energetic insufficiency generated by the lack of oxidative phosphorylation. Thus, the MB-mediated stimulation of SLP might be important in maintaining the energetic competence of mitochondria and in preventing the mitochondrial hydrolysis of glycolytic ATP. The mitochondrial effects of MB are explained by the ability to accept electrons from reducing equivalents and transfer them to cytochrome c bypassing the respiratory Complexes I and III. Copyright © 2017 Elsevier Ltd. All rights reserved.

PETI-298 Prepared by Microwave Synthesis: Neat Resin and Composite Properties

NASA Technical Reports Server (NTRS)

Smith, Joseph G.; Connell, John W.; Li, Chao-Jun; Wu, Wei; Criss, Jim M., Jr.

2004-01-01

PETI-298 is a high temperature/high performance matrix resin that is processable into composites by resin transfer molding (RTM), resin infusion and vacuum assisted RTM techniques. It is typically synthesized in a polar aprotic solvent from the reaction of an aromatic anhydride and a combination of diamines and endcapped with phenylethynylphthalic anhydride. Microwave synthesis of PETI-298 was investigated as a means to eliminate solvent and decrease reaction time. The monomers were manually mixed and placed in a microwave oven for various times to determine optimum reaction conditions. The synthetic process was subsequently scaled-up to 330g. Three batches were synthesized and combined to give 1 kg of material that was characterized for thermal and rheological properties and compared to PETI-298 prepared by the classic solution based synthetic method. The microwave synthesized PETI-298 was subsequently used to fabricate flat laminates on T650 carbon fabric by RTM. The composite panels were analyzed and mechanical properties determined and compared with those fabricated from PETI-298 prepared by the classic solution method. The microwave synthesis process and characterization of neat resin and carbon fiber reinforced composites fabricated by RTM will be presented. KEY WORDS: Resin Transfer Molding, High Temperature Polymers, Phenylethynyl Terminated Imides, Microwave Synthesis

A genetically encoded fluorescent tRNA is active in live-cell protein synthesis

PubMed Central

Masuda, Isao; Igarashi, Takao; Sakaguchi, Reiko; Nitharwal, Ram G.; Takase, Ryuichi; Han, Kyu Young; Leslie, Benjamin J.; Liu, Cuiping; Gamper, Howard; Ha, Taekjip; Sanyal, Suparna

2017-01-01

Abstract Transfer RNAs (tRNAs) perform essential tasks for all living cells. They are major components of the ribosomal machinery for protein synthesis and they also serve in non-ribosomal pathways for regulation and signaling metabolism. We describe the development of a genetically encoded fluorescent tRNA fusion with the potential for imaging in live Escherichia coli cells. This tRNA fusion carries a Spinach aptamer that becomes fluorescent upon binding of a cell-permeable and non-toxic fluorophore. We show that, despite having a structural framework significantly larger than any natural tRNA species, this fusion is a viable probe for monitoring tRNA stability in a cellular quality control mechanism that degrades structurally damaged tRNA. Importantly, this fusion is active in E. coli live-cell protein synthesis allowing peptidyl transfer at a rate sufficient to support cell growth, indicating that it is accommodated by translating ribosomes. Imaging analysis shows that this fusion and ribosomes are both excluded from the nucleoid, indicating that the fusion and ribosomes are in the cytosol together possibly engaged in protein synthesis. This fusion methodology has the potential for developing new tools for live-cell imaging of tRNA with the unique advantage of both stoichiometric labeling and broader application to all cells amenable to genetic engineering. PMID:27956502

Acid/base-regulated reversible electron transfer disproportionation of N–N linked bicarbazole and biacridine derivatives† †Electronic supplementary information (ESI) available: Experimental information, synthesis and characterization data, NMR spectra, solid state NMR data, X-ray data, ESR spectra, UV-Vis-NIR spectra, fluorescence spectra, kinetic experiments, theoretical calculations, Tables S1–S8, Scheme S1, Fig. S1–12, References. CCDC 1025063, 1038914, 1049677 and 1040722. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc00946d

PubMed Central

Pandit, Palash; Yamamoto, Koji; Nakamura, Toshikazu; Nishimura, Katsuyuki; Kurashige, Yuki; Yanai, Takeshi; Nakamura, Go; Masaoka, Shigeyuki; Furukawa, Ko; Yakiyama, Yumi; Kawano, Masaki

2015-01-01

Regulation of electron transfer on organic substances by external stimuli is a fundamental issue in science and technology, which affects organic materials, chemical synthesis, and biological metabolism. Nevertheless, acid/base-responsive organic materials that exhibit reversible electron transfer have not been well studied and developed, owing to the difficulty in inventing a mechanism to associate acid/base stimuli and electron transfer. We discovered a new phenomenon in which N–N linked bicarbazole (BC) and tetramethylbiacridine (TBA) derivatives undergo electron transfer disproportionation by acid stimulus, forming their stable radical cations and reduced species. The reaction occurs through a biradical intermediate generated by the acid-triggered N–N bond cleavage reaction of BC or TBA, which acts as a two electron acceptor to undergo electron transfer reactions with two equivalents of BC or TBA. In addition, in the case of TBA the disproportionation reaction is highly reversible through neutralization with NEt3, which recovers TBA through back electron transfer and N–N bond formation reactions. This highly reversible electron transfer reaction is possible due to the association between the acid stimulus and electron transfer via the acid-regulated N–N bond cleavage/formation reactions which provide an efficient switching mechanism, the ability of the organic molecules to act as multi-electron donors and acceptors, the extraordinary stability of the radical species, the highly selective reactivity, and the balance of the redox potentials. This discovery provides new design concepts for acid/base-regulated organic electron transfer systems, chemical reagents, or organic materials. PMID:29218181

Mimicking the photosynthetic triplet energy-transfer relay

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gust, D.; Moore, T.A.; Moore, A.L.

1993-06-30

In the reaction centers of photosynthetic organisms, chlorophyll triplet states are sometimes formed by recombination of charge-separated intermediates. These triplets are excellent sensitizers for singlet oxygen formation. Carotenoid polyenes can provide photoprotection from singlet oxygen generation by rapidly quenching chlorophyll triplet states via triplet-triplet energy transfer. Because in bacteria the reaction center carotenoid is not located adjacent to the bacteriochlorophyll special pair, which is the origin of the charge separation, it has been postulated that quenching may occur via a triplet relay involving an intermediate chlorophyll monomer. We now report the synthesis and spectroscopic study of a covalently linked carotenoidmore » (C)-porphyrin (P)-pyropheophorbide (Ppd) triad molecule which mimics this triplet relay. The pyropheophorbide singlet-state C-P-[sup 1]Ppd (generated by direct excitation or energy transfer from the attached porphyrin) undergoes intersystem crossing to the triplet C-P-[sup 3]Ppd. In oxygen-free solutions, this triplet decays to [sup 3]C-p-Ppd through a triplet-transfer relay involving an intermediate C-[sup 3]P-Ppd species. In aerated solutions, quenching of C-P-[sup 3]Ppd by the attached carotenoid competes with singlet oxygen sensitization and thus provides a degree of photoprotection. In a similar traid containing a zinc porphyrin moiety, triplet transfer is slow due to the higher energy of the C-[sup 3]P[sub Zn]-Ppd intermediate, and photoprotection via the relay is nonexistent. The triplet relay ceases to function at low temperatures in both the natural and biomimetic cases due to the endergonicity of the first step. 37 refs., 6 figs., 1 tab.« less

Room temperature synthesis of hydrophilic Ln(3+)-doped KGdF4 (Ln = Ce, Eu, Tb, Dy) nanoparticles with controllable size: energy transfer, size-dependent and color-tunable luminescence properties.

PubMed

Yang, Dongmei; Li, Guogang; Kang, Xiaojiao; Cheng, Ziyong; Ma, Ping'an; Peng, Chong; Lian, Hongzhou; Li, Chunxia; Lin, Jun

2012-06-07

In this paper, we demonstrate a simple, template-free, reproducible and one-step synthesis of hydrophilic KGdF(4): Ln(3+) (Ln = Ce, Eu, Tb and Dy) nanoparticles (NPs) via a solution-based route at room temperature. X-Ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), photoluminescence (PL) and cathodoluminescence (CL) spectra are used to characterize the samples. The results indicate that the use of water-diethyleneglycol (DEG) solvent mixture as the reaction medium not only allows facile particle size control but also endows the as-prepared samples with good water-solubility. In particular, the mean size of NPs is monotonously reduced with the increase of DEG content, from 215 to 40 nm. The luminescence intensity and absolute quantum yields for KGdF(4): Ce(3+), Tb(3+) NPs increase remarkably with particle sizes ranging from 40 to 215 nm. Additionally, we systematically investigate the magnetic and luminescence properties of KGdF(4): Ln(3+) (Ln = Ce, Eu, Tb and Dy) NPs. They display paramagnetic and superparamagnetic properties with mass magnetic susceptibility values of 1.03 × 10(-4) emu g(-1)·Oe and 3.09 × 10(-3) emu g(-1)·Oe at 300 K and 2 K, respectively, and multicolor emissions due to the energy transfer (ET) process Ce(3+)→ Gd(3+)→ (Gd(3+))(n)→ Ln(3+), in which Gd(3+) ions play an intermediate role in this process. Representatively, it is shown that the energy transfer from Ce(3+) to Tb(3+) occurs mainly via the dipole-quadrupole interaction by comparison of the theoretical calculation and experimental results. This kind of magnetic/luminescent dual-function materials may have promising applications in multiple biolabels and MR imaging.

Synthesis of monolithic graphene – graphite integrated electronics

PubMed Central

Park, Jang-Ung; Nam, SungWoo; Lee, Mi-Sun; Lieber, Charles M.

2013-01-01

Encoding electronic functionality into nanoscale elements during chemical synthesis has been extensively explored over the past decade as the key to developing integrated nanosystems1 with functions defined by synthesis2-6. Graphene7-12 has been recently explored as a two-dimensional nanoscale material, and has demonstrated simple device functions based on conventional top-down fabrication13-20. However, the synthetic approach to encoding electronic functionality and thus enabling an entire integrated graphene electronics in a chemical synthesis had not previously been demonstrated. Here we report an unconventional approach for the synthesis of monolithically-integrated electronic devices based on graphene and graphite. Spatial patterning of heterogeneous catalyst metals permits the selective growth of graphene and graphite, with controlled number of graphene layers. Graphene transistor arrays with graphitic electrodes and interconnects were formed from synthesis. These functional, all-carbon structures were transferrable onto a variety of substrates. The integrated transistor arrays were used to demonstrate real-time, multiplexed chemical sensing, and more significantly, multiple carbon layers of the graphene-graphite device components were vertically assembled to form a three-dimensional flexible structure which served as a top-gate transistor array. These results represent a substantial progress towards encoding electronic functionality via chemical synthesis and suggest future promise for one-step integration of graphene-graphite based electronics. PMID:22101813

Performance of an ultrafiltration membrane bioreactor (UF-MBR) as a processing strategy for the synthesis of galacto-oligosaccharides at high substrate concentrations.

PubMed

Córdova, Andrés; Astudillo, Carolina; Vera, Carlos; Guerrero, Cecilia; Illanes, Andrés

2016-04-10

The performance of an ultrafiltration membrane bioreactor for galacto-oligosaccharides (GOS) synthesis using high lactose concentrations (470 g/L) and β-galactosidase from Aspergillus oryzae was assessed. Tested processing variables were: transmembrane-pressure (PT), crossflow-velocity (CFV) and temperature. Results showed that processing variables had significant effect on the yield, the enzyme productivity and the flux but did not on GOS concentration and reaction conversion obtained. As expected, the use of high turbulences improved mass transfer and reduced the membrane fouling, but the use of very high crossflow-velocities caused operational instability due to vortex formation and lactose precipitation. The use of a desirability function allowed determining optimal conditions which were: PT (4.38 bar), CFV (7.35 m/s) and temperature (53.1 °C), optimizing simultaneously flux and specific enzyme productivity Under these optimal processing conditions, shear-stress and temperature did not affect the enzyme but long-term operation was limited by flux decay. In comparison to a conventional batch system, at 12.5h of processing time, the continuous GOS synthesis in the UF-MBR increased significantly the amount of processed substrate and a 2.44-fold increase in the amount of GOS produced per unit mass of catalyst was obtained with respect to a conventional batch system. Furthermore, these results can be improved by far by tuning the membranearea/reactionvolume ratio, showing that the use of an UF-MBR is an attractive alternative for the GOS synthesis at very high lactose concentrations. Copyright © 2016 Elsevier B.V. All rights reserved.

Substrate-controlled Rh(II)-catalyzed single-electron-transfer (SET): divergent synthesis of fused indoles.

PubMed

Chen, Kai; Zhu, Zi-Zhong; Liu, Jia-Xin; Tang, Xiang-Ying; Wei, Yin; Shi, Min

2016-01-07

Rh(II)-catalyzed diversified ring expansions controlled by single-electron-transfer (SET) have been disclosed in this communication, producing a series of indole-fused azetidines and 1H-carbazoles or related derivatives in moderate to good yields via Rh2(III,II) nitrene radical intermediates. The direction of ring expansion branches according to different ring sizes of methylenecycloalkanes.

Diastereoselective Synthesis of Seven-Membered Ring trans-Alkenes from Dienes and Aldehydes by Silylene Transfer

PubMed Central

Greene, Margaret A.; Prévost, Michel; Tolopilo, Joshua; Woerpel, K. A.

2012-01-01

Silver-catalyzed silylene transfer to alkenes formed vinylsilacyclopropanes regioselectively. These allylic silanes underwent additions to aldehydes to form seven-membered ring trans-alkenes with high diastereoselectivity. The high reactivity of the trans alkenes is evidenced by their formal [1,3]-sigmatropic rearrangement reactions and their rapid additions of oxygen–hydrogen bonds across the carbon–carbon double bonds. PMID:22780578

Ultrafast excited state deactivation of doped porous anodic alumina membranes

NASA Astrophysics Data System (ADS)

Makhal, Abhinandan; Sarkar, Soumik; Pal, Samir Kumar; Yan, Hongdan; Wulferding, Dirk; Cetin, Fatih; Lemmens, Peter

2012-08-01

Free-standing, bi-directionally permeable and ultra-thin anodic aluminum oxide (AAO) membranes establish attractive templates (host) for the synthesis of nano-dots and rods of various materials (guest). This is due to their chemical and structural integrity and high periodicity on length scales of 5-150 nm which are often used to host photoactive nano-materials for various device applications including dye-sensitized solar cells. In the present study, AAO membranes are synthesized by using electrochemical methods and a detailed structural characterization using FEG-SEM, XRD and TGA confirms the porosity and purity of the material. Defect-mediated photoluminescence quenching of the porous AAO membrane in the presence of an electron accepting guest organic molecule (benzoquinone) is studied by means of steady-state and picosecond/femtosecond-resolved luminescence measurements. Using time-resolved luminescence transients, we have also revealed light harvesting of complexes of porous alumina impregnated with inorganic quantum dots (Maple Red) or gold nanowires. Both the Förster resonance energy transfer and the nano-surface energy transfer techniques are employed to examine the observed quenching behavior as a function of the characteristic donor-acceptor distances. The experimental results will find their relevance in light harvesting devices based on AAOs combined with other materials involving a decisive energy/charge transfer dynamics.

Ultrafast excited state deactivation of doped porous anodic alumina membranes.

PubMed

Makhal, Abhinandan; Sarkar, Soumik; Pal, Samir Kumar; Yan, Hongdan; Wulferding, Dirk; Cetin, Fatih; Lemmens, Peter

2012-08-03

Free-standing, bi-directionally permeable and ultra-thin anodic aluminum oxide (AAO) membranes establish attractive templates (host) for the synthesis of nano-dots and rods of various materials (guest). This is due to their chemical and structural integrity and high periodicity on length scales of 5-150 nm which are often used to host photoactive nano-materials for various device applications including dye-sensitized solar cells. In the present study, AAO membranes are synthesized by using electrochemical methods and a detailed structural characterization using FEG-SEM, XRD and TGA confirms the porosity and purity of the material. Defect-mediated photoluminescence quenching of the porous AAO membrane in the presence of an electron accepting guest organic molecule (benzoquinone) is studied by means of steady-state and picosecond/femtosecond-resolved luminescence measurements. Using time-resolved luminescence transients, we have also revealed light harvesting of complexes of porous alumina impregnated with inorganic quantum dots (Maple Red) or gold nanowires. Both the Förster resonance energy transfer and the nano-surface energy transfer techniques are employed to examine the observed quenching behavior as a function of the characteristic donor-acceptor distances. The experimental results will find their relevance in light harvesting devices based on AAOs combined with other materials involving a decisive energy/charge transfer dynamics.

Antimonide-based membranes synthesis integration and strain engineering

PubMed Central

Anwar, Farhana; Klein, Brianna A.; Rasoulof, Amin; Dawson, Noel M.; Schuler-Sandy, Ted; Deneke, Christoph F.; Ferreira, Sukarno O.; Cavallo, Francesca; Krishna, Sanjay

2017-01-01

Antimonide compounds are fabricated in membrane form to enable materials combinations that cannot be obtained by direct growth and to support strain fields that are not possible in the bulk. InAs/(InAs,Ga)Sb type II superlattices (T2SLs) with different in-plane geometries are transferred from a GaSb substrate to a variety of hosts, including Si, polydimethylsiloxane, and metal-coated substrates. Electron microscopy shows structural integrity of transferred membranes with thickness of 100 nm to 2.5 μm and lateral sizes from 24×24μm2 to 1×1 cm2. Electron microscopy reveals the excellent quality of the membrane interface with the new host. The crystalline structure of the T2SL is not altered by the fabrication process, and a minimal elastic relaxation occurs during the release step, as demonstrated by X-ray diffraction and mechanical modeling. A method to locally strain-engineer antimonide-based membranes is theoretically illustrated. Continuum elasticity theory shows that up to ∼3.5% compressive strain can be induced in an InSb quantum well through external bending. Photoluminescence spectroscopy and characterization of an IR photodetector based on InAs/GaSb bonded to Si demonstrate the functionality of transferred membranes in the IR range. PMID:27986953

Exciton-to-Dopant Energy Transfer in Mn-Doped Cesium Lead Halide Perovskite Nanocrystals.

PubMed

Parobek, David; Roman, Benjamin J; Dong, Yitong; Jin, Ho; Lee, Elbert; Sheldon, Matthew; Son, Dong Hee

2016-12-14

We report the one-pot synthesis of colloidal Mn-doped cesium lead halide (CsPbX 3 ) perovskite nanocrystals and efficient intraparticle energy transfer between the exciton and dopant ions resulting in intense sensitized Mn luminescence. Mn-doped CsPbCl 3 and CsPb(Cl/Br) 3 nanocrystals maintained the same lattice structure and crystallinity as their undoped counterparts with nearly identical lattice parameters at ∼0.2% doping concentrations and no signature of phase separation. The strong sensitized luminescence from d-d transition of Mn 2+ ions upon band-edge excitation of the CsPbX 3 host is indicative of sufficiently strong exchange coupling between the charge carriers of the host and dopant d electrons mediating the energy transfer, essential for obtaining unique properties of magnetically doped quantum dots. Highly homogeneous spectral characteristics of Mn luminescence from an ensemble of Mn-doped CsPbX 3 nanocrystals and well-defined electron paramagnetic resonance spectra of Mn 2+ in host CsPbX 3 nanocrystal lattices suggest relatively uniform doping sites, likely from substitutional doping at Pb 2+ . These observations indicate that CsPbX 3 nanocrystals, possessing many superior optical and electronic characteristics, can be utilized as a new platform for magnetically doped quantum dots expanding the range of optical, electronic, and magnetic functionality.

Application of a Rapid Knowledge Synthesis and Transfer Approach to Assess the Microbial Safety of Low-Moisture Foods

PubMed Central

Young, Ian; Waddell, Lisa; Cahill, Sarah; Kojima, Mina; Clarke, Renata; Rajic, Andrijana

2016-01-01

Low-moisture foods (LMF) are increasingly implicated in outbreaks of foodborne illness resulting in a significant public health burden. To inform the development of a new Codex Alimentarius code of hygienic practice for LMF, we applied a rapid knowledge synthesis and transfer approach to review global research on the burden of illness, prevalence, and interventions to control nine selected microbial hazards in eight categories of LMF. Knowledge synthesis methods included an integrated scoping review (search strategy, relevance screening and confirmation, and evidence mapping), systematic review (detailed data extraction), and meta-analysis of prevalence data. Knowledge transfer of the results was achieved through multiple reporting formats, including evidence summary cards. We identified 214 unique outbreaks and 204 prevalence and 126 intervention studies. ‘Cereals and grains’ (n=142) and Salmonella spp. (n=278) were the most commonly investigated LMF and microbial hazard categories, respectively. Salmonella spp. was implicated in the most outbreaks (n=96, 45%), several of which were large and widespread, resulting in the most hospitalizations (n=895, 89%) and deaths (n=14, 74%). Salmonella spp. had a consistently low prevalence across all LMF categories (0-3%), while other hazards (e.g. B. cereus) were found at highly variable levels. A variety of interventions were investigated in small challenge trials. Key knowledge gaps included under-reporting of LMF outbreaks, limited reporting of microbial concentration data from prevalence studies, and a lack of intervention-efficacy research under commercial conditions. Summary cards were a useful knowledge transfer format to inform complementary risk ranking activities. This review builds upon previous work in this area by synthesizing a broad range of evidence using a structured, transparent, and integrated approach to provide timely evidence-informed inputs into international guidelines. PMID:26613924

Insight into multi-site mechanisms of glycosyl transfer in (1-->4)beta-D-glycans provided by the cereal mixed-linkage (1-->3),(1-->4)beta-D-glucan synthase.

PubMed

Buckeridge, M S; Vergara, C E; Carpita, N C

2001-08-01

Synthases of cellulose, chitin, hyaluronan, and all other polymers containing (1-->4)beta-linked glucosyl, mannosyl and xylosyl units have overcome a substrate orientation problem in catalysis because the (1-->4)beta-linkage requires that each of these sugar units be inverted nearly 180 degrees with respect to its neighbors. We and others have proposed that this problem is solved by two modes of glycosyl transfer within a single catalytic subunit to generate disaccharide units, which, when linked processively, maintain the proper orientation without rotation or re-orientation of the synthetic machinery in 3-dimensional space. A variant of the strict (1-->4)beta-D-linkage structure is the mixed-linkage (1-->3),(1-->4)beta-D-glucan, a growth-specific cell wall polysaccharide found in grasses and cereals. beta-Glucan is composed primarily of cellotriosyl and cellotetraosyl units linked by single (1-->3)beta-D-linkages. In reactions in vitro at high substrate concentration, a polymer composed of almost entirely cellotriosyl and cellopentosyl units is made. These results support a model in which three modes of glycosyl transfer occur within the synthase complex instead of just two. The generation of odd numbered units demands that they are connected by (1-->3)beta-linkages and not (1-->4)beta-. In this short review of beta-glucan synthesis in maize, we show how such a model not only provides simple mechanisms of synthesis for all (1-->4)beta-D-glycans but also explains how the synthesis of callose, or strictly (1-->3)beta-D-glucans, occurs upon loss of the multiple modes of glycosyl transfer to a single one.

Linear summation of outputs in a balanced network model of motor cortex.

PubMed

Capaday, Charles; van Vreeswijk, Carl

2015-01-01

Given the non-linearities of the neural circuitry's elements, we would expect cortical circuits to respond non-linearly when activated. Surprisingly, when two points in the motor cortex are activated simultaneously, the EMG responses are the linear sum of the responses evoked by each of the points activated separately. Additionally, the corticospinal transfer function is close to linear, implying that the synaptic interactions in motor cortex must be effectively linear. To account for this, here we develop a model of motor cortex composed of multiple interconnected points, each comprised of reciprocally connected excitatory and inhibitory neurons. We show how non-linearities in neuronal transfer functions are eschewed by strong synaptic interactions within each point. Consequently, the simultaneous activation of multiple points results in a linear summation of their respective outputs. We also consider the effects of reduction of inhibition at a cortical point when one or more surrounding points are active. The network response in this condition is linear over an approximately two- to three-fold decrease of inhibitory feedback strength. This result supports the idea that focal disinhibition allows linear coupling of motor cortical points to generate movement related muscle activation patterns; albeit with a limitation on gain control. The model also explains why neural activity does not spread as far out as the axonal connectivity allows, whilst also explaining why distant cortical points can be, nonetheless, functionally coupled by focal disinhibition. Finally, we discuss the advantages that linear interactions at the cortical level afford to motor command synthesis.

Dual Catalysis Strategies in Photochemical Synthesis

PubMed Central

2016-01-01

The interaction between an electronically excited photocatalyst and an organic molecule can result in the genertion of a diverse array of reactive intermediates that can be manipulated in a variety of ways to result in synthetically useful bond constructions. This Review summarizes dual-catalyst strategies that have been applied to synthetic photochemistry. Mechanistically distinct modes of photocatalysis are discussed, including photoinduced electron transfer, hydrogen atom transfer, and energy transfer. We focus upon the cooperative interactions of photocatalysts with redox mediators, Lewis and Brønsted acids, organocatalysts, enzymes, and transition metal complexes. PMID:27109441

Dual Catalysis Strategies in Photochemical Synthesis.

PubMed

Skubi, Kazimer L; Blum, Travis R; Yoon, Tehshik P

2016-09-14

The interaction between an electronically excited photocatalyst and an organic molecule can result in the genertion of a diverse array of reactive intermediates that can be manipulated in a variety of ways to result in synthetically useful bond constructions. This Review summarizes dual-catalyst strategies that have been applied to synthetic photochemistry. Mechanistically distinct modes of photocatalysis are discussed, including photoinduced electron transfer, hydrogen atom transfer, and energy transfer. We focus upon the cooperative interactions of photocatalysts with redox mediators, Lewis and Brønsted acids, organocatalysts, enzymes, and transition metal complexes.

Single step synthesis of gold-amino acid composite, with the evidence of the catalytic hydrogen atom transfer (HAT) reaction, for the electrochemical recognition of Serotonin

NASA Astrophysics Data System (ADS)

Choudhary, Meenakshi; Siwal, Samarjeet; Nandi, Debkumar; Mallick, Kaushik

2016-03-01

A composite architecture of amino acid and gold nanoparticles has been synthesized using a generic route of 'in-situ polymerization and composite formation (IPCF)' [1,2]. The formation mechanism of the composite has been supported by a model hydrogen atom (H•≡H++e-) transfer (HAT) type of reaction which belongs to the proton coupled electron transfer (PCET) mechanism. The 'gold-amino acid composite' was used as a catalyst for the electrochemical recognition of Serotonin.

Transfer-free synthesis of graphene-like atomically thin carbon films on SiC by ion beam mixing technique

NASA Astrophysics Data System (ADS)

Zhang, Rui; Chen, Fenghua; Wang, Jinbin; Fu, Dejun

2018-03-01

Here we demonstrate the synthesis of graphene directly on SiC substrates at 900 °C using ion beam mixing technique with energetic carbon cluster ions on Ni/SiC structures. The thickness of 7-8 nm Ni films was evaporated on the SiC substrates, followed by C cluster ion bombarding. Carbon cluster ions C4 were bombarded at 16 keV with the dosage of 4 × 1016 atoms/cm2. After thermal annealing process Ni silicides were formed, whereas C atoms either from the decomposition of the SiC substrates or the implanted contributes to the graphene synthesis by segregating and precipitating process. The limited solubility of carbon atoms in silicides, involving SiC, Ni2Si, Ni5Si2, Ni3Si, resulted in diffusion and precipitation of carbon atoms to form graphene on top of Ni and the interface of Ni/SiC. The ion beam mixing technique provides an attractive production method of a transfer-free graphene growth on SiC and be compatible with current device fabrication.

Ferritin: a zinc detoxicant and a zinc ion donor.

PubMed Central

Price, D; Joshi, J G

1982-01-01

Rats were injected with 1 mg of Zn2+ as zinc sulfate or 2 mg of Cd2+ as cadmium sulfate per kg of body weight on a daily basis. After seven injections, ferritin and metallothionein were isolated from the livers of the rats. Significant amounts of zinc were associated with ferritin. Incubation of such ferritin with apoenzymes of calf intestinal alkaline phosphatase, yeast phosphoglucomutase, and yeast aldolase restored their enzymic activity. The amount of zinc injected was insufficient to stimulate significant synthesis of metallothionein, but similar experiments with injection of cadmium did stimulate the synthesis of metallothionein. The amount of Zn2+ in ferritin of Cd-injected rats was greater than that in ferritin in Zn-injected rats, which was greater than that in ferritin of normal rats. Thus at comparable protein concentration ferritin from Cd-injected rats was a better Zn2+ donor than was ferritin from Zn-injected or normal animals. Ferritin is a normal constituent of several tissues, whereas metallothionein is synthesized under metabolic stress. Thus ferritin may function as a "metal storage and transferring agent" for iron and for zinc. It is suggested that ferritin probably serves as the initial chelator for Zn2+ and perhaps other metal ions as well and that under very high toxic levels of metal ions the synthesis of metallothionein is initiated as the second line of defense. PMID:6212927

Facile and Efficient Preparation of Tri-component Fluorescent Glycopolymers via RAFT-controlled Polymerization.

PubMed

Wang, Wei; Lester, John M; Amorosa, Anthony E; Chance, Deborah L; Mossine, Valeri V; Mawhinney, Thomas P

2015-06-19

Synthetic glycopolymers are instrumental and versatile tools used in various biochemical and biomedical research fields. An example of a facile and efficient synthesis of well-controlled fluorescent statistical glycopolymers using reversible addition-fragmentation chain-transfer (RAFT)-based polymerization is demonstrated. The synthesis starts with the preparation of β-galactose-containing glycomonomer 2-lactobionamidoethyl methacrylamide obtained by reaction of lactobionolactone and N-(2-aminoethyl) methacrylamide (AEMA). 2-Gluconamidoethyl methacrylamide (GAEMA) is used as a structural analog lacking a terminal β-galactoside. The following RAFT-mediated copolymerization reaction involves three different monomers: N-(2-hydroxyethyl) acrylamide as spacer, AEMA as target for further fluorescence labeling, and the glycomonomers. Tolerant of aqueous systems, the RAFT agent used in the reaction is (4-cyanopentanoic acid)-4-dithiobenzoate. Low dispersities (≤1.32), predictable copolymer compositions, and high reproducibility of the polymerizations were observed among the products. Fluorescent polymers are obtained by modifying the glycopolymers with carboxyfluorescein succinimidyl ester targeting the primary amine functional groups on AEMA. Lectin-binding specificities of the resulting glycopolymers are verified by testing with corresponding agarose beads coated with specific glycoepitope recognizing lectins. Because of the ease of the synthesis, the tight control of the product compositions and the good reproducibility of the reaction, this protocol can be translated towards preparation of other RAFT-based glycopolymers with specific structures and compositions, as desired.

One-step synthesis of hybrid inorganic-organic nanocomposite coatings by novel laser adaptive ablation deposition technique

NASA Astrophysics Data System (ADS)

Serbezov, Valery; Sotirov, Sotir

2013-03-01

A novel approach for one-step synthesis of hybrid inorganic-organic nanocomposite coatings by new modification of Pulsed Laser Deposition technology called Laser Adaptive Ablation Deposition (LAAD) is presented. Hybrid nanocomposite coatings including Mg- Rapamycin and Mg- Desoximetasone were produced by UV TEA N2 laser under low vacuum (0.1 Pa) and room temperature onto substrates from SS 316L, KCl and NaCl. The laser fluence for Mg alloy was 1, 8 J/cm2 and for Desoximetasone 0,176 J/cm2 and for Rapamycin 0,118 J/cm2 were respectively. The threedimensional two-segmented single target was used to adapt the interaction of focused laser beam with inorganic and organic material. Magnesium alloy nanoparticles with sizes from 50 nm to 250 nm were obtained in organic matrices. The morphology of nanocomposites films were studied by Bright field / Fluorescence optical microscope and Scanning Electron Microscope (SEM). Fourier Transform Infrared (FTIR) spectroscopy measurements were applied in order to study the functional properties of organic component before and after the LAAD process. Energy Dispersive X-ray Spectroscopy (EDX) was used for identification of Mg alloy presence in hybrid nanocomposites coatings. The precise control of process parameters and particularly of the laser fluence adjustment enables transfer on materials with different physical chemical properties and one-step synthesis of complex inorganic- organic nanocomposites coatings.

Synthesis of one-dimensional gold nanostructures and the electrochemical application of the nanohybrid containing functionalized graphene oxide for cholesterol biosensing.

PubMed

Nandini, Seetharamaiah; Nalini, Seetharamaiah; Reddy, M B Madhusudana; Suresh, Gurukar Shivappa; Melo, Jose Savio; Niranjana, Pathappa; Sanetuntikul, Jakkid; Shanmugam, Sangaraju

2016-08-01

This manuscript reports a new approach for the synthesis of one dimensional gold nanostructure (AuNs) and its application in the development of cholesterol biosensor. Au nanostructures have been synthesized by exploiting β-diphenylalanine (β-FF) as an sacrificial template, whereas the Au nanoparticles (AuNPs) were synthesized by ultrasound irradiation. X-ray diffractometer (XRD), scanning electron microscope (SEM) and energy dispersive analysis of X-rays (EDAX) have been employed to characterize the morphology and composition of the prepared samples. With the aim to develop a highly sensitive cholesterol biosensor, cholesterol oxidase (ChOx) was immobilized on AuNs which were appended on the graphite (Gr) electrode via chemisorption onto thiol-functionalized graphene oxide (GO-SH). This Gr/GO-SH/AuNs/ChOx biosensor has been characterized using cyclic voltammetry (CV), electrochemical impedance spectroscopy and chronoamperometry. CV results indicated a direct electron transfer between the enzyme and the electrode surface. A new potentiostat intermitant titration technique (PITT) has been studied to determine the diffusion coefficient and maxima potential value. The proposed biosensor showed rapid response, high sensitivity, wide linear range and low detection limit. Furthermore, our AuNs modified electrode showed excellent selectivity, repeatability, reproducibility and long term stability. The proposed electrode has also been used successfully to determine cholesterol in serum samples. Copyright © 2016 Elsevier B.V. All rights reserved.

DC Plasma Synthesis of Vertically Aligned Carbon Nanofibers for Biointerfacing

NASA Astrophysics Data System (ADS)

Pearce, Ryan Christopher

Vertically aligned carbon nanofibers (VACNFs) are a class of materials whose nanoscale dimensions and physical properties makes them uniquely suitable as functional elements in many applications for biodetection and biointerfacing on a cellular level. Control of VACNF synthesis by catalytic plasma enhanced chemical vapor deposition (PECVD) presents many challenges in integration into devices and structures designed for biointerfacing, such as transparent or flexible substrates. This dissertation addresses ways to overcome many of these issues in addition to deepening the fundamental understanding of nano-synthesis in catalytic PECVD. First, a survey of the field of VACNF synthesis and biointerfacing is presented, identifying the present challenges and greatest experimental applications. It is followed by experimental observations that elucidate the underlying mechanism to fiber alignment during synthesis, a critical step for deterministic control of fiber growth. Using a grid of electrodes patterned by photolithography on an insulating substrate, it was found that the alignment of the fibers is controlled by the anisotropic etching provided by ions during dc-PECVD synthesis. The VACNFs that have been utilized for many cellular interfacing experiments have unique mechanical and fluorescent properties due to a SiNx coating. The mechanism for SiNx deposition to VACNF sidewalls during synthesis is explored in addition to a detailed study of the optical properties of the coating. To explain the optical properties of this coating it is proposed that the source of photoluminescence for the SiNx coated VACNFs is quantum confinement effects due to the presence of silicon nanoclusters embedded in a Si3N4 matrix. These luminescent fibers have proven useful as registry markers in cell impalefection studies. To realize VACNF arrays used as an inflatable angioplasty balloon with embedded fibers to deliver drugs across the blood-brain barrier, a method for transferring fibers to flexible polydimethylesiloxane (PDMS) is presented. A process has been developed that involves synthesizing fibers on aluminum, followed by spin coating a thin layer of PDMS and then dissolving the underlying aluminum with KOH. Finally, a method of fiber synthesis using just air and acetone as the process gases is presented, enabling the possibility of inatmosphere, large scale VACNF synthesis. It is envisioned that these advancements should assist the viability of large scale VACNF related technologies and will help to bridge the gap between experimental applications and industrial adoption.

Quantum-mechanical analysis of amino acid residues function in the proton transport during F0F1-ATP synthase catalytic cycle

NASA Astrophysics Data System (ADS)

Ivontsin, L. A.; Mashkovtseva, E. V.; Nartsissov, Ya R.

2017-11-01

Implications of quantum-mechanical approach to the description of proton transport in biological systems are a tempting subject for an overlapping of fundamental physics and biology. The model of proton transport through the integrated membrane enzyme FoF1-ATP synthase responsible for ATP synthesis was developed. The estimation of the mathematical expectation of the proton transfer time through the half-channel was performed. Observed set of proton pathways through the inlet half-channel showed the nanosecond timescale highly dependable of some amino acid residues. There were proposed two types of crucial amino acids: critically localized (His245) and being a part of energy conserving system (Asp119).

Silver nanoparticle ink technology: state of the art

PubMed Central

Rajan, Krishna; Roppolo, Ignazio; Chiappone, Annalisa; Bocchini, Sergio; Perrone, Denis; Chiolerio, Alessandro

2016-01-01

Printed electronics will bring to the consumer level great breakthroughs and unique products in the near future, shifting the usual paradigm of electronic devices and circuit boards from hard boxes and rigid sheets into flexible thin layers and bringing disposable electronics, smart tags, and so on. The most promising tool to achieve the target depends upon the availability of nanotechnology-based functional inks. A certain delay in the innovation-transfer process to the market is now being observed. Nevertheless, the most widely diffused product, settled technology, and the highest sales volumes are related to the silver nanoparticle-based ink market, representing the best example of commercial nanotechnology today. This is a compact review on synthesis routes, main properties, and practical applications. PMID:26811673

Silver nanoparticle ink technology: state of the art.

PubMed

Rajan, Krishna; Roppolo, Ignazio; Chiappone, Annalisa; Bocchini, Sergio; Perrone, Denis; Chiolerio, Alessandro

2016-01-01

Printed electronics will bring to the consumer level great breakthroughs and unique products in the near future, shifting the usual paradigm of electronic devices and circuit boards from hard boxes and rigid sheets into flexible thin layers and bringing disposable electronics, smart tags, and so on. The most promising tool to achieve the target depends upon the availability of nanotechnology-based functional inks. A certain delay in the innovation-transfer process to the market is now being observed. Nevertheless, the most widely diffused product, settled technology, and the highest sales volumes are related to the silver nanoparticle-based ink market, representing the best example of commercial nanotechnology today. This is a compact review on synthesis routes, main properties, and practical applications.

Process And Apparatus To Accomplish Autothermal Or Steam Reforming Via A Reciprocating Compression Device

DOEpatents

Lyons, K. David; James, Robert; Berry, David A.; Gardner, Todd

2004-09-21

The invention provides a method and apparatus for producing a synthesis gas from a variety of hydrocarbons. The apparatus (device) consists of a semi-batch, non-constant volume reactor to generate a synthesis gas. While the apparatus feeds mixtures of air, steam, and hydrocarbons into a cylinder where work is performed on the fluid by a piston to adiabatically raise its temperature without heat transfer from an external source.

Of Molecules and Models.

ERIC Educational Resources Information Center

Brinner, Bonnie

1992-01-01

Presents an activity in which models help students visualize both the DNA process and transcription. After constructing DNA, RNA messenger, and RNA transfer molecules; students model cells, protein synthesis, codons, and RNA movement. (MDH)

Exploring Step‐by‐Step Assembly of Nanoparticle:Cytochrome Biohybrid Photoanodes

PubMed Central

Hwang, Ee Taek; Orchard, Katherine L.; Hojo, Daisuke; Beton, Joseph; Lockwood, Colin W. J.; Adschiri, Tadafumi

2017-01-01

Abstract Coupling light‐harvesting semiconducting nanoparticles (NPs) with redox enzymes has been shown to create artificial photosynthetic systems that hold promise for the synthesis of solar fuels. High quantum yields require efficient electron transfer from the nanoparticle to the redox protein, a property that can be difficult to control. Here, we have compared binding and electron transfer between dye‐sensitized TiO2 nanocrystals or CdS quantum dots and two decaheme cytochromes on photoanodes. The effect of NP surface chemistry was assessed by preparing NPs capped with amine or carboxylic acid functionalities. For the TiO2 nanocrystals, binding to the cytochromes was optimal when capped with a carboxylic acid ligand, whereas for the CdS QDs, better adhesion was observed for amine capped ligand shells. When using TiO2 nanocrystals, dye‐sensitized with a phosphonated bipyridine Ru(II) dye, photocurrents are observed that are dependent on the redox state of the decaheme, confirming that electrons are transferred from the TiO2 nanocrystals to the surface via the decaheme conduit. In contrast, when CdS NPs are used, photocurrents are not dependent on the redox state of the decaheme, consistent with a model in which electron transfer from CdS to the photoanode bypasses the decaheme protein. These results illustrate that although the organic shell of NPs nanoparticles crucially affects coupling with proteinaceous material, the coupling can be difficult to predict or engineer. PMID:28920010

One-Step Synthesis of Water-Soluble MoS2 Quantum Dots via a Hydrothermal Method as a Fluorescent Probe for Hyaluronidase Detection.

PubMed

Gu, Wei; Yan, Yinghan; Zhang, Cuiling; Ding, Caiping; Xian, Yuezhong

2016-05-11

In this work, a bottom-up strategy is developed to synthesize water-soluble molybdenum disulfide quantum dots (MoS2 QDs) through a simple, one-step hydrothermal method using ammonium tetrathiomolybdate [(NH4)2MoS4] as the precursor and hydrazine hydrate as the reducing agent. The as-synthesized MoS2 QDs are few-layered with a narrow size distribution, and the average diameter is about 2.8 nm. The resultant QDs show excitation-dependent blue fluorescence due to the polydispersity of the QDs. Moreover, the fluorescence can be quenched by hyaluronic acid (HA)-functionalized gold nanoparticles through a photoinduced electron-transfer mechanism. Hyaluronidase (HAase), an endoglucosidase, can cleave HA into proangiogenic fragments and lead to the aggregation of gold nanoparticles. As a result, the electron transfer is blocked and fluorescence is recovered. On the basis of this principle, a novel fluorescence sensor for HAase is developed with a linear range from 1 to 50 U/mL and a detection limit of 0.7 U/mL.

In situ development of self-reinforced cellulose nanocrystals based thermoplastic elastomers by atom transfer radical polymerization.

PubMed

Yu, Juan; Wang, Chunpeng; Wang, Jifu; Chu, Fuxiang

2016-05-05

Recently, the utilization of cellulose nanocrystals (CNCs) as a reinforcing material has received a great attention due to its high elastic modulus. In this article, a novel strategy for the synthesis of self-reinforced CNCs based thermoplastic elastomers (CTPEs) is presented. CNCs were first surface functionalized with an initiator for surface-initiated atom transfer radical polymerization (SI-ATRP). Subsequently, SI-ATRP of methyl methacrylate (MMA) and butyl acrylate (BA) was carried out in the presence of sacrificial initiator to form CTPEs in situ. The CTPEs together with the simple blends of CNCs and linear poly(MMA-co-BA) copolymer (P(MMA-co-BA)) were characterized for comparative study. The results indicated that P(MMA-co-BA) was successfully grafted onto the surface of CNCs and the compatibility between CNCs and the polymer matrix in CTPEs was greatly enhanced. Specially, the CTPEs containing 2.15wt% CNCs increased Tg by 19.2°C and tensile strength by 100% as compared to the linear P(MMA-co-BA). Copyright © 2016 Elsevier Ltd. All rights reserved.

Formation and Evolution of X-ray Binaries

NASA Astrophysics Data System (ADS)

Fragkos, Anastasios

X-ray binaries - mass-transferring binary stellar systems with compact object accretors - are unique astrophysical laboratories. They carry information about many complex physical processes such as star formation, compact object formation, and evolution of interacting binaries. My thesis work involves the study of the formation and evolution of Galactic and extra-galacticX-ray binaries using both detailed and realistic simulation tools, and population synthesis techniques. I applied an innovative analysis method that allows the reconstruction of the full evolutionary history of known black hole X-ray binaries back to the time of compact object formation. This analysis takes into account all the available observationally determined properties of a system, and models in detail four of its evolutionary evolutionary phases: mass transfer through the ongoing X-ray phase, tidal evolution before the onset of Roche-lobe overflow, motion through the Galactic potential after the formation of the black hole, and binary orbital dynamics at the time of core collapse. Motivated by deep extra-galactic Chandra survey observations, I worked on population synthesis models of low-mass X-ray binaries in the two elliptical galaxies NGC3379 and NGC4278. These simulations were targeted at understanding the origin of the shape and normalization of the observed X-ray luminosity functions. In a follow up study, I proposed a physically motivated prescription for the modeling of transient neutron star low-mass X-ray binary properties, such as duty cycle, outburst duration and recurrence time. This prescription enabled the direct comparison of transient low-mass X-ray binary population synthesis models to the Chandra X-ray survey of the two ellipticals NGC3379 and NGC4278. Finally, I worked on population synthesismodels of black holeX-ray binaries in the MilkyWay. This work was motivated by recent developments in observational techniques for the measurement of black hole spin magnitudes in black hole X-ray binaries. The accuracy of these techniques depend on misalignment of the black hole spin with respect to the orbital angular momentum. In black hole X-ray binaries, this misalignment can occur during the supernova explosion that forms the compact object. In this study, I presented population synthesis models of Galactic black hole X-ray binaries, and examined the distribution of misalignment angles, and its dependence on the model parameters.

Commercializing the transfer orbit stage

NASA Technical Reports Server (NTRS)

Miller, M. W.

1984-01-01

Key milestones necessary to establish the transfer orbit stage are examined. The selection of the project concept and synthesis of the company are described followed by an analysis venture capability support and the selection of a major aerospace company as prime contractor. A landmark agreement with NASA sanctioned the commercial TOS concept and provided the critical support necessary to raise the next round of venture capital. Project management and customer commitments are also discussed.

Dual role of allylsamarium bromide as a Grignard reagent and a single electron transfer reagent in the one-pot synthesis of terminal olefins.

PubMed

Li, Ying; Hu, Yuan-Yuan; Zhang, Song-Lin

2013-11-21

The utility of allylsamarium bromide, both as a nucleophilic reagent and a single-electron transfer reagent, in the reaction of carbonyl compounds with allylsamarium bromide in the presence of diethyl phosphate is reported in this communication. From a synthetic point of view, a simple one-pot method for the preparation of terminal olefins is developed.

Sharing the load: Mex67–Mtr2 cofunctions with Los1 in primary tRNA nuclear export

PubMed Central

Chatterjee, Kunal; Majumder, Shubhra; Wan, Yao; Shah, Vijay; Wu, Jingyan; Huang, Hsiao-Yun

2017-01-01

Eukaryotic transfer RNAs (tRNAs) are exported from the nucleus, their site of synthesis, to the cytoplasm, their site of function for protein synthesis. The evolutionarily conserved β-importin family member Los1 (Exportin-t) has been the only exporter known to execute nuclear export of newly transcribed intron-containing pre-tRNAs. Interestingly, LOS1 is unessential in all tested organisms. As tRNA nuclear export is essential, we previously interrogated the budding yeast proteome to identify candidates that function in tRNA nuclear export. Here, we provide molecular, genetic, cytological, and biochemical evidence that the Mex67–Mtr2 (TAP–p15) heterodimer, best characterized for its essential role in mRNA nuclear export, cofunctions with Los1 in tRNA nuclear export. Inactivation of Mex67 or Mtr2 leads to rapid accumulation of end-matured unspliced tRNAs in the nucleus. Remarkably, merely fivefold overexpression of Mex67–Mtr2 can substitute for Los1 in los1Δ cells. Moreover, in vivo coimmunoprecipitation assays with tagged Mex67 document that the Mex67 binds tRNAs. Our data also show that tRNA exporters surprisingly exhibit differential tRNA substrate preferences. The existence of multiple tRNA exporters, each with different tRNA preferences, may indicate that the proteome can be regulated by tRNA nuclear export. Thus, our data show that Mex67–Mtr2 functions in primary nuclear export for a subset of yeast tRNAs. PMID:29212662

Sharing the load: Mex67-Mtr2 cofunctions with Los1 in primary tRNA nuclear export.

PubMed

Chatterjee, Kunal; Majumder, Shubhra; Wan, Yao; Shah, Vijay; Wu, Jingyan; Huang, Hsiao-Yun; Hopper, Anita K

2017-11-01

Eukaryotic transfer RNAs (tRNAs) are exported from the nucleus, their site of synthesis, to the cytoplasm, their site of function for protein synthesis. The evolutionarily conserved β-importin family member Los1 (Exportin-t) has been the only exporter known to execute nuclear export of newly transcribed intron-containing pre-tRNAs. Interestingly, LOS1 is unessential in all tested organisms. As tRNA nuclear export is essential, we previously interrogated the budding yeast proteome to identify candidates that function in tRNA nuclear export. Here, we provide molecular, genetic, cytological, and biochemical evidence that the Mex67-Mtr2 (TAP-p15) heterodimer, best characterized for its essential role in mRNA nuclear export, cofunctions with Los1 in tRNA nuclear export. Inactivation of Mex67 or Mtr2 leads to rapid accumulation of end-matured unspliced tRNAs in the nucleus. Remarkably, merely fivefold overexpression of Mex67-Mtr2 can substitute for Los1 in los1 Δ cells. Moreover, in vivo coimmunoprecipitation assays with tagged Mex67 document that the Mex67 binds tRNAs. Our data also show that tRNA exporters surprisingly exhibit differential tRNA substrate preferences. The existence of multiple tRNA exporters, each with different tRNA preferences, may indicate that the proteome can be regulated by tRNA nuclear export. Thus, our data show that Mex67-Mtr2 functions in primary nuclear export for a subset of yeast tRNAs. © 2017 Chatterjee et al.; Published by Cold Spring Harbor Laboratory Press.

Quorum-quenching limits quorum-sensing exploitation by signal-negative invaders

NASA Astrophysics Data System (ADS)

Tannières, Mélanie; Lang, Julien; Barnier, Claudie; Shykoff, Jacqui A.; Faure, Denis

2017-01-01

Some bacteria produce and perceive quorum-sensing (QS) signals that coordinate several behaviours, including the costly processes that are exoenzyme production and plasmid transfer. In the case of plasmid transfer, the emergence of QS signal-altered invaders and their policing are poorly documented. In Agrobacterium tumefaciens, the virulence Ti-plasmid encodes both synthesis and sensing of QS-signals, which promote its transfer from a donor to a recipient cell. Here, we reported that QS-altered A. tumefaciens mutants arose during experimental evolution. All showed improved growth compared to their ancestor. Genome sequencing revealed that, though some had lost the Ti-plasmid, most were defective for QS-signal synthesis and Ti-plasmid conjugation (traR mutations) and one exhibited a QS-signal exploitation behaviour, using signal produced by other cells to enhance its own Ti-plasmid transfer. We explored mechanisms that can limit this QS-hijacking. We showed that the A. tumefaciens capacity to inactivate QS-signals by expressing QS-degrading enzyme could attenuate dissemination of the QS signal-negative Ti-plasmids. This work shows that enzymatic QS-disruption whether encoded by the QS-producing Ti-plasmid itself, by a companion plasmid in the same donor cells, or by one in the recipient cells, in all cases can serve as a mechanism for controlling QS exploitation by QS signal-negative mutants.

The placenta. Not just a conduit for maternal fuels.

PubMed

Hay, W W

1991-12-01

The placenta is a specialized organ of exchange that provides nutrients to and excretes waste products from the fetus. The exchange of nutrients between placenta and fetus involves three major mechanisms: 1) direct transfer of nutrients from the maternal to the fetal plasma, 2) placental consumption of nutrients, and 3) placental conversion of nutrients to alternate substrate forms. Although direct transfer has been considered the primary means by which placental-fetal exchange controls the supply of nutrients to the fetus and thereby fetal metabolism and growth, the considerable metabolic activity of the placenta provides a large and fundamentally important contribution to both the quality and quantity of nutrient substrates supplied to the fetus; e.g., placental O2 and glucose consumption rates approach or even exceed those of brain and tumor tissue. Other placental metabolic activities include glycolysis, gluconeogenesis, glycogenesis, oxidation, protein synthesis, amino acid interconversion, triglyceride synthesis, and chain lengthening or shortening of individual fatty acids. Thus, consideration of the metabolism of the placenta is essential for a more complete understanding of how the placenta regulates nutrient transfer to the fetus, fetal energy balance, and fetal growth.

Synthesis and Exciton Dynamics of Triplet Sensitized Conjugated Polymers.

PubMed

Andernach, Rolf; Utzat, Hendrik; Dimitrov, Stoichko D; McCulloch, Iain; Heeney, Martin; Durrant, James R; Bronstein, Hugo

2015-08-19

We report the synthesis of a novel polythiophene-based host-guest copolymer incorporating a Pt-porphyrin complex (TTP-Pt) into the backbone for efficient singlet to triplet polymer exciton sensitization. We elucidated the exciton dynamics in thin films of the material by means of Transient Absorption Spectrosopcy (TAS) on multiple time scales and investigated the mechanism of triplet exciton formation. During sensitization, singlet exciton diffusion is followed by exciton transfer from the polymer backbone to the complex where it undergoes intersystem crossing to the triplet state of the complex. We directly monitored the triplet exciton back transfer from the Pt-porphyrin to the polymer and found that 60% of the complex triplet excitons were transferred with a time constant of 1087 ps. We propose an equilibrium between polymer and porphyrin triplet states as a result of the low triplet diffusion length in the polymer backbone and hence an increased local triplet population resulting in increased triplet-triplet annihilation. This novel system has significant implications for the design of novel materials for triplet sensitized solar cells and upconversion layers.

Transaminases for the synthesis of enantiopure beta-amino acids

PubMed Central

2012-01-01

Optically pure β-amino acids constitute interesting building blocks for peptidomimetics and a great variety of pharmaceutically important compounds. Their efficient synthesis still poses a major challenge. Transaminases (also known as aminotransferases) possess a great potential for the synthesis of optically pure β-amino acids. These pyridoxal 5'-dependent enzymes catalyze the transfer of an amino group from a donor substrate to an acceptor, thus enabling the synthesis of a wide variety of chiral amines and amino acids. Transaminases can be applied either for the kinetic resolution of racemic compounds or the asymmetric synthesis starting from a prochiral substrate. This review gives an overview over microbial transaminases with activity towards β-amino acids and their substrate spectra. It also outlines current strategies for the screening of new biocatalysts. Particular emphasis is placed on activity assays which are applicable to high-throughput screening. PMID:22293122

Molecular replication

NASA Technical Reports Server (NTRS)

Orgel, L. E.

1986-01-01

The object of our research program is to understand how polynucleotide replication originated on the primitive Earth. This is a central issue in studies of the origins of life, since a process similar to modern DNA and RNA synthesis is likely to have formed the basis for the most primitive system of genetic information transfer. The major conclusion of studies so far is that a preformed polynucleotide template under many different experimental conditions will facilitate the synthesis of a new oligonucleotide with a sequence complementary to that of the template. It has been shown, for example, that poly(C) facilitates the synthesis of long oligo(G)s and that the short template CCGCC facilities the synthesis of its complement GGCGG. Very recently we have shown that template-directed synthesis is not limited to the standard oligonucleotide substrates. Nucleic acid-like molecules with a pyrophosphate group replacing the phosphate of the standard nucleic acid backbone are readily synthesized from deoxynucleotide 3'-5'-diphosphates on appropriate templates.

Diastereoselective auxiliary- and catalyst-controlled intramolecular aza-Michael reaction for the elaboration of enantioenriched 3-substituted isoindolinones. Application to the synthesis of a new pazinaclone analogue

PubMed Central

Sallio, Romain; Lebrun, Stéphane; Capet, Frédéric; Agbossou-Niedercorn, Francine

2018-01-01

A new asymmetric organocatalyzed intramolecular aza-Michael reaction by means of both a chiral auxiliary and a catalyst for stereocontrol is reported for the synthesis of optically active isoindolinones. A selected cinchoninium salt was used as phase-transfer catalyst in combination with a chiral nucleophile, a Michael acceptor and a base to provide 3-substituted isoindolinones in good yields and diastereomeric excesses. This methodology was applied to the asymmetric synthesis of a new pazinaclone analogue which is of interest in the field of benzodiazepine-receptor agonists. PMID:29623121

5 CFR 351.303 - Identification of positions with a transferring function.

Code of Federal Regulations, 2013 CFR

2013-01-01

... transferring function. 351.303 Section 351.303 Administrative Personnel OFFICE OF PERSONNEL MANAGEMENT CIVIL SERVICE REGULATIONS REDUCTION IN FORCE Transfer of Function § 351.303 Identification of positions with a transferring function. (a) The competitive area losing the function is responsible for identifying the...

5 CFR 351.303 - Identification of positions with a transferring function.

Code of Federal Regulations, 2014 CFR

2014-01-01

... transferring function. 351.303 Section 351.303 Administrative Personnel OFFICE OF PERSONNEL MANAGEMENT CIVIL SERVICE REGULATIONS REDUCTION IN FORCE Transfer of Function § 351.303 Identification of positions with a transferring function. (a) The competitive area losing the function is responsible for identifying the...

Winter flounder antifreeze protein genes: demonstration of a cold-inducible promoter and gene transfer to other species

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, R.C.; Gourlie, B.; Price, J.

1987-05-01

During the late fall and winter, the winter flounder produces a family of unique antifreeze proteins (AFP) to prevent the lethal formation of ice crystals in its blood. They have been able to induce winter flounder AFP mRNA synthesis in vivo by lowering the ambient temperature of the fish from 18/sup 0/C in the summer months when AFP synthesis is at a minimum to 4/sup 0/C. Furthermore, they have demonstrated and thoroughly investigated this cold induction of AFP mRNA synthesis in vitro in isolated liver tissue and in nuclear preparations isolated from liver tissue. A drug selection vector (pRSV/sub gpt/)more » which uses RSV promoter for the expression of xanthine-guanine phosphoribosyltransferase (gpt) gene and contains an AFP gene and 1.7 kb of its 5' upstream control region has been constructed for studies of gene transfer into cells of other fish species. These studies were made using a variety of gene transfer techniques into tissue culture cell lines derived from rainbow trout, bluegill, and salmon. Drug resistant colonies from all three species have been obtained and the presence of AFP DNA has been positively identified by Southern analysis. In addition, Northern blot analysis has shown that both gpt gene and AFP gene are active in these cells since mRNA/sub gpt/ and mRNA/sub AFP/ can be detected by probing with the respective gene sequences.« less

A novel rapid synthesis of Fe{sub 2}O{sub 3}/graphene nanocomposite using ferrate(VI) and its application as a new kind of nanocomposite modified electrode as electrochemical sensor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Karimi, Mohammad Ali, E-mail: ma_karimi43@yahoo.com; Department of Chemistry & Nanoscience and Nanotechnology Research Laboratory; Banifatemeh, Fatemeh

2015-10-15

Highlights: • A novel rapid synthesis of rGO–Fe{sub 2}O{sub 3} nanocomposite was developed using Fe(VI). • Fe(VI) as an environmentally friendly oxidant was introduced for GO synthesis. • Synthesized rGO–Fe{sub 2}O{sub 3} nanocomposite was applied as electrochemical sensor. • A non-enzymatic sensor was developed for H{sub 2}O{sub 2}. - Abstract: In this study, a novel, simple and sensitive non-enzymatic hydrogen peroxide electrochemical sensor was developed using reduced graphene oxide/Fe{sub 2}O{sub 3} nanocomposite modified glassy carbon electrode. This nanocomposite was synthesized by reaction of sodium ferrate with graphene in alkaline media. This reaction completed in 5 min and the products weremore » stable and its deposition on the surface of electrode is investigated. It has been found the apparent charge transfer rate constant (ks) is 0.52 and transfer coefficient (α) is 0.61 for electron transfer between the modifier and glassy carbon electrode. Electrochemical behavior of this electrode and its ability to catalyze the electro-reduction of H{sub 2}O{sub 2} has been studied by cyclic voltammetry and chronoamperometry at different experimental conditions. The analytical parameters showed the good ability of electrode as a sensor for H{sub 2}O{sub 2} amperometric reduction.« less

Graphene: powder, flakes, ribbons, and sheets.

PubMed

James, Dustin K; Tour, James M

2013-10-15

Graphene's unique physical and electrical properties (high tensile strength, Young's modulus, electron mobility, and thermal conductivity) have led to its nickname of "super carbon." Graphene research involves the study of several different physical forms of the material: powders, flakes, ribbons, and sheets and others not yet named or imagined. Within those forms, graphene can include a single layer, two layers, or ≤10 sheets of sp² carbon atoms. The chemistry and applications available with graphene depend on both the physical form of the graphene and the number of layers in the material. Therefore the available permutations of graphene are numerous, and we will discuss a subset of this work, covering some of our research on the synthesis and use of many of the different physical and layered forms of graphene. Initially, we worked with commercially available graphite, with which we extended diazonium chemistry developed to functionalize single-walled carbon nanotubes to produce graphitic materials. These structures were soluble in common organic solvents and were better dispersed in composites. We developed an improved synthesis of graphene oxide (GO) and explored how the workup protocol for the synthesis of GO can change the electronic structure and chemical functionality of the GO product. We also developed a method to remove graphene layers one-by-one from flakes. These powders and sheets of GO can serve as fluid loss prevention additives in drilling fluids for the oil industry. Graphene nanoribbons (GNRs) combine small width with long length, producing valuable electronic and physical properties. We developed two complementary syntheses of GNRs from multiwalled carbon nanotubes: one simple oxidative method that produces GNRs with some defects and one reductive method that produces GNRs that are less defective and more electrically conductive. These GNRs can be used in low-loss, high permittivity composites, as conductive reinforcement coatings on Kevlar fibers and in the fabrication of large area transparent electrodes. Using solid carbon sources such as polymers, food, insects, and waste, we can grow monolayer and bilayer graphene directly on metal catalysts, and carbon-sources containing nitrogen can produce nitrogen-doped graphene. The resulting graphene can be transferred to other surfaces, such as metal grids, for potential use in transparent touch screens for applications in personal electronics and large area photovoltaic devices. Because the transfer of graphene from one surface to another can lead to defects, low yields, and higher costs, we have developed methods for growing graphene directly on the substrates of interest. We can also produce patterned graphene to make GNRs or graphane/graphene superlattices within a single sheet. These superlattices could have multiple functions for use in sensors and other devices. This Account only touches upon this burgeoning area of materials chemistry, and the field will continue to expand as researchers imagine new forms and applications of graphene.

Enantioselective Synthesis of 5,7-Bicyclic Ring Systems from Axially Chiral Allenes Using a Rh(I)-Catalyzed Cyclocarbonylation Reaction

PubMed Central

Grillet, Francois; Brummond, Kay M.

2013-01-01

A transfer of chirality in an intramolecular Rh(I)-catalyzed allenic Pauson-Khand reaction (APKR) to access tetrahydroazulenones, tetrahydrocyclopenta[c]azepinones and dihydrocyclopenta[c]oxepinones enantioselectively (22 – 99% ee) is described. The substitution pattern of the allene affected the transfer of chiral information. Complete transfer of chirality was obtained for all trisubstituted allenes, but loss of chiral information was observed for disubstituted allenes. This work constitutes the first demonstration of a transfer of chiral information from an allene to the 5-position of a cyclopentenone using a cyclocarbonylation reaction. The absolute configuration of the corresponding cyclocarbonylation product was also established, something that is rarely done. PMID:23485149

Aging Affects Dopaminergic Neural Mechanisms of Cognitive Flexibility

DOE PAGES

Berry, Anne S.; Shah, Vyoma D.; Baker, Suzanne L.; ...

2016-12-14

Aging is accompanied by profound changes in the brain’s dopamine system that affect cognitive function. Evidence of powerful individual differences in cognitive aging has sharpened focus on identifying biological factors underlying relative preservation versus vulnerability to decline. Dopamine represents a key target in these efforts. Alterations of dopamine receptors and dopamine synthesis are seen in aging, with receptors generally showing reduction and synthesis demonstrating increases. Using the PET tracer 6-[ 18F]fluoro-L- m-tyrosine, we found strong support for upregulated striatal dopamine synthesis capacity in healthy older adult humans free of amyloid pathology, relative to young people. We next used fMRI tomore » define the functional impact of elevated synthesis capacity on cognitive flexibility, a core component of executive function. We found clear evidence in young adults that low levels of synthesis capacity were suboptimal, associated with diminished cognitive flexibility and altered frontoparietal activation relative to young adults with highest synthesis values. Critically, these relationships between dopamine, performance, and activation were transformed in older adults with higher synthesis capacity. Variability in synthesis capacity was related to intrinsic frontoparietal functional connectivity across groups, suggesting that striatal dopamine synthesis influences the tuning of networks underlying cognitive flexibility. Altogether, these findings define striatal dopamine’s association with cognitive flexibility and its neural underpinnings in young adults, and reveal the alteration in dopamine-related neural processes in aging.« less

Aging Affects Dopaminergic Neural Mechanisms of Cognitive Flexibility

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berry, Anne S.; Shah, Vyoma D.; Baker, Suzanne L.

Aging is accompanied by profound changes in the brain’s dopamine system that affect cognitive function. Evidence of powerful individual differences in cognitive aging has sharpened focus on identifying biological factors underlying relative preservation versus vulnerability to decline. Dopamine represents a key target in these efforts. Alterations of dopamine receptors and dopamine synthesis are seen in aging, with receptors generally showing reduction and synthesis demonstrating increases. Using the PET tracer 6-[ 18F]fluoro-L- m-tyrosine, we found strong support for upregulated striatal dopamine synthesis capacity in healthy older adult humans free of amyloid pathology, relative to young people. We next used fMRI tomore » define the functional impact of elevated synthesis capacity on cognitive flexibility, a core component of executive function. We found clear evidence in young adults that low levels of synthesis capacity were suboptimal, associated with diminished cognitive flexibility and altered frontoparietal activation relative to young adults with highest synthesis values. Critically, these relationships between dopamine, performance, and activation were transformed in older adults with higher synthesis capacity. Variability in synthesis capacity was related to intrinsic frontoparietal functional connectivity across groups, suggesting that striatal dopamine synthesis influences the tuning of networks underlying cognitive flexibility. Altogether, these findings define striatal dopamine’s association with cognitive flexibility and its neural underpinnings in young adults, and reveal the alteration in dopamine-related neural processes in aging.« less

Extensive horizontal gene transfer, duplication, and loss of chlorophyll synthesis genes in the algae

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hunsperger, Heather M.; Randhawa, Tejinder; Cattolico, Rose Ann

Two non-homologous, isofunctional enzymes catalyze the penultimate step of chlorophyll a synthesis in oxygenic photosynthetic organisms such as cyanobacteria, eukaryotic algae and land plants: the light independent (LIPOR) and light-dependent (POR) protochlorophyllide oxidoreductases. Whereas the distribution of these enzymes in cyanobacteria and land plants is well understood, the presence, loss, duplication, and replacement of these genes have not been surveyed in the polyphyletic and remarkably diverse eukaryotic algal lineages.

Extensive horizontal gene transfer, duplication, and loss of chlorophyll synthesis genes in the algae

DOE PAGES

Hunsperger, Heather M.; Randhawa, Tejinder; Cattolico, Rose Ann

2015-02-10

Two non-homologous, isofunctional enzymes catalyze the penultimate step of chlorophyll a synthesis in oxygenic photosynthetic organisms such as cyanobacteria, eukaryotic algae and land plants: the light independent (LIPOR) and light-dependent (POR) protochlorophyllide oxidoreductases. Whereas the distribution of these enzymes in cyanobacteria and land plants is well understood, the presence, loss, duplication, and replacement of these genes have not been surveyed in the polyphyletic and remarkably diverse eukaryotic algal lineages.

Stereoselective synthesis of unsaturated α-amino acids.

PubMed

Fanelli, Roberto; Jeanne-Julien, Louis; René, Adeline; Martinez, Jean; Cavelier, Florine

2015-06-01

Stereoselective synthesis of unsaturated α-amino acids was performed by asymmetric alkylation. Two methods were investigated and their enantiomeric excess measured and compared. The first route consisted of an enantioselective approach induced by the Corey-Lygo catalyst under chiral phase transfer conditions while the second one involved the hydroxypinanone chiral auxiliary, both implicating Schiff bases as substrate. In all cases, the use of a prochiral Schiff base gave higher enantiomeric excess and yield in the final desired amino acid.

Modular Assembly of Hierarchically Structured Polymers

NASA Astrophysics Data System (ADS)

Leophairatana, Porakrit

The synthesis of macromolecules with complex yet highly controlled molecular architectures has attracted significant attention in the past few decades due to the growing demand for specialty polymers that possess novel properties. Despite recent efforts, current synthetic routes lack the ability to control several important architectural variables while maintaining low polydispersity index. This dissertation explores a new synthetic scheme for the modular assembly of hierarchically structured polymers (MAHP) that allows virtually any complex polymer to be assembled from a few basic molecular building blocks using a single common coupling chemistry. Complex polymer structures can be assembled from a molecular toolkit consisting of (1) copper-catalyzed azide-alkyne cycloaddition (CuAAC), (2) linear heterobifunctional macromonomers, (3) a branching heterotrifunctional molecule, (4) a protection/deprotection strategy, (5) "click" functional solid substrates, and (6) functional and responsive polymers. This work addresses the different challenges that emerged during the development of this synthetic scheme, and presents strategies to overcome those challenges. Chapter 3 investigates the alkyne-alkyne (i.e. Glaser) coupling side reactions associated with the atom transfer radical polymerization (ATRP) synthesis of alkyne-functional macromonomers, as well as with the CuAAC reaction of alkyne functional building blocks. In typical ATRP synthesis of unprotected alkyne functional polymers, Glaser coupling reactions can significantly compromise the polymer functionality and undermine the success of subsequent click reactions in which the polymers are used. Two strategies are reported that effectively eliminate these coupling reactions: (1) maintaining low temperature post-ATRP upon exposure to air, followed by immediate removal of copper catalyst; and (2) adding excess reducing agents post-ATRP, which prevents the oxidation of Cu(I) catalyst required by the Glaser coupling mechanism. Post-ATRP Glaser coupling was also influenced by the ATRP synthesis ligand used. The order of ligand activity for catalyzing Glaser coupling was: linear bidentate > tridentate > tetradentate. Glaser coupling can also occur for alkynes held under CuAAC reaction conditions but again can be eliminated by adding appropriate reducing agents. With the strategy presented in Chapter 3, alkyne-terminated polymers of high-functionality were produced without the need for alkyne protecting groups. These "click" functional building blocks were employed to investigate the overall efficiency of the CuAAC "click" coupling reactions between alkyne- and azide-terminated macromonomers as discussed in Chapter 4. Quantitative convolution modeling of the entire molecular weight distribution post-CuAAC indicates a CuAAC efficiency of about 94% and an azide substitution efficiency of >99%. However, incomplete functionality of the azide-terminated macromonomer (˜92%) proves to be the largest factor compromising the overall efficacy of the coupling reactions, and is attributed primarily to the loss of bromine functionality during synthesis by ATRP. To address this issue, we discuss in Chapter 6 the development of a new set of molecular building blocks consisting of alkyne functional substrates and heterobifunctional degradable linkers that allow the growth and subsequent detachment of polymers from the solid substrate. Complex polymeric structures are created by progressive cycles of CuAAC and deprotection reactions that add building blocks to the growing polymer chain ends. We demonstrate that these building blocks were completely stable under both CuAAC and deprotection reaction conditions. Since the desired product is covalently bound to the solid surface, the unreacted monomers/macromonomers and by-products (i.e. non-functional building blocks) can be easily separated from the product via removal of the polymer-tethered solid substrate in one step. Chapter 5 discusses how MAHP was employed to prepare a variety of hierarchically structured polymers and copolymers with controlled branching architectures. alpha-azido,o-TIPS-alkyne-heterobifunctional and heterotrifunctional building blocks were first prepared via ATRP and organic synthesis. Preliminary NMR and SEC studies demonstrated that these building blocks all satisfied the criteria necessary for MAHP: (1) the TIPS protecting group is stable during ATRP and CuAAC, (2) the "click" functionality is completely regenerated during the deprotection step, and (3) the CuAAC reaction of branching macromonomers is quantitative (>94%). To demonstrate the concept, poly(n-butyl acrylate)-b-dipolystyrene- b-dipoly(tert-butyl acrylate) penta-block branching copolymacromer was prepared via MAHP and quantitively characterized with SEC and NMR. (Abstract shortened by ProQuest.).

Lipoic acid biosynthesis defects.

PubMed

Mayr, Johannes A; Feichtinger, René G; Tort, Frederic; Ribes, Antonia; Sperl, Wolfgang

2014-07-01

Lipoate is a covalently bound cofactor essential for five redox reactions in humans: in four 2-oxoacid dehydrogenases and the glycine cleavage system (GCS). Two enzymes are from the energy metabolism, α-ketoglutarate dehydrogenase and pyruvate dehydrogenase; and three are from the amino acid metabolism, branched-chain ketoacid dehydrogenase, 2-oxoadipate dehydrogenase, and the GCS. All these enzymes consist of multiple subunits and share a similar architecture. Lipoate synthesis in mitochondria involves mitochondrial fatty acid synthesis up to octanoyl-acyl-carrier protein; and three lipoate-specific steps, including octanoic acid transfer to glycine cleavage H protein by lipoyl(octanoyl) transferase 2 (putative) (LIPT2), lipoate synthesis by lipoic acid synthetase (LIAS), and lipoate transfer by lipoyltransferase 1 (LIPT1), which is necessary to lipoylate the E2 subunits of the 2-oxoacid dehydrogenases. The reduced form dihydrolipoate is reactivated by dihydrolipoyl dehydrogenase (DLD). Mutations in LIAS have been identified that result in a variant form of nonketotic hyperglycinemia with early-onset convulsions combined with a defect in mitochondrial energy metabolism with encephalopathy and cardiomyopathy. LIPT1 deficiency spares the GCS, and resulted in a combined 2-oxoacid dehydrogenase deficiency and early death in one patient and in a less severely affected individual with a Leigh-like phenotype. As LIAS is an iron-sulphur-cluster-dependent enzyme, a number of recently identified defects in mitochondrial iron-sulphur cluster synthesis, including NFU1, BOLA3, IBA57, GLRX5 presented with deficiency of LIAS and a LIAS-like phenotype. As in DLD deficiency, a broader clinical spectrum can be anticipated for lipoate synthesis defects depending on which of the affected enzymes is most rate limiting.

Foundations of low-temperature plasma enhanced materials synthesis and etching

NASA Astrophysics Data System (ADS)

Oehrlein, Gottlieb S.; Hamaguchi, Satoshi

2018-02-01

Low temperature plasma (LTP)-based synthesis of advanced materials has played a transformational role in multiple industries, including the semiconductor industry, liquid crystal displays, coatings and renewable energy. Similarly, the plasma-based transfer of lithographically defined resist patterns into other materials, e.g. silicon, SiO2, Si3N4 and other electronic materials, has led to the production of nanometer scale devices that are the basis of the information technology, microsystems, and many other technologies based on patterned films or substrates. In this article we review the scientific foundations of both LTP-based materials synthesis at low substrate temperature and LTP-based isotropic and directional etching used to transfer lithographically produced resist patterns into underlying materials. We cover the fundamental principles that are the basis of successful application of the LTP techniques to technological uses and provide an understanding of technological factors that may control or limit material synthesis or surface processing with the use of LTP. We precede these sections with a general discussion of plasma surface interactions, the LTP-generated particle fluxes including electrons, ions, radicals, excited neutrals and photons that simultaneously contact and modify surfaces. The surfaces can be in the line of sight of the discharge or hidden from direct interaction for structured substrates. All parts of the article are extensively referenced, which is intended to help the reader study the topics discussed here in more detail.

Sunlight-Induced photochemical synthesis of Au nanodots on α-Fe2O3@Reduced graphene oxide nanocomposite and their enhanced heterogeneous catalytic properties.

PubMed

Bharath, G; Anwer, Shoaib; Mangalaraja, R V; Alhseinat, Emad; Banat, Fawzi; Ponpandian, N

2018-04-09

In this present study, we report the synthesis of Au nanodots on α-Fe 2 O 3 @reduced graphene oxide (RGO) based hetero-photocatalytic nanohybrids through a chlorophyll mediated photochemical synthesis. In this process, chlorophyll induces a rapid reduction (30 min) of Au 3+ ions to Au° metallic nanodots on α-Fe 2 O 3 @RGO surface under sunlight irradiation. The nucleation growth process, photo-induced electron-transfer mechanism and physico-chemical properties of the Au@α-Fe 2 O 3 @RGO ternary nanocomposites were systematically studied with various analytical techniques. This novel photochemical synthesis process is a cost-effective, convenient, surfactant-less, and scalable method. Moreover, the prepared ternary nanocomposites enhanced catalytic activity as compared to pure α-Fe 2 O 3 and α-Fe 2 O 3 @RGO. The advantages and synergistic effect of Au@α-Fe 2 O 3 @RGO exhibit, (i) a broader range of visible-light absorption due to visible light band gap of α-Fe 2 O 3 , (ii) lower recombination possibility of photo-generated electrons and holes due to effect of Au and (iii) faster electron transfer due to higher conductivity of RGO. Therefore, the prepared Au@α-Fe 2 O 3 @RGO hetero-photocatalytic nanohybrids exhibited a remarkable photocatalytic activity, thus enabling potential active hetero-photocatalyst for industrial and environmental applications.

DNA Conjugation and DNA Directed Self-Assembly of Quantum Dots for Nanophotonic Applications

NASA Astrophysics Data System (ADS)

Samanta, Anirban

Colloidal quantum dots (QDs) or semiconductor nanocrystals are often used to describe 2--20 nm solution processed nanoparticles of various semiconductor materials that display quantum confinement effects. Compared to traditional fluorescent organic dyes, QDs provide many advantages. For biological applications it is necessary to develop reliable methods to functionalize QDs with hydrophilic biomolecules so that they may maintain their stability and functionality in physiological conditions. DNA, a molecule that encodes genetic information, is arguably the smartest molecule that nature has ever produced and one of the most explored bio-macromolecules. QDs that are functionalized with DNA can potentially be organized with nanometer precision by DNA directed self-assembly, and the resulting arrangements may facilitate the display of novel optical properties. The goal of this dissertation was to achieve a robust reliable yet simple strategy to link DNA to QDs so that they can be used for DNA directed self assembly by which we can engineer their optical properties. Presented here is a series of studies to achieve this goal. First we demonstrate the aqueous synthesis of colloidal nanocrystal heterostructures consisting of the CdTe core encapsulated by CdS/ZnS or CdSe/ZnS shells using glutathione (GSH), a tripeptide, as the capping ligand. We next employed this shell synthesis strategy to conjugate PS-PO chimeric DNA to QDs at the time of shell synthesis. We synthesized a library of DNA linked QDs emitting from UV to near IR that are very stable in high salt concentrations. These DNA functionalized QDs were further site-specifically organized on DNA origami in desired patterns directed by DNA self-assembly. We further extended our capability to functionalize DNA to real IR emitting CdxPb 1-xTe alloyed QDs, and demonstrated their stability by self-assembling them on DNA origami. The photo-physical properties of the QDs were further engineered by attaching a QD and a gold nanoparticle in controlled distances on the same DNA origami, which revealed a much longer range quenching effect than usual Forster Resonance Energy Transfer. We are currently engaged in enhancing the photoluminescence intensity of the QDs by bringing them in the plasmonic hot spots generated by a cluster of larger plasmonic nanoparticles.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sessler, J. L.; Sathiosatham, M.; Brown, C. T.

The synthesis of a new, noncovalent anthracene-dimethylaniline dyad (ensemble I) held together via guanosine-cytidine Watson-Crick base-pairing interactions is reported. Upon excitation at 420 nm, photoinduced electron-transfer from the dimethylaniline donor to the singlet excited state of the anthracene acceptor occurs, as inferred from a combination of time-resolved fluorescence quenching and transient absorption measurements. In toluene at room temperature, the rate constants for photoinduced intraensemble electron-transfer and subsequent back-electron-transfer (charge recombination) are k{sub CS} = (3.5 {+-} 0.03) x 10{sup 10} s{sup -1} and k{sub CR} = (1.42 {+-} 0.03) x 10{sup 9} s{sup -1}, respectively.

Synthesis, spectroscopic (FT-IR, FT-Raman, NMR, UV-Visible), Fukui function, antimicrobial and molecular docking study of (E)-1-(3-bromobenzylidene)semicarbazide by DFT method

NASA Astrophysics Data System (ADS)

Raja, M.; Raj Muhamed, R.; Muthu, S.; Suresh, M.; Muthu, K.

2017-02-01

The title compound, (E)-1-(3-bromobenzylidene)semicarbazide (3BSC) was synthesized and characterized by FT-IR, FT-Raman, UV, 1HNMR and 13CNMR spectral analysis. The optimized molecular geometry, the vibrational wavenumbers, the infrared intensities and the Raman scattering activities were calculated by using density functional theory (DFT) B3LYP method with 6-311++G(d,p) basis set. The calculated HOMO and LUMO energies show that charge transfer within the molecule. Stability of the molecule arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital analysis (NBO). The hyperpolarizability calculation reveals the present material has a reasonably good propensity for nonlinear optical activity. Molecular electrostatic potential (MEP) and Fukui functions were also performed. The thermodynamic properties (heat capacity, entropy, and enthalpy) of the 3BSC at different temperatures have been calculated. The biological applications of 3BSC have been screened for its antimicrobial activity and found to exhibit antifungal and antibacterial effects. In addition, the Molecular docking was also performed for the different receptors.

New Aminoacyl-tRNA Synthetase-like Protein in Insecta with an Essential Mitochondrial Function*♦

PubMed Central

Guitart, Tanit; Leon Bernardo, Teresa; Sagalés, Jessica; Stratmann, Thomas; Bernués, Jordi; Ribas de Pouplana, Lluís

2010-01-01

Aminoacyl-tRNA synthetases (ARS) are modular enzymes that aminoacylate transfer RNAs (tRNA) for their use by the ribosome during protein synthesis. ARS are essential and universal components of the genetic code that were almost completely established before the appearance of the last common ancestor of all living species. This long evolutionary history explains the growing number of functions being discovered for ARS, and for ARS homologues, beyond their canonical role in gene translation. Here we present a previously uncharacterized paralogue of seryl-tRNA synthetase named SLIMP (seryl-tRNA synthetase-like insect mitochondrial protein). SLIMP is the result of a duplication of a mitochondrial seryl-tRNA synthetase (SRS) gene that took place in early metazoans and was fixed in Insecta. Here we show that SLIMP is localized in the mitochondria, where it carries out an essential function that is unrelated to the aminoacylation of tRNA. The knockdown of SLIMP by RNA interference (RNAi) causes a decrease in respiration capacity and an increase in mitochondrial mass in the form of aberrant mitochondria. PMID:20870726

Synthesis, spectroscopic (FT-IR, FT-Raman, NMR, UV-Visible), NLO, NBO, HOMO-LUMO, Fukui function and molecular docking study of (E)-1-(5-bromo-2-hydroxybenzylidene)semicarbazide

NASA Astrophysics Data System (ADS)

Raja, M.; Raj Muhamed, R.; Muthu, S.; Suresh, M.

2017-08-01

The title compound, (E)-1-(5-bromo-2-hydroxybenzylidene)semicarbazide (15BHS) was synthesized and characterized by FT-IR, FT-Raman, UV, 1HNMR and 13CNMR spectral analysis. The optimized molecular geometry, the vibrational wavenumbers, the infrared intensities and the Raman scattering activities were calculated by using density functional theory(DFT) B3LYP method with 6-311++G(d,p) basis set. The detailed interpretation of the vibrational spectra has been carried out by VEDA program. The calculated HOMO and LUMO energies show that charge transfer within the molecule. Stability of the molecule arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital analysis (NBO). The first order hyperpolarizability, Molecular electrostatic potential (MEP) and Fukui functions were also performed. To study the biological activity of the investigation molecule, molecular docking was done to identify the hydrogen bond lengths and binding energy with different antifungal proteins. The thermodynamic properties (heat capacity, entropy, and enthalpy) of the 15BHS at different temperatures have been calculated.

Synthesis and in vivo magnetic resonance imaging evaluation of biocompatible branched copolymer nanocontrast agents.

PubMed

Jackson, Alexander W; Chandrasekharan, Prashant; Shi, Jian; Rannard, Steven P; Liu, Quan; Yang, Chang-Tong; He, Tao

2015-01-01

Branched copolymer nanoparticles (D(h) =20-35 nm) possessing 1,4,7, 10-tetraazacyclododecane-N,N',N″,N‴-tetraacetic acid macrocycles within their cores have been synthesized and applied as magnetic resonance imaging (MRI) nanosized contrast agents in vivo. These nanoparticles have been generated from novel functional monomers via reversible addition-fragmentation chain transfer polymerization. The process is very robust and synthetically straightforward. Chelation with gadolinium and preliminary in vivo experiments have demonstrated promising characteristics as MRI contrast agents with prolonged blood retention time, good biocompatibility, and an intravascular distribution. The ability of these nanoparticles to perfuse and passively target tumor cells through the enhanced permeability and retention effect is also demonstrated. These novel highly functional nanoparticle platforms have succinimidyl ester-activated benzoate functionalities within their corona, which make them suitable for future peptide conjugation and subsequent active cell-targeted MRI or the conjugation of fluorophores for bimodal imaging. We have also demonstrated that these branched copolymer nanoparticles are able to noncovalently encapsulate hydrophobic guest molecules, which could allow simultaneous bioimaging and drug delivery.

λ5-Phosphorus-Containing α-Diazo Compounds: A Valuable Tool for Accessing Phosphorus-Functionalized Molecules.

PubMed

Marinozzi, Maura; Pertusati, Fabrizio; Serpi, Michaela

2016-11-23

The compounds characterized by the presence of a λ 5 -phosphorus functionality at the α-position with respect to the diazo moiety, here referred to as λ 5 -phosphorus-containing α-diazo compounds (PCDCs), represent a vast class of extremely versatile reagents in organic chemistry and are particularly useful in the preparation of phosphonate- and phosphinoxide-functionalized molecules. Indeed, thanks to the high reactivity of the diazo moiety, PCDCs can be induced to undergo a wide variety of chemical transformations. Among them are carbon-hydrogen, as well as heteroatom-hydrogen insertion reactions, cyclopropanation, ylide formation, Wolff rearrangement, and cycloaddition reactions. PCDCs can be easily prepared from readily accessible precursors by a variety of different methods, such as diazotization, Bamford-Stevens-type elimination, and diazo transfer reactions. This evidence along with their relative stability and manageability make them appealing tools in organic synthesis. This Review aims to demonstrate the ongoing utility of PCDCs in the modern preparation of different classes of phosphorus-containing compounds, phosphonates, in particular. Furthermore, to address the lack of precedent collective papers, this Review also summarizes the methods for PCDCs preparation.

Methods for Kinetic and Thermodynamic Analysis of Aminoacyl-tRNA Synthetases

PubMed Central

Francklyn, Christopher S.; First, Eric A.; Perona, John J.; Hou, Ya-Ming

2008-01-01

The accuracy of protein synthesis relies on the ability of aminoacyl-tRNA synthetases (aaRSs) to discriminate among true and near cognate substrates. To date, analysis of aaRSs function, including identification of residues of aaRS participating in amino acid and tRNA discrimination, has largely relied on the steady state kinetic pyrophosphate exchange and aminoacylation assays. Pre-steady state kinetic studies investigating a more limited set of aaRS systems have also been undertaken to assess the energetic contributions of individual enzyme-substrate interactions, particularly in the adenylation half reaction. More recently, a renewed interest in the use of rapid kinetics approaches for aaRSs has led to their application to several new aaRS systems, resulting in the identification of mechanistic differences that distinguish the two structurally distinct aaRS classes. Here, we review the techniques for thermodynamic and kinetic analysis of aaRS function. Following a brief survey of methods for the preparation of materials and for steady state kinetic analysis, this review will describe pre-steady state kinetic methods employing rapid quench and stopped-flow fluorescence for analysis of the activation and aminoacyl transfer reactions. Application of these methods to any aaRS system allows the investigator to derive detailed kinetic mechanisms for the activation and aminoacyl transfer reactions, permitting issues of substrate specificity, stereochemical mechanism, and inhibitor interaction to be addressed in a rigorous and quantitative fashion. PMID:18241792

Functional analysis of the zebrafish ortholog of HMGCS1 reveals independent functions for cholesterol and isoprenoids in craniofacial development

PubMed Central

Hernandez, Jose A.; Gonzalez, Cesar G.

2017-01-01

There are 8 different human syndromes caused by mutations in the cholesterol synthesis pathway. A subset of these disorders such as Smith-Lemli-Opitz disorder, are associated with facial dysmorphia. However, the molecular and cellular mechanisms underlying such facial deficits are not fully understood, primarily because of the diverse functions associated with the cholesterol synthesis pathway. Recent evidence has demonstrated that mutation of the zebrafish ortholog of HMGCR results in orofacial clefts. Here we sought to expand upon these data, by deciphering the cholesterol dependent functions of the cholesterol synthesis pathway from the cholesterol independent functions. Moreover, we utilized loss of function analysis and pharmacological inhibition to determine the extent of sonic hedgehog (Shh) signaling in animals with aberrant cholesterol and/or isoprenoid synthesis. Our analysis confirmed that mutation of hmgcs1, which encodes the first enzyme in the cholesterol synthesis pathway, results in craniofacial abnormalities via defects in cranial neural crest cell differentiation. Furthermore targeted pharmacological inhibition of the cholesterol synthesis pathway revealed a novel function for isoprenoid synthesis during vertebrate craniofacial development. Mutation of hmgcs1 had no effect on Shh signaling at 2 and 3 days post fertilization (dpf), but did result in a decrease in the expression of gli1, a known Shh target gene, at 4 dpf, after morphological deficits in craniofacial development and chondrocyte differentiation were observed in hmgcs1 mutants. These data raise the possibility that deficiencies in cholesterol modulate chondrocyte differentiation by a combination of Shh independent and Shh dependent mechanisms. Moreover, our results describe a novel function for isoprenoids in facial development and collectively suggest that cholesterol regulates craniofacial development through versatile mechanisms. PMID:28686747

Styrene-spaced copolymers including anthraquinone and β-O-4 lignin model units: synthesis, characterization and reactivity under alkaline pulping conditions.

PubMed

Megiatto, Jackson D; Cazeils, Emmanuel; Ham-Pichavant, Frédérique; Grelier, Stéphane; Gardrat, Christian; Castellan, Alain

2012-05-14

A series of random copoly(styrene)s has been synthesized via radical polymerization of functionalized anthraquinone (AQ) and β-O-4 lignin model monomers. The copolymers were designed to have a different number of styrene spacer groups between the AQ and β-O-4 lignin side chains aiming at investigating the distance effects on AQ/β-O-4 electron transfer mechanisms. A detailed molecular characterization, including techniques such as size exclusion chromatography, MALDI-TOF mass spectrometry, and (1)H, (13)C, (31)P NMR and UV-vis spectroscopies, afforded quantitative information about the composition of the copolymers as well as the average distribution of the AQ and β-O-4 groups in the macromolecular structures. TGA and DSC thermal analysis have indicated that the copolymers were thermally stable under regular pulping conditions, revealing the inertness of the styrene polymer backbone in the investigation of electron transfer mechanisms. Alkaline pulping experiments showed that close contact between the redox active side chains in the copolymers was fundamental for an efficient degradation of the β-O-4 lignin model units, highlighting the importance of electron transfer reactions in the lignin degradation mechanisms catalyzed by AQ. In the absence of glucose, AQ units oxidized phenolic β-O-4 lignin model parts, mainly by electron transfer leading to vanillin as major product. By contrast, in presence of glucose, anthrahydroquinone units (formed by reduction of AQ) reduced the quinone-methide units (issued by dehydration of phenolic β-O-4 lignin model part) mainly by electron transfer leading to guaiacol as major product. Both processes were distance dependent.

Fluorescent probes for tracking the transfer of iron–sulfur cluster and other metal cofactors in biosynthetic reaction pathways

DOE PAGES

Vranish, James N.; Russell, William K.; Yu, Lusa E.; ...

2014-12-05

Iron–sulfur (Fe–S) clusters are protein cofactors that are constructed and delivered to target proteins by elaborate biosynthetic machinery. Mechanistic insights into these processes have been limited by the lack of sensitive probes for tracking Fe–S cluster synthesis and transfer reactions. Here we present fusion protein- and intein-based fluorescent labeling strategies that can probe Fe–S cluster binding. The fluorescence is sensitive to different cluster types ([2Fe–2S] and [4Fe–4S] clusters), ligand environments ([2Fe–2S] clusters on Rieske, ferredoxin (Fdx), and glutaredoxin), and cluster oxidation states. The power of this approach is highlighted with an extreme example in which the kinetics of Fe–S clustermore » transfer reactions are monitored between two Fdx molecules that have identical Fe–S spectroscopic properties. This exchange reaction between labeled and unlabeled Fdx is catalyzed by dithiothreitol (DTT), a result that was confirmed by mass spectrometry. DTT likely functions in a ligand substitution reaction that generates a [2Fe–2S]–DTT species, which can transfer the cluster to either labeled or unlabeled Fdx. The ability to monitor this challenging cluster exchange reaction indicates that real-time Fe–S cluster incorporation can be tracked for a specific labeled protein in multicomponent assays that include several unlabeled Fe–S binding proteins or other chromophores. Such advanced kinetic experiments are required to untangle the intricate networks of transfer pathways and the factors affecting flux through branch points. High sensitivity and suitability with high-throughput methodology are additional benefits of this approach. Lastly, we anticipate that this cluster detection methodology will transform the study of Fe–S cluster pathways and potentially other metal cofactor biosynthetic pathways.« less

A molecular dynamics simulation study of amino acid selectivity of LeuRS editing domain from Thermus thermophilus.

PubMed

Rayevsky, Alexey; Sharifi, Mohsen; Tukalo, Michael

2018-06-18

The accuracy of protein synthesis is provided by the editing functions of aminoacyl-tRNA synthetases (aaRSs), a mechanism that eliminates misactivated amino acids or mischarged tRNAs. Despite research efforts, some molecular bases of these mechanisms are still unclear. The post-transfer editing pathway of leucyl-tRNA synthetase (LeuRS) carried out in a special insertion domain (the Connective Polypeptide 1 or CP1), as editing domain. Recently, it was shown by in vivo studies and was supported by mutagenesis, and the kinetics approaches that the CP1 domain of LeuRS has discriminatory power for different substrates. The goal of this work is to investigate the structural basis for amino acid recognition of LeuRS post-transfer editing processes with molecular dynamics (MD) simulation method. To pursue this aim, the molecular modeling studies on Thermus thermophiles LeuRS (LeuRSTT) with two post-transfer substrates (norvalyl-tRNA Leu and isoleucyl-tRNA Leu ) was performed. Our results revealed that post-transfer substrate norvalyl-tRNA Leu is more favorable. Moreover, the MD simulations show that branched side chain of Ile-A76 cannot allow water molecules to get close, which leads to a significant decrease in the rate of hydrolysis. Finally, the study showed that site mutation Asp347Ala has elucidated a number of fine structural differences in the binding mode of two post-transfer substrates to the active centre of LeuRS editing domain and two conserved threonines, namely Thr247 and Thr248, are responsible for the amino acid selection through the interaction with substrates. Copyright © 2018 Elsevier Inc. All rights reserved.

Catalytic enantioselective alkene aminohalogenation/cyclization involving atom transfer.

PubMed

Bovino, Michael T; Chemler, Sherry R

2012-04-16

Problem solved: the title reaction was used for the synthesis of chiral 2-bromo, chloro, and iodomethyl indolines and 2-iodomethyl pyrrolidines. Stereocenter formation is believed to occur by enantioselective cis aminocupration and C-X bond formation is believed to occur by atom transfer. The ultility of the products as versatile synthetic intermediates was demonstrated, as was a radical cascade cyclization sequence. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of Cyclic α-Diazo-β-keto Sulfoxides in Batch and Continuous Flow.

PubMed

McCaw, Patrick G; Buckley, Naomi M; Eccles, Kevin S; Lawrence, Simon E; Maguire, Anita R; Collins, Stuart G

2017-04-07

Diazo transfer to β-keto sulfoxides to form stable isolable α-diazo-β-keto sulfoxides has been achieved for the first time. Both monocyclic and benzofused ketone derived β-keto sulfoxides were successfully explored as substrates for diazo transfer. Use of continuous flow leads to isolation of the desired compounds in enhanced yields relative to standard batch conditions, with short reaction times, increased safety profile, and potential to scale up.

Resolving the negative potential side (n-side) water-accessible proton pathway of F-type ATP synthase by molecular dynamics simulations.

PubMed

Gohlke, Holger; Schlieper, Daniel; Groth, Georg

2012-10-19

The rotation of F(1)F(o)-ATP synthase is powered by the proton motive force across the energy-transducing membrane. The protein complex functions like a turbine; the proton flow drives the rotation of the c-ring of the transmembrane F(o) domain, which is coupled to the ATP-producing F(1) domain. The hairpin-structured c-protomers transport the protons by reversible protonation/deprotonation of a conserved Asp/Glu at the outer transmembrane helix (TMH). An open question is the proton transfer pathway through the membrane at atomic resolution. The protons are thought to be transferred via two half-channels to and from the conserved cAsp/Glu in the middle of the membrane. By molecular dynamics simulations of c-ring structures in a lipid bilayer, we mapped a water channel as one of the half-channels. We also analyzed the suppressor mutant cP24D/E61G in which the functional carboxylate is shifted to the inner TMH of the c-protomers. Current models concentrating on the "locked" and "open" conformations of the conserved carboxylate side chain are unable to explain the molecular function of this mutant. Our molecular dynamics simulations revealed an extended water channel with additional water molecules bridging the distance of the outer to the inner TMH. We suggest that the geometry of the water channel is an important feature for the molecular function of the membrane part of F(1)F(o)-ATP synthase. The inclination of the proton pathway isolates the two half-channels and may contribute to a favorable clockwise rotation in ATP synthesis mode.

Bacterial α2-macroglobulins: colonization factors acquired by horizontal gene transfer from the metazoan genome?

PubMed Central

Budd, Aidan; Blandin, Stephanie; Levashina, Elena A; Gibson, Toby J

2004-01-01

Background Invasive bacteria are known to have captured and adapted eukaryotic host genes. They also readily acquire colonizing genes from other bacteria by horizontal gene transfer. Closely related species such as Helicobacter pylori and Helicobacter hepaticus, which exploit different host tissues, share almost none of their colonization genes. The protease inhibitor α2-macroglobulin provides a major metazoan defense against invasive bacteria, trapping attacking proteases required by parasites for successful invasion. Results Database searches with metazoan α2-macroglobulin sequences revealed homologous sequences in bacterial proteomes. The bacterial α2-macroglobulin phylogenetic distribution is patchy and violates the vertical descent model. Bacterial α2-macroglobulin genes are found in diverse clades, including purple bacteria (proteobacteria), fusobacteria, spirochetes, bacteroidetes, deinococcids, cyanobacteria, planctomycetes and thermotogae. Most bacterial species with bacterial α2-macroglobulin genes exploit higher eukaryotes (multicellular plants and animals) as hosts. Both pathogenically invasive and saprophytically colonizing species possess bacterial α2-macroglobulins, indicating that bacterial α2-macroglobulin is a colonization rather than a virulence factor. Conclusions Metazoan α2-macroglobulins inhibit proteases of pathogens. The bacterial homologs may function in reverse to block host antimicrobial defenses. α2-macroglobulin was probably acquired one or more times from metazoan hosts and has then spread widely through other colonizing bacterial species by more than 10 independent horizontal gene transfers. yfhM-like bacterial α2-macroglobulin genes are often found tightly linked with pbpC, encoding an atypical peptidoglycan transglycosylase, PBP1C, that does not function in vegetative peptidoglycan synthesis. We suggest that YfhM and PBP1C are coupled together as a periplasmic defense and repair system. Bacterial α2-macroglobulins might provide useful targets for enhancing vaccine efficacy in combating infections. PMID:15186489

Synthesis and chirality of amino acids under interstellar conditions.

PubMed

Giri, Chaitanya; Goesmann, Fred; Meinert, Cornelia; Evans, Amanda C; Meierhenrich, Uwe J

2013-01-01

Amino acids are the fundamental building blocks of proteins, the biomolecules that provide cellular structure and function in all living organisms. A majority of amino acids utilized within living systems possess pre-specified orientation geometry (chirality); however the original source for this specific orientation remains uncertain. In order to trace the chemical evolution of life, an appreciation of the synthetic and evolutional origins of the first chiral amino acids must first be gained. Given that the amino acids in our universe are likely to have been synthesized in molecular clouds in interstellar space, it is necessary to understand where and how the first synthesis might have occurred. The asymmetry of the original amino acid synthesis was probably the result of exposure to chiral photons in the form of circularly polarized light (CPL), which has been detected in interstellar molecular clouds. This chirality transfer event, from photons to amino acids, has been successfully recreated experimentally and is likely a combination of both asymmetric synthesis and enantioselective photolysis. A series of innovative studies have reported successful simulation of these environments and afforded production of chiral amino acids under realistic circumstellar and interstellar conditions: irradiation of interstellar ice analogues (CO, CO2, NH3, CH3OH, and H2O) with circularly polarized ultraviolet photons at low temperatures does result in enantiomer enriched amino acid structures (up to 1.3% ee). This topical review summarizes current knowledge and recent discoveries about the simulated interstellar environments within which amino acids were probably formed. A synopsis of the COSAC experiment onboard the ESA cometary mission ROSETTA concludes this review: the ROSETTA mission will soft-land on the nucleus of the comet 67P/Churyumov-Gerasimenko in November 2014, anticipating the first in situ detection of asymmetric organic molecules in cometary ices.

Partitioning of glutamine synthesised by the isolated perfused human placenta between the maternal and fetal circulations☆

PubMed Central

Day, P.E.L.; Cleal, J.K.; Lofthouse, E.M.; Goss, V.; Koster, G.; Postle, A.; Jackson, J.M.; Hanson, M.A.; Jackson, A.A.; Lewis, R.M.

2013-01-01

Introduction Placental glutamine synthesis has been demonstrated in animals and is thought to increase the availability of this metabolically important amino acid to the fetus. Glutamine is of fundamental importance for cellular replication, cellular function and inter-organ nitrogen transfer. The objective of this study was to investigate the role of glutamate/glutamine metabolism by the isolated perfused human placenta in the provision of glutamine to the fetus. Methods Glutamate metabolism was investigated in the isolated dually perfused human placental cotyledon. U–13C-glutamate was used to investigate the movement of carbon and 15N-leucine to study movement of amino-nitrogen. Labelled amino acids were perfused via maternal or fetal arteries at defined flow rates. The enrichment and concentration of amino acids in the maternal and fetal veins were measured following 5 h of perfusion. Results Glutamate taken up from the maternal and fetal circulations was primarily converted into glutamine the majority of which was released into the maternal circulation. The glutamine transporter SNAT5 was localised to the maternal-facing membrane of the syncytiotrophoblast. Enrichment of 13C or 15N glutamine in placental tissue was lower than in either the maternal or fetal circulation, suggesting metabolic compartmentalisation within the syncytiotrophoblast. Discussion Placental glutamine synthesis may help ensure the placenta's ability to supply this amino acid to the fetus does not become limiting to fetal growth. Glutamine synthesis may also influence placental transport of other amino acids, metabolism, nitrogen flux and cellular regulation. Conclusions Placental glutamine synthesis may therefore be a central mechanism in ensuring that the human fetus receives adequate nutrition and is able to maintain growth. PMID:24183194

Testate amoeba transfer function performance along localised hydrological gradients.

PubMed

Tsyganov, Andrey N; Mityaeva, Olga A; Mazei, Yuri A; Payne, Richard J

2016-09-01

Testate amoeba transfer functions are widely used for reconstruction of palaeo-hydrological regime in peatlands. However, the limitations of this approach have become apparent with increasing attention to validation and assessing sources of uncertainty. This paper investigates effects of peatland type and sampling depth on the performance of a transfer function using an independent test-set from four Sphagnum-dominated sites in European Russia (Penza Region). We focus on transfer function performance along localised hydrological gradients, which is a useful analogue for predictive ability through time. The performance of the transfer function with the independent test-set was generally weaker than for the leave-one-out or bootstrap cross-validations. However, the transfer function was robust for the reconstruction of relative changes in water-table depth, provided the presence of good modern analogues and overlap in water-table depth ranges. When applied to subsurface samples, the performance of the transfer function was reduced due to selective decomposition, the presence of deep-dwelling taxa or vertical transfer of shells. Our results stress the importance of thorough testing of transfer functions, and highlight the role of taphonomic processes in determining results. Further studies of stratification, taxonomy and taphonomy of testate amoebae will be needed to improve the robustness of transfer function output. Copyright © 2015 Elsevier GmbH. All rights reserved.

Transfer function characteristics of super resolving systems

NASA Technical Reports Server (NTRS)

Milster, Tom D.; Curtis, Craig H.

1992-01-01

Signal quality in an optical storage device greatly depends on the optical system transfer function used to write and read data patterns. The problem is similar to analysis of scanning optical microscopes. Hopkins and Braat have analyzed write-once-read-many (WORM) optical data storage devices. Herein, transfer function analysis of magnetooptic (MO) data storage devices is discussed with respect to improving transfer-function characteristics. Several authors have described improving the transfer function as super resolution. However, none have thoroughly analyzed the MO optical system and effects of the medium. Both the optical system transfer function and effects of the medium of this development are discussed.

Synthesis of Graphene Based Membranes: Effect of Substrate Surface Properties on Monolayer Graphene Transfer.

PubMed

Kafiah, Feras; Khan, Zafarullah; Ibrahim, Ahmed; Atieh, Muataz; Laoui, Tahar

2017-01-21

In this work, we report the transfer of graphene onto eight commercial microfiltration substrates having different pore sizes and surface characteristics. Monolayer graphene grown on copper by the chemical vapor deposition (CVD) process was transferred by the pressing method over the target substrates, followed by wet etching of copper to obtain monolayer graphene/polymer membranes. Scanning electron microscopy (SEM), atomic force microscopy (AFM), and contact angle (CA) measurements were carried out to explore the graphene layer transferability. Three factors, namely, the substrate roughness, its pore size, and its surface wetting (degree of hydrophobicity) are found to affect the conformality and coverage of the transferred graphene monolayer on the substrate surface. A good quality graphene transfer is achieved on the substrate with the following characteristics; being hydrophobic (CA > 90°), having small pore size, and low surface roughness, with a CA to RMS (root mean square) ratio higher than 2.7°/nm.

In silico analysis of the fucosylation-associated genome of the human blood fluke Schistosoma mansoni: cloning and characterization of the enzymes involved in GDP-L-fucose synthesis and Golgi import

PubMed Central

2013-01-01

Background Carbohydrate structures of surface-expressed and secreted/excreted glycoconjugates of the human blood fluke Schistosoma mansoni are key determinants that mediate host-parasite interactions in both snail and mammalian hosts. Fucose is a major constituent of these immunologically important glycans, and recent studies have sought to characterize fucosylation-associated enzymes, including the Golgi-localized fucosyltransferases that catalyze the transfer of L-fucose from a GDP-L-fucose donor to an oligosaccharide acceptor. Importantly, GDP-L-fucose is the only nucleotide-sugar donor used by fucosyltransferases and its availability represents a bottleneck in fucosyl-glycotope expression. Methods A homology-based genome-wide bioinformatics approach was used to identify and molecularly characterize the enzymes that contribute to GDP-L-fucose synthesis and Golgi import in S. mansoni. Putative functions were further investigated through molecular phylogenetic and immunocytochemical analyses. Results We identified homologs of GDP-D-mannose-4,6-dehydratase (GMD) and GDP-4-keto-6-deoxy-D-mannose-3,5-epimerase-4-reductase (GMER), which constitute a de novo pathway for GDP-L-fucose synthesis, in addition to a GDP-L-fucose transporter (GFT) that putatively imports cytosolic GDP-L-fucose into the Golgi. In silico primary sequence analyses identified characteristic Rossman loop and short-chain dehydrogenase/reductase motifs in GMD and GMER as well as 10 transmembrane domains in GFT. All genes are alternatively spliced, generating variants of unknown function. Observed quantitative differences in steady-state transcript levels between miracidia and primary sporocysts may contribute to differential glycotope expression in early larval development. Additionally, analyses of protein expression suggest the occurrence of cytosolic GMD and GMER in the ciliated epidermal plates and tegument of miracidia and primary sporocysts, respectively, which is consistent with previous localization of highly fucosylated glycotopes. Conclusions This study is the first to identify and characterize three key genes that are putatively involved in the synthesis and Golgi import of GDP-L-fucose in S. mansoni and provides fundamental information regarding their genomic organization, genetic variation, molecular phylogenetics, and developmental expression in intramolluscan larval stages. PMID:23835114

In silico analysis of the fucosylation-associated genome of the human blood fluke Schistosoma mansoni: cloning and characterization of the enzymes involved in GDP-L-fucose synthesis and Golgi import.

PubMed

Peterson, Nathan A; Anderson, Tavis K; Wu, Xiao-Jun; Yoshino, Timothy P

2013-07-09

Carbohydrate structures of surface-expressed and secreted/excreted glycoconjugates of the human blood fluke Schistosoma mansoni are key determinants that mediate host-parasite interactions in both snail and mammalian hosts. Fucose is a major constituent of these immunologically important glycans, and recent studies have sought to characterize fucosylation-associated enzymes, including the Golgi-localized fucosyltransferases that catalyze the transfer of L-fucose from a GDP-L-fucose donor to an oligosaccharide acceptor. Importantly, GDP-L-fucose is the only nucleotide-sugar donor used by fucosyltransferases and its availability represents a bottleneck in fucosyl-glycotope expression. A homology-based genome-wide bioinformatics approach was used to identify and molecularly characterize the enzymes that contribute to GDP-L-fucose synthesis and Golgi import in S. mansoni. Putative functions were further investigated through molecular phylogenetic and immunocytochemical analyses. We identified homologs of GDP-D-mannose-4,6-dehydratase (GMD) and GDP-4-keto-6-deoxy-D-mannose-3,5-epimerase-4-reductase (GMER), which constitute a de novo pathway for GDP-L-fucose synthesis, in addition to a GDP-L-fucose transporter (GFT) that putatively imports cytosolic GDP-L-fucose into the Golgi. In silico primary sequence analyses identified characteristic Rossman loop and short-chain dehydrogenase/reductase motifs in GMD and GMER as well as 10 transmembrane domains in GFT. All genes are alternatively spliced, generating variants of unknown function. Observed quantitative differences in steady-state transcript levels between miracidia and primary sporocysts may contribute to differential glycotope expression in early larval development. Additionally, analyses of protein expression suggest the occurrence of cytosolic GMD and GMER in the ciliated epidermal plates and tegument of miracidia and primary sporocysts, respectively, which is consistent with previous localization of highly fucosylated glycotopes. This study is the first to identify and characterize three key genes that are putatively involved in the synthesis and Golgi import of GDP-L-fucose in S. mansoni and provides fundamental information regarding their genomic organization, genetic variation, molecular phylogenetics, and developmental expression in intramolluscan larval stages.

Synthesis and Structure Property Studies of Toughened Epoxy Resins Via Functionalized Polysiloxanes.

DTIC Science & Technology

1987-09-30

34 87S N4 SYNTHESIS RNO STRUCTURE PROPERTY STUDIES OF OP NDD mEPOXY RESINS YIN FU.. (U) VIROINIR POLYTECHNIC INST OM STNTE UNIY RCKSBURG DEPT OF C.. J...Classification) Synthesis and Structure Property Studies of Toughened Epoxy Resins Via Functionalized Polysiloxanes 12. PERSONALAUTHOR(S) J. 5. HitTIe... Resins , Toughening 19. ABSTRACT (Continue on reverse if necessary and identify by block number) Epoxy resins chemically modified with functionally

Selective sp3 C-H alkylation via polarity-match-based cross-coupling.

PubMed

Le, Chip; Liang, Yufan; Evans, Ryan W; Li, Ximing; MacMillan, David W C

2017-07-06

The functionalization of carbon-hydrogen (C-H) bonds is one of the most attractive strategies for molecular construction in organic chemistry. The hydrogen atom is considered to be an ideal coupling handle, owing to its relative abundance in organic molecules and its availability for functionalization at almost any stage in a synthetic sequence. Although many C-H functionalization reactions involve C(sp 3 )-C(sp 2 ) coupling, there is a growing demand for C-H alkylation reactions, wherein sp 3 C-H bonds are replaced with sp 3 C-alkyl groups. Here we describe a polarity-match-based selective sp 3 C-H alkylation via the combination of photoredox, nickel and hydrogen-atom transfer catalysis. This methodology simultaneously uses three catalytic cycles to achieve hydridic C-H bond abstraction (enabled by polarity matching), alkyl halide oxidative addition, and reductive elimination to enable alkyl-alkyl fragment coupling. The sp 3 C-H alkylation is highly selective for the α-C-H of amines, ethers and sulphides, which are commonly found in pharmaceutically relevant architectures. This cross-coupling protocol should enable broad synthetic applications in de novo synthesis and late-stage functionalization chemistry.

Selective sp3 C–H alkylation via polarity-match-based cross-coupling

PubMed Central

Le, Chip; Liang, Yufan; Evans, Ryan W.; Li, Ximing; MacMillan, David W. C.

2017-01-01

The functionalization of carbon–hydrogen (C–H) bonds is one of the most attractive strategies for molecular construction in organic chemistry. The hydrogen atom is considered to be an ideal coupling handle, owing to its relative abundance in organic molecules and its availability for functionalization at almost any stage in a synthetic sequence1. Although many C–H functionalization reactions involve C(sp3)–C(sp2) coupling, there is a growing demand for C–H alkylation reactions, wherein sp3 C–H bonds are replaced with sp3 C–alkyl groups. Here we describe a polarity-match-based selective sp3 C–H alkylation via the combination of photoredox, nickel and hydrogen-atom transfer catalysis. This methodology simultaneously uses three catalytic cycles to achieve hydridic C–H bond abstraction (enabled by polarity matching), alkyl halide oxidative addition, and reductive elimination to enable alkyl–alkyl fragment coupling. The sp3 C–H alkylation is highly selective for the α-C–H of amines, ethers and sulphides, which are commonly found in pharmaceutically relevant architectures. This cross-coupling protocol should enable broad synthetic applications in de novo synthesis and late-stage functionalization chemistry. PMID:28636596

Selective sp3 C-H alkylation via polarity-match-based cross-coupling

NASA Astrophysics Data System (ADS)

Le, Chip; Liang, Yufan; Evans, Ryan W.; Li, Ximing; MacMillan, David W. C.

2017-07-01

The functionalization of carbon-hydrogen (C-H) bonds is one of the most attractive strategies for molecular construction in organic chemistry. The hydrogen atom is considered to be an ideal coupling handle, owing to its relative abundance in organic molecules and its availability for functionalization at almost any stage in a synthetic sequence. Although many C-H functionalization reactions involve C(sp3)-C(sp2) coupling, there is a growing demand for C-H alkylation reactions, wherein sp3 C-H bonds are replaced with sp3 C-alkyl groups. Here we describe a polarity-match-based selective sp3 C-H alkylation via the combination of photoredox, nickel and hydrogen-atom transfer catalysis. This methodology simultaneously uses three catalytic cycles to achieve hydridic C-H bond abstraction (enabled by polarity matching), alkyl halide oxidative addition, and reductive elimination to enable alkyl-alkyl fragment coupling. The sp3 C-H alkylation is highly selective for the α-C-H of amines, ethers and sulphides, which are commonly found in pharmaceutically relevant architectures. This cross-coupling protocol should enable broad synthetic applications in de novo synthesis and late-stage functionalization chemistry.

Mathematical Model of Heat Transfer in the Catalyst Granule with Point Reaction Centers

NASA Astrophysics Data System (ADS)

Derevich, I. V.; Fokina, A. Yu.

2018-01-01

This paper considers a catalyst granule with a porous ceramic chemically inert base and active point centers, at which an exothermic reaction of synthesis takes place. The rate of a chemical reaction depends on temperature by the Arrhenius law. The heat is removed from the catalyst granule surface to the synthesis products by heat transfer. Based on the idea of self-consistent field, a closed system of equations is constructed for calculating the temperatures of the active centers. As an example, a catalyst granule of the Fischer-Tropsch synthesis with active metallic cobalt particles is considered. The stationary temperatures of the active centers are calculated by the timedependent technique by solving a system of ordinary differential equations. The temperature distribution inside the granule has been found for the local centers located on one diameter of the granule and distributed randomly in the granule's volume. The existence of the critical temperature inside the reactor has been established, the excess of which leads to substantial superheating of local centers. The temperature distribution with local reaction centers differs qualitatively from the granule temperature calculated in the homogeneous approximation. The results of calculations are given.

A Systematic Investigation of Quaternary Ammonium Ions as Asymmetric Phase Transfer Catalysts. Synthesis of Catalyst Libraries and Evaluation of Catalyst Activity

PubMed Central

Denmark, Scott E.; Gould, Nathan D.; Wolf, Larry M.

2011-01-01

Despite over three decades of research into asymmetric phase transfer catalysis (APTC), a fundamental understanding of the factors that affect the rate and stereoselectivity of this important process are still obscure. This paper describes the initial stages of a long-term program aimed at elucidating the physical organic foundations of APTC employing a chemoinformatic analysis of the alkylation of a protected glycine imine with a libraries of enantiomerically enriched quaternary ammonium ions. The synthesis of the quaternary ammonium ions follows a diversity oriented approach wherein the tandem inter[4+2]/intra[3+2] cycloaddition of nitroalkenes serves as the key transformation. A two part synthetic strategy comprised of: (1) preparation of enantioenriched scaffolds and (2) development of parallel synthesis procedures is described. The strategy allows for the facile introduction of four variable groups in the vicinity of a stereogenic quaternary ammonium ion. The quaternary ammonium ions exhibited a wide range of activity and to a lesser degree enantioselectivity. Catalyst activity and selectivity are rationalized in a qualitative way based on the effective positive potential of the ammonium ion. PMID:21446721

The intestinal-renal axis for arginine synthesis is present and functional in the neonatal pig

USDA-ARS?s Scientific Manuscript database

The intestinal-renal axis for endogenous arginine synthesis is an interorgan process in which citrulline produced in the small intestine is utilized by the kidney for arginine synthesis. The function of this axis in neonates has been questioned because during this period the enzymes needed for argin...

Organization of chlorophyll biosynthesis and insertion of chlorophyll into the chlorophyll-binding proteins in chloroplasts.

PubMed

Wang, Peng; Grimm, Bernhard

2015-12-01

Oxygenic photosynthesis requires chlorophyll (Chl) for the absorption of light energy, and charge separation in the reaction center of photosystem I and II, to feed electrons into the photosynthetic electron transfer chain. Chl is bound to different Chl-binding proteins assembled in the core complexes of the two photosystems and their peripheral light-harvesting antenna complexes. The structure of the photosynthetic protein complexes has been elucidated, but mechanisms of their biogenesis are in most instances unknown. These processes involve not only the assembly of interacting proteins, but also the functional integration of pigments and other cofactors. As a precondition for the association of Chl with the Chl-binding proteins in both photosystems, the synthesis of the apoproteins is synchronized with Chl biosynthesis. This review aims to summarize the present knowledge on the posttranslational organization of Chl biosynthesis and current attempts to envision the proceedings of the successive synthesis and integration of Chl into Chl-binding proteins in the thylakoid membrane. Potential auxiliary factors, contributing to the control and organization of Chl biosynthesis and the association of Chl with the Chl-binding proteins during their integration into photosynthetic complexes, are discussed in this review.

Codon-usage-based inhibition of HIV protein synthesis by human schlafen 11

PubMed Central

Li, Manqing; Kao, Elaine; Gao, Xia; Sandig, Hilary; Limmer, Kirsten; Pavon-Eternod, Mariana; Jones, Thomas E.; Landry, Sebastien; Pan, Tao; Weitzman, Matthew D.; David, Michael

2013-01-01

In mammals, one of the most pronounced consequences of viral infection is the induction of type I interferons, cytokines with potent antiviral activity. Schlafen (Slfn) genes are a subset of interferon-stimulated early response genes (ISGs) that are also induced directly by pathogens via the interferon regulatory factor 3 (IRF3) pathway1. However, many ISGs are of unknown or incompletely understood function. Here we show that human SLFN11 potently and specifically abrogates the production of retroviruses such as human immunodeficiency virus 1 (HIV-1). Our study revealed that SLFN11 has no effect on the early steps of the retroviral infection cycle, including reverse transcription, integration and transcription. Rather, SLFN11 acts at the late stage of virus production by selectively inhibiting the expression of viral proteins in a codon-usage-dependent manner. We further find that SLFN11 binds transfer RNA, and counteracts changes in the tRNA pool elicited by the presence of HIV. Our studies identified a novel antiviral mechanism within the innate immune response, in which SLFN11 selectively inhibits viral protein synthesis in HIV-infected cells by means of codon-bias discrimination. PMID:23000900

Codon-usage-based inhibition of HIV protein synthesis by human schlafen 11.

PubMed

Li, Manqing; Kao, Elaine; Gao, Xia; Sandig, Hilary; Limmer, Kirsten; Pavon-Eternod, Mariana; Jones, Thomas E; Landry, Sebastien; Pan, Tao; Weitzman, Matthew D; David, Michael

2012-11-01

In mammals, one of the most pronounced consequences of viral infection is the induction of type I interferons, cytokines with potent antiviral activity. Schlafen (Slfn) genes are a subset of interferon-stimulated early response genes (ISGs) that are also induced directly by pathogens via the interferon regulatory factor 3 (IRF3) pathway. However, many ISGs are of unknown or incompletely understood function. Here we show that human SLFN11 potently and specifically abrogates the production of retroviruses such as human immunodeficiency virus 1 (HIV-1). Our study revealed that SLFN11 has no effect on the early steps of the retroviral infection cycle, including reverse transcription, integration and transcription. Rather, SLFN11 acts at the late stage of virus production by selectively inhibiting the expression of viral proteins in a codon-usage-dependent manner. We further find that SLFN11 binds transfer RNA, and counteracts changes in the tRNA pool elicited by the presence of HIV. Our studies identified a novel antiviral mechanism within the innate immune response, in which SLFN11 selectively inhibits viral protein synthesis in HIV-infected cells by means of codon-bias discrimination.

Substrate-Induced Formation of Ribosomal Decoding Center for Accurate and Rapid Genetic Code Translation.

PubMed

Pavlov, Michael Y; Ehrenberg, Måns

2018-05-20

Accurate translation of genetic information is crucial for synthesis of functional proteins in all organisms. We use recent experimental data to discuss how induced fit affects accuracy of initial codon selection on the ribosome by aminoacyl transfer RNA in ternary complex ( T 3 ) with elongation factor Tu (EF-Tu) and guanosine-5'-triphosphate (GTP). We define actual accuracy ([Formula: see text]) of a particular protein synthesis system as its current accuracy and the effective selectivity ([Formula: see text]) as [Formula: see text] in the limit of zero ribosomal binding affinity for T 3 . Intrinsic selectivity ([Formula: see text]), defined as the upper thermodynamic limit of [Formula: see text], is determined by the free energy difference between near-cognate and cognate T 3 in the pre-GTP hydrolysis state on the ribosome. [Formula: see text] is much larger than [Formula: see text], suggesting the possibility of a considerable increase in [Formula: see text] and [Formula: see text] at negligible kinetic cost. Induced fit increases [Formula: see text] and [Formula: see text] without affecting [Formula: see text], and aminoglycoside antibiotics reduce [Formula: see text] and [Formula: see text] at unaltered [Formula: see text].

A Polymerase With Potential: The Fe-S Cluster in Human DNA Primase.

PubMed

Holt, Marilyn E; Salay, Lauren E; Chazin, Walter J

2017-01-01

Replication of DNA in eukaryotes is primarily executed by the combined action of processive DNA polymerases δ and ɛ. These enzymes cannot initiate synthesis of new DNA without the presence of a primer on the template ssDNA. The primers on both the leading and lagging strands are generated by DNA polymerase α-primase (pol-prim). DNA primase is a DNA-dependent RNA polymerase that synthesizes the first ~10 nucleotides and then transfers the substrate to polymerase α to complete primer synthesis. The mechanisms governing the coordination and handoff between primase and polymerase α are largely unknown. Isolated DNA primase contains a [4Fe-4S] 2+ cluster that has been shown to serve as a redox switch modulating DNA binding affinity. This discovery suggests a mechanism for modulating the priming activity of primase and handoff to polymerase α. In this chapter, we briefly discuss the current state of knowledge of primase structure and function, including the role of its iron-sulfur cluster. This is followed by providing the methods for expressing, purifying, and biophysically/structurally characterizing primase and its iron-sulfur cluster-containing domain, p58C. © 2017 Elsevier Inc. All rights reserved.

Design, synthesis and biological evaluations of N-Hydroxy thienopyrimidine-2,4-diones as inhibitors of HIV reverse transcriptase-associated RNase H.

PubMed

Kankanala, Jayakanth; Kirby, Karen A; Huber, Andrew D; Casey, Mary C; Wilson, Daniel J; Sarafianos, Stefan G; Wang, Zhengqiang

2017-12-01

Human immunodeficiency virus (HIV) reverse transcriptase (RT) associated ribonuclease H (RNase H) is the only HIV enzymatic function not targeted by current antiviral drugs. Although various chemotypes have been reported to inhibit HIV RNase H, few have shown significant antiviral activities. We report herein the design, synthesis and biological evaluation of a novel N-hydroxy thienopyrimidine-2,3-dione chemotype (11) which potently and selectively inhibited RNase H with considerable potency against HIV-1 in cell culture. Current structure-activity-relationship (SAR) identified analogue 11d as a nanomolar inhibitor of RNase H (IC 50  = 0.04 μM) with decent antiviral potency (EC 50  = 7.4 μM) and no cytotoxicity (CC 50  > 100 μM). In extended biochemical assays compound 11d did not inhibit RT polymerase (pol) while inhibiting integrase strand transfer (INST) with 53 fold lower potency (IC 50  = 2.1 μM) than RNase H inhibition. Crystallographic and molecular modeling studies confirmed the RNase H active site binding mode. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Mechanistic study of methanol synthesis from CO₂ and H₂ on a modified model Mo₆S₈ cluster

DOE PAGES

Liu, Cheng; Liu, Ping

2015-01-12

We report the methanol synthesis from CO₂ and H₂ on metal (M = K, Ti, Co, Rh, Ni, and Cu)-modified model Mo₆S₈ catalyst using density functional theory (DFT). The results show that the catalytic behavior of a Mo₆S₈ cluster is changed significantly due to the modifiers, via the electron transfer from M to Mo₆S₈ and therefore the reduction of the Mo cation (ligand effect) and the direct participation of M in the reaction (ensemble effect) to promote some elementary steps. With the most positively charged modifier, the ligand effect in the case of K-Mo₆S₈ is the most obvious among themore » systems studied; however it cannot compete with the ensemble effect, which plays a dominate role in determining activity via the electrostatic attraction in particular to stabilize the CH xO y species adsorbed at the Mo sites of Mo₆S₈. In comparison, the ligand effect is weaker and the ensemble effect is more important when the other modifiers are used. In addition, the modifiers also vary the optimal reaction pathway for methanol synthesis on Mo₆S₈, ranging from the reverse water-gas shift (RWGS) + CO hydrogenation as that of Mo₆S₈ to the formate pathway. Finally, K is able to accelerate the methanol synthesis on Mo₆S₈ the most; while the promotion by Rh is relatively small. Using the modifiers like Ti, Co, Ni, and Cu, the activity of Mo₆S₈ is decreased instead. The relative stability between *HCOO and *HOCO is identified as a descriptor to capture the variation in mechanism and scales well with the estimated activity. Our study not only provides better understanding of the reaction mechanism and actives on the modified Mo₆S₈, but also predicts some possible candidates, which can be used a promoter to facilitate the CH₃OH synthesis on Mo sulfides.« less

Protein synthesis and its regulation: a background study related to the biological effects of radiation. Progress report, July 1, 1976--August 31, 1977

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zamecnik, P.C.

Results of studies are reported on delineation of the steps involved in protein synthesis and the role of transfer and messenger RNAs in the translation process. During the past year we have studied the mechanisms by which an oncogenic RNA virus modifies the growth process, and have begun to elucidate the role a novel dinucleotide, discovered in these laboratories, plays in rapidly growing cells in tissue culture.

Synthesis and characterization of nickel oxide/graphene sheet/graphene ribbon composite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lavanya, J.; Gomathi, N., E-mail: sivakumar.gomathi@gmail.com

2016-04-13

A novel and simple hydrothermal synthesis of nickel oxide (NiO)/graphene sheets (GNS)/graphene ribbon (GR) hybrid material is reported for the first time. The crystalline property and surface morphology of NiO/GNS/GR (NiO/HG) hybrid material is characterized by X-ray diffraction, Raman spectroscopy and Transmission electron spectroscopy. The fast electron transfer of GNS/GR along with NiO contributes an excellent electrochemical performance in the field of non-enzymatic glucose sensor.

Visible-Light-Mediated Nickel(II)-Catalyzed C-N Cross-Coupling in Water: Green and Regioselective Access for the Synthesis of Pyrazole-Containing Compounds.

PubMed

You, Guirong; Wang, Kai; Wang, Xiaodan; Wang, Guodong; Sun, Jian; Duan, Guiyun; Xia, Chengcai

2018-06-26

A regioselective green approach for the nickel(II)-catalyzed C-N cross-coupling between arylamines and pyrazoles through a photoredox process is reported. Moderate to good yield was observed for this reaction, performed in water under air at room temperature. This strategy provides a powerful tool for the green synthesis of pyrazole-containing bioactive molecules. In addition, a single-electron-transfer mechanism is proposed in this report.

Graphene-based organic-inorganic hybrids with optoelectronic and magneto-optic functions (Conference Presentation)

NASA Astrophysics Data System (ADS)

Lee, Kwang-Sup; Kim, Sung-Hyun; Jung, Juhyoung; Teng, Xue-Cheng; Prabhakaran, Prem

2017-02-01

Groups around the world are pursuing optoelctronic and magneto-optic properties of graphene-based materials since they hold a lot of promise for future technologies. Quantum dot (QD) decorated graphenic nanohybrids can be candidates for demonstrating energy transfer, while magnetic nanoparticles (MNPs) on graphene give rise to interesting electronic phenomena like magneto-optical effects. Graphene containing MNPs are also good candidates for exploring quantum-hall effect. In medicine these materials have demonstrated applications in bioimaging, drug delivery, photothermal treatment and magnetic resonance imaging. A majority of groups working on QD or MNPs have focused on chemical functionalization methods for making graphene-MNP nanohybrids. We have developed a set of small molecule as well as polymeric ligands for noncovalent self-assembly of nanoparticles on graphene. The ligands contain pyrene as an anchor group for graphene and also thiol or dipamine as anchor groups for QD or MNPs. In this presentation we discuss the synthesis and characterization of these materials and outline some early results regarding exploratory device fabrication involving these materials.

Writing and compiling code into biochemistry.

PubMed

Shea, Adam; Fett, Brian; Riedel, Marc D; Parhi, Keshab

2010-01-01

This paper presents a methodology for translating iterative arithmetic computation, specified as high-level programming constructs, into biochemical reactions. From an input/output specification, we generate biochemical reactions that produce output quantities of proteins as a function of input quantities performing operations such as addition, subtraction, and scalar multiplication. Iterative constructs such as "while" loops and "for" loops are implemented by transferring quantities between protein types, based on a clocking mechanism. Synthesis first is performed at a conceptual level, in terms of abstract biochemical reactions - a task analogous to high-level program compilation. Then the results are mapped onto specific biochemical reactions selected from libraries - a task analogous to machine language compilation. We demonstrate our approach through the compilation of a variety of standard iterative functions: multiplication, exponentiation, discrete logarithms, raising to a power, and linear transforms on time series. The designs are validated through transient stochastic simulation of the chemical kinetics. We are exploring DNA-based computation via strand displacement as a possible experimental chassis.

Chemoselective synthesis and analysis of naturally occurring phosphorylated cysteine peptides

PubMed Central

Bertran-Vicente, Jordi; Penkert, Martin; Nieto-Garcia, Olaia; Jeckelmann, Jean-Marc; Schmieder, Peter; Krause, Eberhard; Hackenberger, Christian P. R.

2016-01-01

In contrast to protein O-phosphorylation, studying the function of the less frequent N- and S-phosphorylation events have lagged behind because they have chemical features that prevent their manipulation through standard synthetic and analytical methods. Here we report on the development of a chemoselective synthetic method to phosphorylate Cys side-chains in unprotected peptides. This approach makes use of a reaction between nucleophilic phosphites and electrophilic disulfides accessible by standard methods. We achieve the stereochemically defined phosphorylation of a Cys residue and verify the modification using electron-transfer higher-energy dissociation (EThcD) mass spectrometry. To demonstrate the use of the approach in resolving biological questions, we identify an endogenous Cys phosphorylation site in IICBGlc, which is known to be involved in the carbohydrate uptake from the bacterial phosphotransferase system (PTS). This new chemical and analytical approach finally allows further investigating the functions and significance of Cys phosphorylation in a wide range of crucial cellular processes. PMID:27586301

Research on accuracy analysis of laser transmission system based on Zemax and Matlab

NASA Astrophysics Data System (ADS)

Chen, Haiping; Liu, Changchun; Ye, Haixian; Xiong, Zhao; Cao, Tingfen

2017-05-01

Laser transmission system is important in high power solid-state laser facilities and its function is to transfer and focus the light beam in accordance with the physical function of the facility. This system is mainly composed of transmission mirror modules and wedge lens module. In order to realize the precision alignment of the system, the precision alignment of the system is required to be decomposed into the allowable range of the calibration error of each module. The traditional method is to analyze the error factors of the modules separately, and then the linear synthesis is carried out, and the influence of the multi-module and multi-factor is obtained. In order to analyze the effect of the alignment error of each module on the beam center and focus more accurately, this paper aims to combine with the Monte Carlo random test and ray tracing, analyze influence of multi-module and multi-factor on the center of the beam, and evaluate and optimize the results of accuracy decomposition.

Does menaquinone participate in brain astrocyte electron transport?

PubMed

Lovern, Douglas; Marbois, Beth

2013-10-01

Quinone compounds act as membrane resident carriers of electrons between components of the electron transport chain in the periplasmic space of prokaryotes and in the mitochondria of eukaryotes. Vitamin K is a quinone compound in the human body in a storage form as menaquinone (MK); distribution includes regulated amounts in mitochondrial membranes. The human brain, which has low amounts of typical vitamin K dependent function (e.g., gamma carboxylase) has relatively high levels of MK, and different regions of brain have different amounts. Coenzyme Q (Q), is a quinone synthesized de novo, and the levels of synthesis decline with age. The levels of MK are dependent on dietary intake and generally increase with age. MK has a characterized role in the transfer of electrons to fumarate in prokaryotes. A newly recognized fumarate cycle has been identified in brain astrocytes. The MK precursor menadione has been shown to donate electrons directly to mitochondrial complex III. Vitamin K compounds function in the electron transport chain of human brain astrocytes. Copyright © 2013 Elsevier Ltd. All rights reserved.

Function Transfer in Human Operant Experiments: The Role of Stimulus Pairings

ERIC Educational Resources Information Center

Tonneau, Francois; Gonzalez, Carmen

2004-01-01

Although function transfer often has been studied in complex operant procedures (such as matching to sample), whether operant reinforcement actually produces function transfer in such settings has not been established. The present experiments, with high school students as subjects, suggest that stimulus pairings can promote function transfer in…

Linear summation of outputs in a balanced network model of motor cortex

PubMed Central

Capaday, Charles; van Vreeswijk, Carl

2015-01-01

Given the non-linearities of the neural circuitry's elements, we would expect cortical circuits to respond non-linearly when activated. Surprisingly, when two points in the motor cortex are activated simultaneously, the EMG responses are the linear sum of the responses evoked by each of the points activated separately. Additionally, the corticospinal transfer function is close to linear, implying that the synaptic interactions in motor cortex must be effectively linear. To account for this, here we develop a model of motor cortex composed of multiple interconnected points, each comprised of reciprocally connected excitatory and inhibitory neurons. We show how non-linearities in neuronal transfer functions are eschewed by strong synaptic interactions within each point. Consequently, the simultaneous activation of multiple points results in a linear summation of their respective outputs. We also consider the effects of reduction of inhibition at a cortical point when one or more surrounding points are active. The network response in this condition is linear over an approximately two- to three-fold decrease of inhibitory feedback strength. This result supports the idea that focal disinhibition allows linear coupling of motor cortical points to generate movement related muscle activation patterns; albeit with a limitation on gain control. The model also explains why neural activity does not spread as far out as the axonal connectivity allows, whilst also explaining why distant cortical points can be, nonetheless, functionally coupled by focal disinhibition. Finally, we discuss the advantages that linear interactions at the cortical level afford to motor command synthesis. PMID:26097452

Cardiac Expression of Microsomal Triglyceride Transfer Protein Is Increased in Obesity and Serves to Attenuate Cardiac Triglyceride Accumulation

PubMed Central

Bartels, Emil D.; Nielsen, Jan M.; Hellgren, Lars I.; Ploug, Thorkil; Nielsen, Lars B.

2009-01-01

Obesity causes lipid accumulation in the heart and may lead to lipotoxic heart disease. Traditionally, the size of the cardiac triglyceride pool is thought to reflect the balance between uptake and β-oxidation of fatty acids. However, triglycerides can also be exported from cardiomyocytes via secretion of apolipoproteinB-containing (apoB) lipoproteins. Lipoprotein formation depends on expression of microsomal triglyceride transfer protein (MTP); the mouse expresses two isoforms of MTP, A and B. Since many aspects of the link between obesity-induced cardiac disease and cardiac lipid metabolism remain unknown, we investigated how cardiac lipoprotein synthesis affects cardiac expression of triglyceride metabolism-controlling genes, insulin sensitivity, and function in obese mice. Heart-specific ablation of MTP-A in mice using Cre-loxP technology impaired upregulation of MTP expression in response to increased fatty acid availability during fasting and fat feeding. This resulted in cardiac triglyceride accumulation but unaffected cardiac insulin-stimulated glucose uptake. Long-term fat-feeding of male C57Bl/6 mice increased cardiac triglycerides, induced cardiac expression of triglyceride metabolism-controlling genes and attenuated heart function. Abolishing cardiac triglyceride accumulation in fat-fed mice by overexpression of an apoB transgene in the heart prevented the induction of triglyceride metabolism-controlling genes and improved heart function. The results suggest that in obesity, the physiological increase of cardiac MTP expression serves to attenuate cardiac triglyceride accumulation albeit without major effects on cardiac insulin sensitivity. Nevertheless, the data suggest that genetically increased lipoprotein secretion prevents development of obesity-induced lipotoxic heart disease. PMID:19390571

Human frataxin activates Fe-S cluster biosynthesis by facilitating sulfur transfer chemistry.

PubMed

Bridwell-Rabb, Jennifer; Fox, Nicholas G; Tsai, Chi-Lin; Winn, Andrew M; Barondeau, David P

2014-08-05

Iron-sulfur clusters are ubiquitous protein cofactors with critical cellular functions. The mitochondrial Fe-S assembly complex, which consists of the cysteine desulfurase NFS1 and its accessory protein (ISD11), the Fe-S assembly protein (ISCU2), and frataxin (FXN), converts substrates l-cysteine, ferrous iron, and electrons into Fe-S clusters. The physiological function of FXN has received a tremendous amount of attention since the discovery that its loss is directly linked to the neurodegenerative disease Friedreich's ataxia. Previous in vitro results revealed a role for human FXN in activating the cysteine desulfurase and Fe-S cluster biosynthesis activities of the Fe-S assembly complex. Here we present radiolabeling experiments that indicate FXN accelerates the accumulation of sulfur on ISCU2 and that the resulting persulfide species is viable in the subsequent synthesis of Fe-S clusters. Additional mutagenesis, enzyme kinetic, UV-visible, and circular dichroism spectroscopic studies suggest conserved ISCU2 residue C104 is critical for FXN activation, whereas C35, C61, and C104 are all essential for Fe-S cluster formation on the assembly complex. These results cannot be fully explained by the hypothesis that FXN functions as an iron donor for Fe-S cluster biosynthesis, and further support an allosteric regulator role for FXN. Together, these results lead to an activation model in which FXN accelerates persulfide formation on NFS1 and favors a helix-to-coil interconversion on ISCU2 that facilitates the transfer of sulfur from NFS1 to ISCU2 as an initial step in Fe-S cluster biosynthesis.

Human Frataxin Activates Fe–S Cluster Biosynthesis by Facilitating Sulfur Transfer Chemistry

PubMed Central

2015-01-01

Iron–sulfur clusters are ubiquitous protein cofactors with critical cellular functions. The mitochondrial Fe–S assembly complex, which consists of the cysteine desulfurase NFS1 and its accessory protein (ISD11), the Fe–S assembly protein (ISCU2), and frataxin (FXN), converts substrates l-cysteine, ferrous iron, and electrons into Fe–S clusters. The physiological function of FXN has received a tremendous amount of attention since the discovery that its loss is directly linked to the neurodegenerative disease Friedreich’s ataxia. Previous in vitro results revealed a role for human FXN in activating the cysteine desulfurase and Fe–S cluster biosynthesis activities of the Fe–S assembly complex. Here we present radiolabeling experiments that indicate FXN accelerates the accumulation of sulfur on ISCU2 and that the resulting persulfide species is viable in the subsequent synthesis of Fe–S clusters. Additional mutagenesis, enzyme kinetic, UV–visible, and circular dichroism spectroscopic studies suggest conserved ISCU2 residue C104 is critical for FXN activation, whereas C35, C61, and C104 are all essential for Fe–S cluster formation on the assembly complex. These results cannot be fully explained by the hypothesis that FXN functions as an iron donor for Fe–S cluster biosynthesis, and further support an allosteric regulator role for FXN. Together, these results lead to an activation model in which FXN accelerates persulfide formation on NFS1 and favors a helix-to-coil interconversion on ISCU2 that facilitates the transfer of sulfur from NFS1 to ISCU2 as an initial step in Fe–S cluster biosynthesis. PMID:24971490

Experiences and Outcomes of Transition from Pediatric to Adult Health Care Services for Young People with Congenital Heart Disease: A Systematic Review.

PubMed

Heery, Emily; Sheehan, Aisling M; While, Alison E; Coyne, Imelda

2015-01-01

This review synthesizes the empirical literature on outcomes and experiences of transfer and transition from pediatric to adult care for young people with congenital heart disease. A systematic review of papers published between January 2001 and May 2013 that examined outcomes or experiences of transfer and transition among young people with congenital heart disease was conducted. Data were extracted by two independent reviewers with the outcomes data combined using narrative synthesis and the experiences data integrated using thematic synthesis. Thirteen papers were included in the review: six reported outcomes following transfer, six reported experiences of transfer and transition, and one reported both outcomes and experiences. The review data indicate that high proportions of young people were lost to follow-up or experienced long gaps in care after leaving pediatric cardiology. Factors that protected against loss to follow-up or lapse in care included: beliefs that specialized adult care was necessary; poorer health status; attendance at pediatric appointments without parents; and pediatric referral to an adult congenital heart disease center. Data on experiences highlighted that many young people were unconcerned about transition, but lacked knowledge about their condition and were insufficiently prepared for transfer. In terms of adult services, many young people desired continuity in the quality of care, youth-oriented facilities, a personalized approach, and for their parents to remain involved in their care, but in a secondary, supportive capacity. In conclusion, the high proportions of young people lost to follow-up highlight the need for formal transition programs, which ensure a planned and coordinated transfer. Patients with congenital heart disease need education throughout adolescence about the implications of their condition, the differences between pediatric and adult services, and self-care management. © 2015 Wiley Periodicals, Inc.

THE PENETRATION OF REOVIRUS RNA AND INITIATION OF ITS GENETIC FUNCTION IN L-STRAIN FIBROBLASTS

PubMed Central

Silverstein, Samuel C.; Dales, Samuel

1968-01-01

Reovirus type 3 is phagocytized by L cells and rapidly sequestered inside lysosomes. Hydrolases within these organelles are capable of stripping the viral coat proteins, but they fail to degrade the double-stranded RNA genome. These observations support the view that sojourn of reovirus in lysosomes, when the lytic enzymes uncoat its genome, is an obligatory step in the sequence of infection. Although the mechanism for transferring the uncoated RNA out of lysosomes remains to be elucidated, evidence is presented suggesting that progeny genomes are bound to site(s) possessing the fine structure of viral inclusions or factories. It appears that both the synthesis of single- and double-stranded viral RNA and the morphogenesis of progeny virus particles occur in such factories. PMID:19806702

Design of a mesoscale continuous flow route towards lithiated methoxyallene.

PubMed

Seghers, Sofie; Heugebaert, Thomas S A; Moens, Matthias; Sonck, Jolien; Thybaut, Joris; Stevens, Chris Victor

2018-05-11

The unique nucleophilic properties of lithiated methoxyallene allow for C-C bond formation with a wide variety of electrophiles, thus introducing an allenic group for further functionalization. This approach has yielded a tremendously broad range of (hetero)cyclic scaffolds, including API precursors. To date, however, its valorization at scale is hampered by the batch synthesis protocol which suffers from serious safety issues. Hence, the attractive heat and mass transfer properties of flow technology were exploited to establish a mesoscale continuous flow route towards lithiated methoxyallene. An excellent conversion of 94% was obtained, corresponding to a methoxyallene throughput of 8.2 g/h. The process is characterized by short reaction times, mild reaction conditions and a stoichiometric use of reagents. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation, Single-Molecule Manipulation, and Energy Transfer Investigation of a Polyfluorene-graft-DNA polymer.

PubMed

Madsen, Mikael; Christensen, Rasmus S; Krissanaprasit, Abhichart; Bakke, Mette R; Riber, Camilla F; Nielsen, Karina S; Zelikin, Alexander N; Gothelf, Kurt V

2017-08-04

Conjugated polymers have been intensively studied due to their unique optical and electronic properties combined with their physical flexibility and scalable bottom up synthesis. Although the bulk qualities of conjugated polymers have been extensively utilized in research and industry, the ability to handle and manipulate conjugated polymers at the nanoscale lacks significantly behind. Here, the toolbox for controlled manipulation of conjugated polymers was expanded through the synthesis of a polyfluorene-DNA graft-type polymer (poly(F-DNA)). The polymer possesses the characteristics associated with the conjugated polyfluorene backbone, but the protruding single-stranded DNA provides the material with an exceptional addressability. This study demonstrates controlled single-molecule patterning of poly(F-DNA), as well as energy transfer between two different polymer-DNA conjugates. Finally, highly efficient DNA-directed quenching of polyfluorene fluorescence was shown. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and characterization of an anomeric sulfur analogue of CMP-sialic acid.

PubMed

Cohen, S B; Halcomb, R L

2000-09-22

alpha-2,3-Sialyltransferase catalyzes the transfer of sialic acid from CMP-sialic acid (1) to a lactose acceptor. An analogue of 1 was synthesized in which the anomeric oxygen atom was replaced with a sulfur atom (1S). The key step in the synthesis of 1S was a tetrazole-promoted coupling of a cytidine-5'-phosphoramidite with a glycosyl thiol of a protected sialic acid. Compounds 1 and 1S were characterized for their activity in a sialyl transfer assay. The rate of solvolysis in aqueous buffer of analogue 1S was 50-fold slower than that of 1. Analogue 1S was found to be substrate for alpha-2,3-sialyltransferase. The K(m) of 1S was just 3-fold higher than that of 1, while the k(cat) of 1S was 2 orders of magnitude lower compared to 1.

Cooperative upconversion luminescence in Tb{sup 3+}:Yb{sup 3+} co-doped Y{sub 2}SiO{sub 5} powders prepared by combustion synthesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rakov, Nikifor, E-mail: nikifor.gomez@univasf.edu.br; Vieira, Simone A.; Guimarães, Renato B.

2014-03-15

Frequency upconversion (UC) luminescence via cooperative energy transfer (CET) process between pairs of Yb{sup 3+} and Tb{sup 3+} ions was investigated in Tb{sup 3+}:Yb{sup 3+}:Y{sub 2}SiO{sub 5} crystalline ceramic powders prepared by combustion synthesis. Surface morphology and structure of the powders were investigated by scanning electronic microscopy and X-ray powder diffraction. Photoluminescence experiments were performed in Tb{sup 3+}-singly doped samples using ultraviolet light (λ=255 nm) and in Tb{sup 3+}:Yb{sup 3+} co-doped samples using a near-infrared (NIR) diode laser (λ=975 nm). Upon excitation with the NIR diode laser, UC luminescence with an intense emission band centered at ∼549 nm, corresponding tomore » the 4f intraband {sup 5}D{sub 4}→{sup 7}F{sub 5} transition of Tb{sup 3+}, along with less intense emission bands at ∼490, ∼590 and ∼620 nm, corresponding to other {sup 5}D{sub 4}→{sup 7}F{sub J} transitions, was detected. The CET rate was estimated by analyzing the dynamics of UC luminescence with rate equations model of the electronic populations. -- Graphical Abstract: Left: Cooperative upconversion luminescence spectra of three powder samples prepared by combustion synthesis. Right: The SEM image of the powder showing that it consists of agglomerated flake-like shaped particles of various sizes. Full scale bar is 20 μm. Highlights: • Yttrium orthosilicate (Y{sub 2}SiO{sub 5}) powders were prepared by combustion synthesis. • Cooperative upconversion is observed for the first time in Tb{sup 3+}–Yb{sup 3+} doped Y{sub 2}SiO{sub 5}. • Energy transfer and back-transfer rates between Tb{sup 3+} and Yb{sup 3+} pairs were estimated.« less

Designing a multiroute synthesis scheme in combinatorial chemistry.

PubMed

Akavia, Adi; Senderowitz, Hanoch; Lerner, Alon; Shamir, Ron

2004-01-01

Solid-phase mix-and-split combinatorial synthesis is often used to produce large arrays of compounds to be tested during the various stages of the drug development process. This method can be represented by a synthesis graph in which nodes correspond to grow operations and arcs to beads transferred among the different reaction vessels. In this work, we address the problem of designing such a graph which maximizes the number of produced target compounds (namely, compounds out of an input library of desired molecules), given constraints on the number of beads used for library synthesis and on the number of reaction vessels available for concurrent grow steps. We present a heuristic based on a discrete search for solving this problem, test our solution on several data sets, explore its behavior, and show that it achieves good performance.

Synthesis of Hadamard transformers by use of multimode interference optical waveguides.

PubMed

Gupta, Atma Ram; Tsutsumi, Kiyoshi; Nakayama, Junichi

2003-05-20

We propose a synthesis method of optical Hadamard transformer using multimode interference (MMI) couplers. By using the signal transfer matrix of 2 x 2, 4 x 4, and 8 x 8 MMI couplers, we show that sum and difference units of input signals can be synthesized. An interchange unit of two signals can also be synthesized. One synthesis method of Hadamard transformers is a combination of only 2 x 2 units, and the other is a combination of N x N(N > or = 4) units as well as 2 x 2 units. The design examples of operation units are shown, and the size and the output power of Hadamard transformers are estimated.

Comparison of (31)P saturation and inversion magnetization transfer in human liver and skeletal muscle using a clinical MR system and surface coils.

PubMed

Buehler, Tania; Kreis, Roland; Boesch, Chris

2015-02-01

(31)P MRS magnetization transfer ((31)P-MT) experiments allow the estimation of exchange rates of biochemical reactions, such as the creatine kinase equilibrium and adenosine triphosphate (ATP) synthesis. Although various (31)P-MT methods have been successfully used on isolated organs or animals, their application on humans in clinical scanners poses specific challenges. This study compared two major (31)P-MT methods on a clinical MR system using heteronuclear surface coils. Although saturation transfer (ST) is the most commonly used (31)P-MT method, sequences such as inversion transfer (IT) with short pulses might be better suited for the specific hardware and software limitations of a clinical scanner. In addition, small NMR-undetectable metabolite pools can transfer MT to NMR-visible pools during long saturation pulses, which is prevented with short pulses. (31)P-MT sequences were adapted for limited pulse length, for heteronuclear transmit-receive surface coils with inhomogeneous B1 , for the need for volume selection and for the inherently low signal-to-noise ratio (SNR) on a clinical 3-T MR system. The ST and IT sequences were applied to skeletal muscle and liver in 10 healthy volunteers. Monte-Carlo simulations were used to evaluate the behavior of the IT measurements with increasing imperfections. In skeletal muscle of the thigh, ATP synthesis resulted in forward reaction constants (k) of 0.074 ± 0.022 s(-1) (ST) and 0.137 ± 0.042 s(-1) (IT), whereas the creatine kinase reaction yielded 0.459 ± 0.089 s(-1) (IT). In the liver, ATP synthesis resulted in k = 0.267 ± 0.106 s(-1) (ST), whereas the IT experiment yielded no consistent results. ST results were close to literature values; however, the IT results were either much larger than the corresponding ST values and/or were widely scattered. To summarize, ST and IT experiments can both be implemented on a clinical body scanner with heteronuclear transmit-receive surface coils; however, ST results are much more robust against experimental imperfections than the current implementation of IT. Copyright © 2014 John Wiley & Sons, Ltd.

The mitochondrial Hsp70 chaperone Ssq1 facilitates Fe/S cluster transfer from Isu1 to Grx5 by complex formation.

PubMed

Uzarska, Marta A; Dutkiewicz, Rafal; Freibert, Sven-Andreas; Lill, Roland; Mühlenhoff, Ulrich

2013-06-01

The mitochondrial Hsp70 chaperone Ssq1 plays a dedicated role in the maturation of iron-sulfur (Fe/S) proteins, an essential process of mitochondria. Similar to its bacterial orthologue HscA, Ssq1 binds to the scaffold protein Isu1, thereby facilitating dissociation of the newly synthesized Fe/S cluster on Isu1 and its transfer to target apoproteins. Here we use in vivo and in vitro approaches to show that Ssq1 also interacts with the monothiol glutaredoxin 5 (Grx5) at a binding site different from that of Isu1. Grx5 binding does not stimulate the ATPase activity of Ssq1 and is most pronounced for the ADP-bound form of Ssq1, which interacts with Isu1 most tightly. The vicinity of Isu1 and Grx5 on the Hsp70 chaperone facilitates rapid Fe/S cluster transfer from Isu1 to Grx5. Grx5 and its bound Fe/S cluster are required for maturation of all cellular Fe/S proteins, regardless of the type of bound Fe/S cofactor and subcellular localization. Hence Grx5 functions as a late-acting component of the core Fe/S cluster (ISC) assembly machinery linking the Fe/S cluster synthesis reaction on Isu1 with late assembly steps involving Fe/S cluster targeting to dedicated apoproteins.

Large scale 2D/3D hybrids based on gallium nitride and transition metal dichalcogenides.

PubMed

Zhang, Kehao; Jariwala, Bhakti; Li, Jun; Briggs, Natalie C; Wang, Baoming; Ruzmetov, Dmitry; Burke, Robert A; Lerach, Jordan O; Ivanov, Tony G; Haque, Md; Feenstra, Randall M; Robinson, Joshua A

2017-12-21

Two and three-dimensional (2D/3D) hybrid materials have the potential to advance communication and sensing technologies by enabling new or improved device functionality. To date, most 2D/3D hybrid devices utilize mechanical exfoliation or post-synthesis transfer, which can be fundamentally different from directly synthesized layers that are compatible with large scale industrial needs. Therefore, understanding the process/property relationship of synthetic heterostructures is priority for industrially relevant material architectures. Here we demonstrate the scalable synthesis of molybdenum disulfide (MoS 2 ) and tungsten diselenide (WSe 2 ) via metal organic chemical vapor deposition (MOCVD) on gallium nitride (GaN), and elucidate the structure, chemistry, and vertical transport properties of the 2D/3D hybrid. We find that the 2D layer thickness and transition metal dichalcogenide (TMD) choice plays an important role in the transport properties of the hybrid structure, where monolayer TMDs exhibit direct tunneling through the layer, while transport in few layer TMDs on GaN is dominated by p-n diode behavior and varies with the 2D/3D hybrid structure. Kelvin probe force microscopy (KPFM), low energy electron microscopy (LEEM) and X-ray photoelectron spectroscopy (XPS) reveal a strong intrinsic dipole and charge transfer between n-MoS 2 and p-GaN, leading to a degraded interface and high p-type leakage current. Finally, we demonstrate integration of heterogeneous 2D layer stacks of MoS 2 /WSe 2 on GaN with atomically sharp interface. Monolayer MoS 2 /WSe 2 /n-GaN stacks lead to near Ohmic transport due to the tunneling and non-degenerated doping, while few layer stacking is Schottky barrier dominated.

Energetics and kinetics of the prebiotic synthesis of simple organic acids and amino acids with the FeS-H2S/FeS2 redox couple as reductant

NASA Technical Reports Server (NTRS)

Schoonen, M. A.; Xu, Y.; Bebie, J.

1999-01-01

The thermodynamics of the FeS-H2S/FeS2 redox couple and a select number of reactions critical to the synthesis of simple carboxylic acids and amino acids have been evaluated as a function of temperature. This thermodynamic evaluation shows that the reducing power of the FeS-H2S/FeS2 redox couple decreases drastically with temperature. By contrast the equilibria describing the reduction of CO2 and the formation of simple carboxylic acids and amino acids require an increasingly higher reducing power with temperature. Given these two opposite trends, the thermodynamic driving force for CO2 reduction and amino acid formation with the FeS-H2S/FeS2 redox couple as reductant diminishes with increasing temperature. An evaluation of the mechanism of CO2 reduction by the FeS-H2S/FeS2 couple suggests that the electron transfer from pyrrhotite to CO2 is hindered by a high activation energy, even though the overall reaction is thermodynamically favorable. By comparison the electron transfer from pyrrhotite to either CS2, CO, or HCOOH are far more facile. This theoretical analysis explains the results of experimental work by Keefe et al. (1995), Heinen and Lauwers (1996) and Huber and Wachtershauser (1997). The implication is that a reaction sequence involving the reduction of CO2 with the FeS-H2S/FeS2 couple as reductant is unlikely to initiate a proposed prebiotic carbon fixation cycle (Wachtershauser, 1988b; 1990b, 1990a, 1992, 1993).

RAFT Aqueous Dispersion Polymerization Yields Poly(ethylene glycol)-Based Diblock Copolymer Nano-Objects with Predictable Single Phase Morphologies

PubMed Central

2013-01-01

A poly(ethylene glycol) (PEG) macromolecular chain transfer agent (macro-CTA) is prepared in high yield (>95%) with 97% dithiobenzoate chain-end functionality in a three-step synthesis starting from a monohydroxy PEG113 precursor. This PEG113-dithiobenzoate is then used for the reversible addition–fragmentation chain transfer (RAFT) aqueous dispersion polymerization of 2-hydroxypropyl methacrylate (HPMA). Polymerizations conducted under optimized conditions at 50 °C led to high conversions as judged by 1H NMR spectroscopy and relatively low diblock copolymer polydispersities (Mw/Mn < 1.25) as judged by GPC. The latter technique also indicated good blocking efficiencies, since there was minimal PEG113 macro-CTA contamination. Systematic variation of the mean degree of polymerization of the core-forming PHPMA block allowed PEG113-PHPMAx diblock copolymer spheres, worms, or vesicles to be prepared at up to 17.5% w/w solids, as judged by dynamic light scattering and transmission electron microscopy studies. Small-angle X-ray scattering (SAXS) analysis revealed that more exotic oligolamellar vesicles were observed at 20% w/w solids when targeting highly asymmetric diblock compositions. Detailed analysis of SAXS curves indicated that the mean number of membranes per oligolamellar vesicle is approximately three. A PEG113-PHPMAx phase diagram was constructed to enable the reproducible targeting of pure phases, as opposed to mixed morphologies (e.g., spheres plus worms or worms plus vesicles). This new RAFT PISA formulation is expected to be important for the rational and efficient synthesis of a wide range of biocompatible, thermo-responsive PEGylated diblock copolymer nano-objects for various biomedical applications. PMID:24400622

De Novo Synthesis and Degradation of Lx and V Cycle Pigments during Shade and Sun Acclimation in Avocado Leaves1

PubMed Central

Förster, Britta; Osmond, C. Barry; Pogson, Barry J.

2009-01-01

The photoprotective role of the universal violaxanthin cycle that interconverts violaxanthin (V), antheraxanthin (A), and zeaxanthin (Z) is well established, but functions of the analogous conversions of lutein-5,6-epoxide (Lx) and lutein (L) in the selectively occurring Lx cycle are still unclear. We investigated carotenoid pools in Lx-rich leaves of avocado (Persea americana) during sun or shade acclimation at different developmental stages. During sun exposure of mature shade leaves, an unusual decrease in L preceded the deepoxidation of Lx to L and of V to A+Z. In addition to deepoxidation, de novo synthesis increased the L and A+Z pools. Epoxidation of L was exceptionally slow, requiring about 40 d in the shade to restore the Lx pool, and residual A+Z usually persisted overnight. In young shade leaves, the Lx cycle was reversed initially, with Lx accumulating in the sun and declining in the shade. De novo synthesis of xanthophylls did not affect α- and β-carotene pools on the first day, but during long-term acclimation α-carotene pools changed noticeably. Nonetheless, the total change in α- and β-branch carotenoid pools was equal. We discuss the implications for regulation of metabolic flux through the α- and β-branches of carotenoid biosynthesis and potential roles for L in photoprotection and Lx in energy transfer to photosystem II and explore physiological roles of both xanthophyll cycles as determinants of photosystem II efficiency. PMID:19060099

Proteomic analysis of Arabidopsis thaliana leaves in response to acute boron deficiency and toxicity reveals effects on photosynthesis, carbohydrate metabolism, and protein synthesis.

PubMed

Chen, Mei; Mishra, Sasmita; Heckathorn, Scott A; Frantz, Jonathan M; Krause, Charles

2014-02-15

Boron (B) stress (deficiency and toxicity) is common in plants, but as the functions of this essential micronutrient are incompletely understood, so too are the effects of B stress. To investigate mechanisms underlying B stress, we examined protein profiles in leaves of Arabidopsis thaliana plants grown under normal B (30 μM), compared to plants transferred for 60 and 84 h (i.e., before and after initial visible symptoms) in deficient (0 μM) or toxic (3 mM) levels of B. B-responsive polypeptides were sequenced by mass spectrometry, following 2D gel electrophoresis, and 1D gels and immunoblotting were used to confirm the B-responsiveness of some of these proteins. Fourteen B-responsive proteins were identified, including: 9 chloroplast proteins, 6 proteins of photosynthetic/carbohydrate metabolism (rubisco activase, OEC23, photosystem I reaction center subunit II-1, ATPase δ-subunit, glycolate oxidase, fructose bisphosphate aldolase), 6 stress proteins, and 3 proteins involved in protein synthesis (note that the 14 proteins may fall into multiple categories). Most (8) of the B-responsive proteins decreased under both B deficiency and toxicity; only 3 increased with B stress. Boron stress decreased, or had no effect on, 3 of 4 oxidative stress proteins examined, and did not affect total protein. Hence, our results indicate relatively early specific effects of B stress on chloroplasts and protein synthesis. Copyright © 2013 Elsevier GmbH. All rights reserved.

Polymer-Based Protein Engineering: Synthesis and Characterization of Armored, High Graft Density Polymer-Protein Conjugates.

PubMed

Carmali, Sheiliza; Murata, Hironobu; Cummings, Chad; Matyjaszewski, Krzysztof; Russell, Alan J

2017-01-01

Atom transfer radical polymerization (ATRP) from the surface of a protein can generate remarkably dense polymer shells that serve as armor and rationally tune protein function. Using straightforward chemistry, it is possible to covalently couple or display multiple small molecule initiators onto a protein surface. The chemistry is fine-tuned to be sequence specific (if one desires a single targeted site) at controlled density. Once the initiator is anchored on the protein surface, ATRP is used to grow polymers on protein surface, in situ. The technique is so powerful that a single-protein polymer conjugate molecule can contain more than 90% polymer coating by weight. If desired, stimuli-responsive polymers can be "grown" from the initiated sites to prepare enzyme conjugates that respond to external triggers such as temperature or pH, while still maintaining enzyme activity and stability. Herein, we focus mainly on the synthesis of chymotrypsin-polymer conjugates. Control of the number of covalently coupled initiator sites by changing the stoichiometric ratio between enzyme and the initiator during the synthesis of protein-initiator complexes allowed fine-tuning of the grafting density. For example, very high grafting density chymotrypsin conjugates were prepared from protein-initiator complexes to grow the temperature-responsive polymers, poly(N-isopropylacrylamide), and poly[N,N'-dimethyl(methacryloyloxyethyl) ammonium propane sulfonate]. Controlled growth of polymers from protein surfaces enables one to predictably manipulate enzyme kinetics and stability without the need for molecular biology-dependent mutagenesis. © 2017 Elsevier Inc. All rights reserved.

SIMULTANEOUS PRODUCTION OF TWO CAPSULAR POLYSACCHARIDES BY PNEUMOCOCCUS

PubMed Central

Austrian, Robert; Bernheimer, Harriet P.; Smith, Evelyn E. B.; Mills, George T.

1959-01-01

Study of the capsular genome of pneumococcus has shown that it controls a multiplicity of biochemical reactions essential to the synthesis of capsular polysaccharide. Mutation affecting any one of several biochemical reactions concerned with capsular synthesis may result in loss of capsulation without alteration of other biochemical functions similarly concerned. Mutations affecting the synthesis of uronic acids are an important cause of loss of capsulation and of virulence by strains of pneumococcus Type I and Type III. The capsular genome appears to have a specific location in the total genome of the cell, this locus being occupied by the capsular genome of whatever capsular type is expressed by the cell. Transformation of capsulated or of non-capsulated pneumococci to heterologous capsular type results probably from a genetic exchange followed by the development of a new biosynthetic pathway in the transformed cell. The new capsular genome is transferred to the transformed cell as a single particle of DNA. Binary capsulation results from the simultaneous presence within the pneumococcal cell of two capsular genomes, one mutated, the other normal. Interaction between the biochemical pathways controlled by the two capsular genomes leads to augmentation of the phenotypic expression of the product controlled by one and to partial suppression of the product determined by the other. Knowledge of the biochemical basis of binary capsulation can be used to indicate the presence of uronic acid in the capsular polysaccharide of a pneurnococcal type the composition of the capsule of which is unknown. PMID:13795197

Synthesis and functionalization of monodisperse near-ultraviolet and visible excitable multifunctional Eu(3+), Bi(3+):REVO4 nanophosphors for bioimaging and biosensing applications.

PubMed

Escudero, Alberto; Carrillo-Carrión, Carolina; Zyuzin, Mikhail V; Ashraf, Sumaira; Hartmann, Raimo; Núñez, Nuria O; Ocaña, Manuel; Parak, Wolfgang J

2016-06-16

Near-ultraviolet and visible excitable Eu- and Bi-doped NPs based on rare earth vanadates (REVO4, RE = Y, Gd) have been synthesized by a facile route from appropriate RE precursors, europium and bismuth nitrate, and sodium orthovanadate, by homogeneous precipitation in an ethylene glycol/water mixture at 120 °C. The NPs can be functionalized either by a one-pot synthesis with polyacrylic acid (PAA) or by a Layer-by-Layer approach with poly(allylamine hydrochloride) (PAH) and PAA. In the first case, the particle size can also be tuned by adjusting the amount of PAA. The Eu- Bi-doped REVO4 based nanophosphors show the typical red luminescence of Eu(iii), which can be excited through an energy transfer process from the vanadate anions, resulting in a much higher luminescence intensity in comparison to the direct excitation of the europium cations. The incorporation of Bi into the REVO4 structure shifts the original absorption band of the vanadate anions towards longer wavelengths, giving rise to nanophosphors with an excitation maximum at 342 nm, which can also be excited in the visible range. The suitability of such nanophosphors for bioimaging and biosensing applications, as well as their colloidal stability in different buffer media of biological interest, their cytotoxicity, their degradability at low pH, and their uptake by HeLa cells have been evaluated. Their suitability for bioimaging and biosensing applications is also demonstrated.

Transparent Flexible Electronics By Directed Integration of Inorganic Micro and Nanomaterials

NASA Astrophysics Data System (ADS)

Cole, Jesse J.

This thesis focuses on nanomanufacturing processes for the heterogeneous integration of nanomaterials. Our approaches involved local adjustment of electrostatics at the surfaces to control material flux. Templating of surface electrostatics was implemented differently for three broad concepts resulting in control over nanomaterial synthesis, deposition, and printing. These three general concepts are: (A) Tailored ZnO nanowire synthesis and integration out of the liquid phase; (B) Arc discharge synthesis and continuous nanocluster deposition from the gas phase; (C) Contact electrification and xerographic printing of nanoparticles from the gas phase. Concept (A): We report a method to fabricate and transfer crystalline ZnO with control over location, orientation, size, and shape. The process uses an oxygen plasma treatment in combination with a photoresist pattern on Magnesium-doped GaN substrates to define narrow nucleation regions and attachment points with 100 nanometer scale dimensions. Lateral epitaxial overgrowth follows nucleation to produce single crystalline ZnO which were fabricated into LEDs and photovoltaic cells. Concept (B): We report a gas phase nanoparticle deposition system which shares characteristics with liquid phase electrodeposition. Clusters of charged nanoparticles selectively deposit onto electrically grounded surfaces. Similar to electroplating, the continued deposition of Au nanoparticles onto underlying resistive traces increased overall line conductivity. Alternatively, semiconducting ZnO and Ge nanomaterial sequentially deposited between interdigitated electrodes and served as addressable sensor active areas. Concept (C): We report patterned transfer of charge between conformal material interfaces through a concept referred to as nanocontact electrification. Nanocontacts of different size and shape are formed between surface functionalized polydimethylsiloxane (PDMS) stamps and other dielectric materials (PMMA, SiO 2). Forced delamination and cleavage of the interface yields a well defined charge pattern with a minimal feature size of 100 nm. The process produces charged surfaces and associated fields that exceed the breakdown strength of air leading to strong long range adhesive forces and force distance curves which are recorded over macroscopic distances. The process is applied to fabricate charge patterned surfaces for nanoxerography demonstrating 200 nm resolution nanoparticle prints and applied to thin film electronics where the patterned charges are used to shift the threshold voltages of underlying transistors by over 500 mV.

Symbolic Regression for the Estimation of Transfer Functions of Hydrological Models

NASA Astrophysics Data System (ADS)

Klotz, D.; Herrnegger, M.; Schulz, K.

2017-11-01

Current concepts for parameter regionalization of spatially distributed rainfall-runoff models rely on the a priori definition of transfer functions that globally map land surface characteristics (such as soil texture, land use, and digital elevation) into the model parameter space. However, these transfer functions are often chosen ad hoc or derived from small-scale experiments. This study proposes and tests an approach for inferring the structure and parametrization of possible transfer functions from runoff data to potentially circumvent these difficulties. The concept uses context-free grammars to generate possible proposition for transfer functions. The resulting structure can then be parametrized with classical optimization techniques. Several virtual experiments are performed to examine the potential for an appropriate estimation of transfer function, all of them using a very simple conceptual rainfall-runoff model with data from the Austrian Mur catchment. The results suggest that a priori defined transfer functions are in general well identifiable by the method. However, the deduction process might be inhibited, e.g., by noise in the runoff observation data, often leading to transfer function estimates of lower structural complexity.

First-and Second-Order Displacement Transfer Functions for Structural Shape Calculations Using Analytically Predicted Surface Strains

NASA Technical Reports Server (NTRS)

Ko, William L.; Fleischer, Van Tran

2012-01-01

New first- and second-order displacement transfer functions have been developed for deformed shape calculations of nonuniform cross-sectional beam structures such as aircraft wings. The displacement transfer functions are expressed explicitly in terms of beam geometrical parameters and surface strains (uniaxial bending strains) obtained at equally spaced strain stations along the surface of the beam structure. By inputting the measured or analytically calculated surface strains into the displacement transfer functions, one could calculate local slopes, deflections, and cross-sectional twist angles of the nonuniform beam structure for mapping the overall structural deformed shapes for visual display. The accuracy of deformed shape calculations by the first- and second-order displacement transfer functions are determined by comparing these values to the analytically predicted values obtained from finite element analyses. This comparison shows that the new displacement transfer functions could quite accurately calculate the deformed shapes of tapered cantilever tubular beams with different tapered angles. The accuracy of the present displacement transfer functions also are compared to those of the previously developed displacement transfer functions.

Parallel Histories of Horizontal Gene Transfer Facilitated Extreme Reduction of Endosymbiont Genomes in Sap-Feeding Insects

PubMed Central

Sloan, Daniel B.; Nakabachi, Atsushi; Richards, Stephen; Qu, Jiaxin; Murali, Shwetha Canchi; Gibbs, Richard A.; Moran, Nancy A.

2014-01-01

Bacteria confined to intracellular environments experience extensive genome reduction. In extreme cases, insect endosymbionts have evolved genomes that are so gene-poor that they blur the distinction between bacteria and endosymbiotically derived organelles such as mitochondria and plastids. To understand the host’s role in this extreme gene loss, we analyzed gene content and expression in the nuclear genome of the psyllid Pachypsylla venusta, a sap-feeding insect that harbors an ancient endosymbiont (Carsonella) with one of the most reduced bacterial genomes ever identified. Carsonella retains many genes required for synthesis of essential amino acids that are scarce in plant sap, but most of these biosynthetic pathways have been disrupted by gene loss. Host genes that are upregulated in psyllid cells housing Carsonella appear to compensate for endosymbiont gene losses, resulting in highly integrated metabolic pathways that mirror those observed in other sap-feeding insects. The host contribution to these pathways is mediated by a combination of native eukaryotic genes and bacterial genes that were horizontally transferred from multiple donor lineages early in the evolution of psyllids, including one gene that appears to have been directly acquired from Carsonella. By comparing the psyllid genome to a recent analysis of mealybugs, we found that a remarkably similar set of functional pathways have been shaped by independent transfers of bacterial genes to the two hosts. These results show that horizontal gene transfer is an important and recurring mechanism driving coevolution between insects and their bacterial endosymbionts and highlight interesting similarities and contrasts with the evolutionary history of mitochondria and plastids. PMID:24398322

Synthesis, characterization, crystal structure and solution studies of a novel proton transfer (charge transfer) complex of 2,2‧-dipyridylamine with 2,6-pyridine dicarboxylic acid

NASA Astrophysics Data System (ADS)

Ghasemi, Khaled; Rezvani, Ali Reza; Shokrollahi, Ardeshir; Zarghampour, Fereshteh; Moghimi, Abolghasem; García-Granda, Santiago; Mendoza-Meroño, Rafael

2015-06-01

Reaction between 2,2‧-dipyridylamine (DPA) and 2,6-pyridine dicarboxylic acid (dipicolinic acid, dipicH2), in water results in the formation of a proton transfer or charge transfer (CT) complex, (DPAH)+(dipicH)-·H2O, 1. The characterization was performed using 1H NMR and FTIR spectroscopy, elemental analysis and X-ray crystallography. The crystal system is triclinic with space group P1. The structural investigations exhibit that the hydrogen bonds and π-π stacking interactions stabilize the crystal structure of proton transfer complex. The protonation constants of 2,6-pyridine dicarboxylic acid, 2,2‧-dipyridylamine and the equilibrium constants for dipic-DPA (1:1) proton transfer system were calculated by potentiometric pH titration method using Hyperquad2008 program. The stoichiometries of the proton transfer species in solution was in agreement with the solid state result.

Squid Giant Axon Contains Neurofilament Protein mRNA but does not Synthesize Neurofilament Proteins.

PubMed

Gainer, Harold; House, Shirley; Kim, Dong Sun; Chin, Hemin; Pant, Harish C

2017-04-01

When isolated squid giant axons are incubated in radioactive amino acids, abundant newly synthesized proteins are found in the axoplasm. These proteins are translated in the adaxonal Schwann cells and subsequently transferred into the giant axon. The question as to whether any de novo protein synthesis occurs in the giant axon itself is difficult to resolve because the small contribution of the proteins possibly synthesized intra-axonally is not easily distinguished from the large amounts of the proteins being supplied from the Schwann cells. In this paper, we reexamine this issue by studying the synthesis of endogenous neurofilament (NF) proteins in the axon. Our laboratory previously showed that NF mRNA and protein are present in the squid giant axon, but not in the surrounding adaxonal glia. Therefore, if the isolated squid axon could be shown to contain newly synthesized NF protein de novo, it could not arise from the adaxonal glia. The results of experiments in this paper show that abundant 3H-labeled NF protein is synthesized in the squid giant fiber lobe containing the giant axon's neuronal cell bodies, but despite the presence of NF mRNA in the giant axon no labeled NF protein is detected in the giant axon. This lends support to the glia-axon protein transfer hypothesis which posits that the squid giant axon obtains newly synthesized protein by Schwann cell transfer and not through intra-axonal protein synthesis, and further suggests that the NF mRNA in the axon is in a translationally repressed state.

On-line Monitoring of Continuous Flow Chemical Synthesis Using a Portable, Small Footprint Mass Spectrometer

NASA Astrophysics Data System (ADS)

Bristow, Tony W. T.; Ray, Andrew D.; O'Kearney-McMullan, Anne; Lim, Louise; McCullough, Bryan; Zammataro, Alessio

2014-10-01

For on-line monitoring of chemical reactions (batch or continuous flow), mass spectrometry (MS) can provide data to (1) determine the fate of starting materials and reagents, (2) confirm the presence of the desired product, (3) identify intermediates and impurities, (4) determine steady state conditions and point of completion, and (5) speed up process optimization. Recent developments in small footprint atmospheric pressure ionization portable mass spectrometers further enable this coupling, as the mass spectrometer can be easily positioned with the reaction system to be studied. A major issue for this combination is the transfer of a sample that is representative of the reaction and also compatible with the mass spectrometer. This is particularly challenging as high concentrations of reagents and products can be encountered in organic synthesis. The application of a portable mass spectrometer for on-line characterization of flow chemical synthesis has been evaluated by coupling a Microsaic 4000 MiD to the Future Chemistry Flow Start EVO chemistry system. Specifically, the Hofmann rearrangement has been studied using the on-line mass spectrometry approach. Sample transfer from the flow reactor is achieved using a mass rate attenuator (MRA) and a sampling make-up flow from a high pressure pump. This enables the appropriate sample dilution, transfer, and preparation for electrospray ionization. The capability of this approach to provide process understanding is described using an industrial pharmaceutical process that is currently under development. The effect of a number of key experimental parameters, such as the composition of the sampling make-up flow and the dilution factor on the mass spectrometry data, is also discussed.

Applications of cell-free protein synthesis in synthetic biology: Interfacing bio-machinery with synthetic environments.

PubMed

Lee, Kyung-Ho; Kim, Dong-Myung

2013-11-01

Synthetic biology is built on the synthesis, engineering, and assembly of biological parts. Proteins are the first components considered for the construction of systems with designed biological functions because proteins carry out most of the biological functions and chemical reactions inside cells. Protein synthesis is considered to comprise the most basic levels of the hierarchical structure of synthetic biology. Cell-free protein synthesis has emerged as a powerful technology that can potentially transform the concept of bioprocesses. With the ability to harness the synthetic power of biology without many of the constraints of cell-based systems, cell-free protein synthesis enables the rapid creation of protein molecules from diverse sources of genetic information. Cell-free protein synthesis is virtually free from the intrinsic constraints of cell-based methods and offers greater flexibility in system design and manipulability of biological synthetic machinery. Among its potential applications, cell-free protein synthesis can be combined with various man-made devices for rapid functional analysis of genomic sequences. This review covers recent efforts to integrate cell-free protein synthesis with various reaction devices and analytical platforms. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Localized Synthesis of Conductive Copper-Tetracyanoquinodimethane Nanostructures in Ultrasmall Microchambers for Nanoelectronics.

PubMed

Xing, Yanlong; Sun, Guoguang; Speiser, Eugen; Esser, Norbert; Dittrich, Petra S

2017-05-24

In this work, the microfluidic-assisted synthesis of copper-tetracyanoquinodimethane (Cu-TCNQ) nanostructures in an ambient environment is reported for the first time. A two-layer microfluidic device comprising parallel actuated microchambers was used for the synthesis and enabled excellent fluid handling for the continuous and multiple chemical reactions in confined ultrasmall chambers. Different precautions were applied to ensure the reduction state of copper (Cu) for the synthesis of Cu-TCNQ charge-transfer compounds. The localized synthesis of Cu and in situ transformation to Cu-TCNQ complexes in solution were achieved by applying different gas pressures in the control layer. Additionally, various diameters of the Cu-TCNQ nano/microstructures were obtained by adjusting the concentration of the precursors and reaction time. After the synthesis, platinum (Pt) microelectrode arrays, which were aligned at the microchambers, could enable the in situ measurements of the electronic properties of the synthesized nanostructures without further manipulation. The as-prepared Cu-TCNQ wire bundles showed good conductivity and a reversible hysteretic switching effect, which proved the possibility in using them to build advanced nanoelectronics.

NifX and NifEN exchange NifB cofactor and the VK-cluster, a newly isolated intermediate of the iron-molybdenum cofactor biosynthetic pathway.

PubMed

Hernandez, Jose A; Igarashi, Robert Y; Soboh, Basem; Curatti, Leonardo; Dean, Dennis R; Ludden, Paul W; Rubio, Luis M

2007-01-01

The iron-molybdenum cofactor of nitrogenase (FeMo-co) is synthesized in a multistep process catalysed by several Nif proteins and is finally inserted into a pre-synthesized apo-dinitrogenase to generate mature dinitrogenase protein. The NifEN complex serves as scaffold for some steps of this synthesis, while NifX belongs to a family of small proteins that bind either FeMo-co precursors or FeMo-co during cofactor synthesis. In this work, the binding of FeMo-co precursors and their transfer between purified Azotobacter vinelandii NifX and NifEN proteins was studied to shed light on the role of NifX on FeMo-co synthesis. Purified NifX binds NifB cofactor (NifB-co), a precursor to FeMo-co, with high affinity and is able to transfer it to the NifEN complex. In addition, NifEN and NifX exchange another [Fe-S] cluster that serves as a FeMo-co precursor, and we have designated it as the VK-cluster. In contrast to NifB-co, the VK-cluster is electronic paramagnetic resonance (EPR)-active in the reduced and the oxidized states. The NifX/VK-cluster complex is unable to support in vitro FeMo-co synthesis in the absence of NifEN because further processing of the VK-cluster into FeMo-co requires the simultaneous activities of NifEN and NifH. Our in vitro studies suggest that the role of NifX in vivo is to serve as transient reservoir of FeMo-co precursors and thus help control their flux during FeMo-co synthesis.

Nonparametric Transfer Function Models

PubMed Central

Liu, Jun M.; Chen, Rong; Yao, Qiwei

2009-01-01

In this paper a class of nonparametric transfer function models is proposed to model nonlinear relationships between ‘input’ and ‘output’ time series. The transfer function is smooth with unknown functional forms, and the noise is assumed to be a stationary autoregressive-moving average (ARMA) process. The nonparametric transfer function is estimated jointly with the ARMA parameters. By modeling the correlation in the noise, the transfer function can be estimated more efficiently. The parsimonious ARMA structure improves the estimation efficiency in finite samples. The asymptotic properties of the estimators are investigated. The finite-sample properties are illustrated through simulations and one empirical example. PMID:20628584

Mechanism for priming DNA synthesis by yeast DNA Polymerase α

PubMed Central

Perera, Rajika L; Torella, Rubben; Klinge, Sebastian; Kilkenny, Mairi L; Maman, Joseph D; Pellegrini, Luca

2013-01-01

The DNA Polymerase α (Pol α)/primase complex initiates DNA synthesis in eukaryotic replication. In the complex, Pol α and primase cooperate in the production of RNA-DNA oligonucleotides that prime synthesis of new DNA. Here we report crystal structures of the catalytic core of yeast Pol α in unliganded form, bound to an RNA primer/DNA template and extending an RNA primer with deoxynucleotides. We combine the structural analysis with biochemical and computational data to demonstrate that Pol α specifically recognizes the A-form RNA/DNA helix and that the ensuing synthesis of B-form DNA terminates primer synthesis. The spontaneous release of the completed RNA-DNA primer by the Pol α/primase complex simplifies current models of primer transfer to leading- and lagging strand polymerases. The proposed mechanism of nucleotide polymerization by Pol α might contribute to genomic stability by limiting the amount of inaccurate DNA to be corrected at the start of each Okazaki fragment. DOI: http://dx.doi.org/10.7554/eLife.00482.001 PMID:23599895

Physiological effects in bovine lymphocytes of inhibiting polyamine synthesis with ethylglyoxal bis(guanylhydrazone).

PubMed

Igarashi, K; Morris, D R

1984-11-01

Previous results have suggested that ethylglyoxal bis(guanylhydrazone) is a more specific inhibitor of polyamine biosynthesis than the widely used methylglyoxal bis(guanylhydrazone). The physiological effects on mitogenically activated lymphocytes of polyamine depletion with ethylglyoxal bis(guanylhydrazone) were examined. In the presence of ethylglyoxal bis(guanylhydrazone) and the ornithine decarboxylase inhibitor alpha-difluoromethylornithine, the cellular contents of putrescine, spermidine, and spermine were decreased by 75 to 90, 65 to 80, and 40 to 60%, respectively, compared with control cultures. Inhibition of DNA synthesis in these polyamine-deficient cells was always greater than that of protein synthesis. Upon addition of spermidine to the deficient cells, the cellular spermidine content was restored within 4 hr, but the complete recovery of macromolecular synthesis took 10 to 20 hr. Thymidine kinase and DNA polymerase alpha activities in polyamine-deficient cells were lower than those in normal cells, whereas RNA polymerase II and leucyl transfer RNA synthase activities were nearly equal to those in normal cells. These results and studies with 2-dimensional gel electrophoresis raise the possibility that polyamines may regulate the synthesis of specific proteins. Decreased synthesis of replication proteins in polyamine-deficient cells may be one reason for the reduced synthesis of DNA.

Role of Fatty-acid Synthesis in Dendritic Cell Generation and Function

PubMed Central

Rehman, Adeel; Hemmert, Keith C.; Ochi, Atsuo; Jamal, Mohsin; Henning, Justin R.; Barilla, Rocky; Quesada, Juan P.; Zambirinis, Constantinos P.; Tang, Kerry; Ego-Osuala, Melvin; Rao, Raghavendra S.; Greco, Stephanie; Deutsch, Michael; Narayan, Suchithra; Pachter, H. Leon; Graffeo, Christopher S.; Acehan, Devrim; Miller, George

2013-01-01

Dendritic cells (DC) are professional antigen presenting cells that regulate innate and adaptive immunity. The role of fatty-acid synthesis in DC development and function is uncertain. We found that blockade of fatty-acid synthesis markedly decreases dendropoiesis in the liver and in primary and secondary lymphoid organs in mice. Human DC development from PBMC precursors was also diminished by blockade of fatty-acid synthesis. This was associated with higher rates of apoptosis in precursor cells and increased expression of Cleaved Caspase 3 and BCL-xL, and down-regulation of Cyclin B1. Further, blockade of fatty-acid synthesis decreased DC expression of MHCII, ICAM-1, B7-1, B7-2 but increased their production of selected pro-inflammatory cytokines including IL-12 and MCP-1. Accordingly, inhibition of fatty-acid synthesis enhanced DC capacityto activate allogeneic as well as antigen-restricted CD4+ and CD8+ T cells and induce CTL responses. Further, blockade of fatty-acid synthesis increased DC expression of Notch ligands and enhanced their ability to activate NK cell immune-phenotype and IFN-γ production. Since endoplasmic reticular (ER)-stress can augment the immunogenic function of APC, we postulated that this may account for the higher DC immunogenicity. We found that inhibition of fatty-acid synthesis resulted in elevated expression of numerous markers of ER stress in humans and mice and was associated with increased MAP kinase and Akt signaling. Further, lowering ER-stress by 4-phenylbutyrate mitigated the enhanced immune-stimulation associated with fatty-acid synthesis blockade. Our findings elucidate the role of fatty-acid synthesis in DC development and function and have implications to the design of DC vaccines for immunotherapy. PMID:23536633

Role of fatty-acid synthesis in dendritic cell generation and function.

PubMed

Rehman, Adeel; Hemmert, Keith C; Ochi, Atsuo; Jamal, Mohsin; Henning, Justin R; Barilla, Rocky; Quesada, Juan P; Zambirinis, Constantinos P; Tang, Kerry; Ego-Osuala, Melvin; Rao, Raghavendra S; Greco, Stephanie; Deutsch, Michael; Narayan, Suchithra; Pachter, H Leon; Graffeo, Christopher S; Acehan, Devrim; Miller, George

2013-05-01

Dendritic cells (DC) are professional APCs that regulate innate and adaptive immunity. The role of fatty-acid synthesis in DC development and function is uncertain. We found that blockade of fatty-acid synthesis markedly decreases dendropoiesis in the liver and in primary and secondary lymphoid organs in mice. Human DC development from PBMC precursors was also diminished by blockade of fatty-acid synthesis. This was associated with higher rates of apoptosis in precursor cells and increased expression of cleaved caspase-3 and BCL-xL and downregulation of cyclin B1. Further, blockade of fatty-acid synthesis decreased DC expression of MHC class II, ICAM-1, B7-1, and B7-2 but increased their production of selected proinflammatory cytokines including IL-12 and MCP-1. Accordingly, inhibition of fatty-acid synthesis enhanced DC capacity to activate allogeneic as well as Ag-restricted CD4(+) and CD8(+) T cells and induce CTL responses. Further, blockade of fatty-acid synthesis increased DC expression of Notch ligands and enhanced their ability to activate NK cell immune phenotype and IFN-γ production. Because endoplasmic reticulum (ER) stress can augment the immunogenic function of APC, we postulated that this may account for the higher DC immunogenicity. We found that inhibition of fatty-acid synthesis resulted in elevated expression of numerous markers of ER stress in humans and mice and was associated with increased MAPK and Akt signaling. Further, lowering ER stress by 4-phenylbutyrate mitigated the enhanced immune stimulation associated with fatty-acid synthesis blockade. Our findings elucidate the role of fatty-acid synthesis in DC development and function and have implications to the design of DC vaccines for immunotherapy.